JP2006084867A - Diffusion transfer film unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color diffusion transfer film unit comprising a thin film unit, exhibiting rapid progress of transfer and low in the concentration of an unexposed part. <P>SOLUTION: The diffusion transfer film unit comprises a photosensitive sheet (1) provided with a silver halide emulsion layer formed by combining an image receiving layer, a white light diffusion layer and a dyestuff image forming material on the side surface of a transparent cover sheet of a transparent supporting body, the transparent cover sheet (2) provided with a neutralization layer and a neutralization timing layer on the side surface of the photosensitive sheet of another transparent supporting body and an alkali treatment composition (3) spread between the photosensitive sheet and the transparent cover sheet and containing carbon black and is formed so as to arrange (1)-(3) to be exposed through the transparent cover sheet. A silver halide emulsion and a non-photosensitive silver precipitation nucleus are contained between a white light diffusion layer and a light shielding layer in the photosensitive sheet and a silver halide solvent is contained in the alkali treatment composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a diffusion transfer film unit. More specifically, the present invention relates to an integrated color diffusion transfer film unit. The present invention also relates to a color diffusion transfer film unit having a thin film unit, a rapid transfer progress, and a low density in an unexposed area.

  The color diffusion transfer film unit includes an integral type and a divided type. One typical example of the split type is a so-called peel-apart type, in which the photosensitive element and the dye-receiving element are coated on different supports, and after image exposure, the photosensitive element and the dye-receiving element are separated. The dye image transferred to the dye image-receiving layer is obtained by superimposing and developing the treatment composition between them, and then peeling off the dye-receiving element. The feature of this embodiment is that the dye image can be directly observed instead of observing the image through the support as in the case of the integrated type described later, and shows excellent color reproducibility without deterioration in image quality. However, in this embodiment, there is an inconvenience in operation in which the photosensitive element and the image receiving element are superposed in the camera, and an inconvenience in handling the processed film in which the alkaline processing liquid is sticky and easily adheres to the periphery after peeling. is there.

  In this operation, the one that improves inconvenience in handling is an integrated form. The integrated diffusion transfer film unit is well known in many documents such as Non-Patent Documents 1 and 2. In the integrated type, a dye image-receiving element, a photosensitive element, and a neutralization timing element are coated between a transparent support and the other support, and the photosensitive element is coated on the same transparent support as the image-receiving element. And a form coated on another support (hereinafter referred to as the latter).

  In the former case, a white light diffusion layer is coated between the image receiving element and the photosensitive element. In the latter case, the image is received by adding a white pigment to the processing composition developed between the image receiving element and the photosensitive element. The dye image transferred to the layer can be observed with reflected light. The present invention relates to the former form, a photosensitive sheet having an image receiving layer, a white light diffusing layer, a light shielding layer, at least one silver halide emulsion layer combined with at least one dye image forming material on a transparent support, transparent A color diffusion comprising a transparent cover sheet having at least a neutralization layer and a neutralization timing layer on a support, and a light-shielding alkaline treatment composition adapted to be developed between the photosensitive sheet and the transparent cover sheet It relates to a transfer film unit.

Here, the roles of the light shielding layer, the light-shielding alkali treatment composition, and the white light diffusion layer will be described in detail. The role of the light-shielding layer and the light-shielding alkaline processing composition is an element necessary for darkening the silver halide emulsion layer after processing. After processing, the film unit released from the film pack will be completely exposed to light. In the absence of a light-shielding layer, light reaches the silver halide emulsion layer after processing, so the unexposed areas are also exposed, developed, and colored when stored after processing. For this reason, it is necessary to make a dark room by sandwiching with a light shielding layer. However, when the silver halide emulsion layer is darkened from the beginning, imagewise exposure cannot be performed. For this purpose, the exposure side is designed to allow light to pass through during exposure, and a light-shielding alkaline processing composition is developed during processing, and the other side is covered to achieve a dark room. A light shielding layer is necessary for darkening, but the light shielding layer must be black in order to shield light of all wavelengths. However, if the film unit is black, the image transferred like an image cannot be confirmed. In order to solve this problem, a white light diffusion layer is necessary. The white light diffusion layer is placed between the image receiving layer and the shielding layer and covers the black color of the shielding layer to form a white background. Due to the presence of the white light diffusion layer, an image in which the unexposed portion is white can be obtained.
A fine powder of titanium oxide is used for the white light diffusion layer of the current color diffusion transfer film unit. Titanium oxide fine powder is originally a transparent substance, but diffuses light at the interface with air to form a white color. Titanium oxide has the highest refractive index among existing materials, and is the most excellent material for forming a white background using light diffusion.
However, even when this titanium oxide is used, an enormous amount of titanium oxide is required to hide the black color of the shielding layer. This enormous amount of titanium oxide occupies a large portion of the film thickness of the current color diffusion transfer film unit, which causes a delay in transfer progress.
Under such circumstances, it has been desired to develop a technique for reducing the amount of titanium oxide and speeding up the transfer while maintaining sufficient whiteness of the unexposed area.
Research Disclosure, 1976, Volume 151 No. 15162 Photographic Science and Engineering, July 18, 1976, Volume 20, Issue 4

  Accordingly, an object of the present invention is to provide a color diffusion transfer film unit having a thin film unit, a rapid transfer progress, and a low density of an unexposed portion.

The above problems have been achieved by the following means. That is, the present invention
(1) A photosensitive sheet (i) provided with an image receiving layer, a white light diffusing layer, a light shielding layer, and a silver halide emulsion layer combined with a dye image forming substance on the side of the transparent cover sheet below of the transparent support;
A transparent cover sheet (ii) provided with a neutralization layer and a neutralization timing layer on the side surface of the photosensitive sheet of a transparent support different from the above; and carbon black developed between the photosensitive sheet and the transparent cover sheet A white light diffusing layer in the photosensitive sheet, comprising the alkaline processing composition (iii), and (i) to (iii) arranged to be exposed through the transparent cover sheet. A diffusion transfer film unit comprising a silver halide emulsion and a non-photosensitive silver precipitation nucleus between the light-shielding layer and a silver halide solvent in the alkali treatment composition,
(2) The diffusion transfer film unit according to (1), wherein an average grain size of the silver halide emulsion between the white light diffusion layer and the light shielding layer is 0.5 μm or less,
(3) The diffusion transfer film unit according to the above (1) or (2), other than the silver halide emulsion in the diffusion transfer film unit photosensitive sheet and between the white light diffusion layer and the light shielding layer A diffusion transfer film unit, wherein the silver halide emulsion is a negative silver halide emulsion,
(4) The diffusion transfer film unit according to the above (1) or (2), other than the silver halide emulsion in the diffusion transfer film unit photosensitive sheet and between the white light diffusion layer and the light shielding layer A diffusion transfer film unit, wherein the silver halide emulsion is an internal latent image type direct positive silver halide emulsion, and (5) (1), (2), (3), (4) or The diffusion transfer film unit according to any one of (5), wherein the diffusion transfer film unit is exposed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions. It is to provide.

The diffusion transfer film unit of the present invention is thin, the transfer progresses quickly, and the white color of the unexposed area can be maintained.

Examples of each component that can be used in the diffusion transfer film unit of the present invention will be described below.
First, the silver halide emulsion between the white light diffusion layer and the light shielding layer of the present invention will be described.
The silver halide emulsion used in the present invention may be, for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, and is soluble in a silver halide solvent. From a high point, silver chloride and silver chlorobromide having a silver chloride content of 90 mol% or more are preferably used.
The crystal habit of silver halide grains has regular crystals such as cubes and tetradecahedrons with octagons or octahedrons (they have rounded vertices and higher order planes). (Which may have), spherical, having an irregular crystal system such as a flat plate having a high aspect ratio of {100} plane or {111} plane, having a crystal defect such as a twin plane, Alternatively, any of those composite systems and others may be used. In the present invention, a cubic shape is preferable.

The emulsion in the light-sensitive material of the present invention preferably has a silver bromide localized layer.
The silver bromide content of the silver bromide localized phase is preferably in the range of 1 to 80 mol%, and most preferably in the range of 5 to 70 mol%. The silver bromide localized phase is preferably composed of 0.1 to 30 mol% of silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 20 mol% of silver. More preferably, it is configured. The silver bromide localized phase preferably contains a Group VIII metal complex ion such as an iridium ion. The amount of these compounds added varies widely depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol per mol of silver halide.

  In the present invention, transition metal ions may be added in the process of forming and / or growing silver halide grains, and the metal ions may be incorporated into and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, iridium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any one of the above metal ions of iron, ruthenium, iridium, osmium, lead, cadmium, or zinc. It is also preferable to use it in the molecule.

When an organic compound is used as the ligand, it is common to other transition metals, but preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered ring or a 6-membered ring. The heterocyclic compound can be mentioned. More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to the metal, most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.
Among these, a preferred ligand for iridium ions is particularly preferably 5-methylthiazole among thiazole ligands.

As a combination of a metal ion and a ligand, a combination of iron ion, ruthenium ion and cyanide ion is preferable. In these compounds, cyanide ions preferably account for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine. Or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. Complexes are preferably added 1 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver in the grain formation for these cyanide ion as a ligand, 1 × 10 ^-6 mol to 5 × 10 ^- It is most preferable to add ⁴ moles.

As the iridium ion, it is preferable to use not only an organic ligand but also a fluoride ion, a chloride ion, a bromide ion, and an iodide ion, and particularly a chloride ion or a bromide ion. As the iridium complex, the following specific compounds can be used in addition to those having the above-mentioned organic ligands.
[IrCl ₆ ] ³⁻ , [IrCl ₆ ] ²⁻ , [IrCl ₅ (H ₂ O)] ^{2 −} , [IrCl ₅ (H ₂ O)] ⁻ , [IrCl ₄ (H ₂ O) ₂ ] ⁻ , [ IrCl ₄ (H ₂ O) ₂ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁺ , [IrBr ₆ ] ³⁻ , [IrBr ₆ ] ²⁻ , [ IrBr ₅ (H ₂ O)] ²⁻ , [IrBr ₅ (H ₂ O)] ⁻ , [IrBr ₄ (H ₂ O) ₂ ] ⁻ , [IrBr ₄ (H ₂ O) ₂ ] ⁰ , [IrBr ₃ ( H ₂ O) ₃ ] ⁰ and [IrBr ₃ (H ₂ O) ³ ] ⁺ .

These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, most preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol. preferable. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol, more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol, per mol of silver during grain formation. It is.

  In the present invention, the above complex is added directly to the reaction solution at the time of silver halide grain formation, or is added to an aqueous halide solution for forming silver halide grains, or to other solutions, thereby forming a grain formation reaction. It is preferably incorporated into the silver halide grains by adding to the solution. Furthermore, it is also preferable that these methods are combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, it is preferable that they be uniformly present inside the grains. However, as disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. In addition, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing no complex only on the particle surface and adding a layer containing no complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Furthermore, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, and the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer, and the silver iodobromide layer should each contain the complex. Is also preferable.

  The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.01 μm to 2 μm. Is preferred. From the viewpoint of accelerating dissolution with a silver halide solvent, the average grain size is preferably 0.5 μm or less, more preferably 0.2 μm or less, and particularly preferably 0.1 μm or less. Further, the particle size distribution is preferably a so-called monodispersed material having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, desirably 25% or less, more preferably 20% or less. .

  The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.

  In order to sensitize the silver halide emulsion used in the present invention, gold (I) complexes having various inorganic gold compounds and inorganic ligands and gold (I) compounds having organic ligands are used. be able to. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate compound such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. It is preferable to use a compound such as a gold dithiosulfate compound such as sodium.

Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as gold (I) tetrafluoroborate bis (1,4,5). -Trimethyl-1,2,4-triazolium-3-thiolate), organic mercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) Phenyl] -5-mercaptotetrazole potassium salt) orate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan Toinert) gold (I) sodium salt tetrahydrate, etc. can be used. Further, a gold (I) thiolate compound described in US Pat. No. 3,503,749, a gold compound described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, Compounds described in U.S. Pat. Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 Can also be used.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, per mol of silver halide. is there.

Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics Vol. 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B, 263, 1328, 1966, etc. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. The amount added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol as a gold atom per mol of silver halide. .
In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds.
The amount of silver halide emulsion used in the present invention between the white light diffusing layer and the light shielding layer is preferably between 0.1 g / m ² and 20 g / m ² , and preferably 0.2 g / m ^{2 to} 10 g / m ² . More preferably between m ² and more preferably between 0.5 g / m ² and 5 g / m ² . If it is less than this, the light reflectivity of the silver produced will be insufficient, and if it is more than this, the effect of speeding up the thin layer, which is the object of the present invention, will not be sufficient.

  In the present invention, the layer containing the silver halide emulsion of the present invention must be able to pass the diffusing dye. Therefore, it is necessary to disperse in a water-soluble binder. Gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl A variety of synthetic hydrophilic polymer materials such as a single or copolymer such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid and polyacrylamide can be used.

  As gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme dispersion may also be used. Examples of gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like. What is obtained by reacting is used. The binder amount of the silver halide emulsion used in the present invention is 1 to 1000 parts by weight, preferably 5 to 100 parts by weight, and particularly preferably 10 to 50 parts by weight with respect to 100 parts by weight of the silver halide emulsion.

  It is preferable to use a surfactant in combination with the layer containing the silver halide emulsion of the present invention. Any surfactant can be used as the surfactant, but nonionic surfactants are preferred.

  Next, the nonionic surfactant used in the present invention will be described. Nonionic surfactants are represented by the following general formulas (W-II), (W-III), (W-IV), (W-V), (W-VI) and (W-VII). Can be used.

In the general formulas (W-II) to (W-VII), R, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an alkenyl group having 8 or more carbon atoms, and R, R ¹ , R ² and R ³ may be the same or different, except for those that are all hydrogen atoms. R ⁴ represents an alkyl group or alkenyl group having 8 or more carbon atoms, and n represents a positive integer of 5 to 100. R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aryl group, and these groups include those having a substituent. R ₂₁ is preferably an alkyl group having 4 to 24 carbon atoms, an alkenyl group, or an aryl group, and particularly preferably a hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, 2,4-di- t-butylphenyl group, 2,4-di-t-pentylphenyl group, p-dodecylphenyl group, n-pentadecaphenyl group, t-octylphenyl group, 2,4-dinonylphenyl group, octylnaphthyl group, etc. It is. A is —O—, —S—, —COO—, —OCO—, —N (R ₃₀ ) —, —CON (R ₃₀ ) — or —SO ₂ N (R ₃₀ ) — (where R ₃₀ is hydrogen). Represents an alkyl group including those having an atom or a substituent. R ₂₂ , R ₂₃ , R ₂₇ and R ₂₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, These groups include those each having a substituent. R ₂₆ and R _{28 each} represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and these groups each have a substituent. Is also included. R ₂₆ and R ₂₈ are preferably an aryl group such as an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a p-chlorophenyl group, and —OR ₃₅ (wherein R ₃₅ represents an alkyl group or aryl group having 1 to 20 carbon atoms). These groups include those having a substituent. The same shall apply hereinafter.) Alkyl groups and aryloxy groups, halogen atoms such as chlorine atoms and bromine atoms, and acyl groups represented by —COR ₃₅ An amide group represented by the group, —NR ₃₆ COR ₃₅ (wherein R ₃₆ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; the same shall apply hereinafter), represented by —NR ₃₆ SO ₂ R _35. A sulfonamide group, a carbamoyl group represented by —CON (R ₃₆ ) ₂ or a sulfamoyl group represented by —SO ₂ N (R ₃₆ ) ₂ . Of these, R ₂₆ and R ₂₈ are more preferably an alkyl group or a halogen atom, and most preferably a tertiary alkyl group such as a t-butyl group, a t-amyl group, or a t-octyl group. R ₂₂ , R ₂₃ , R ₂₇ and R ₂₉ are preferably hydrogen atoms or the groups listed as preferred for R ₂₆ and R ₂₈ above. Of these, R ₂₇ and R ₂₉ are particularly preferably hydrogen atoms. R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group or an aryl group, and these groups include those having a substituent. R ₂₄ and R ₂₅ are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a furyl group, or the like. R ₂₄ and R ₂₅ , R ₂₆ and R _27, and R ₂₈ and R ₂₉ may be linked to each other to form a ring, for example, a cyclohexyl ring. In the general formula (W-VI), the substituent on the phenyl ring may be asymmetrical. R ₃₁ represents a hydrogen atom or an alkyl group, and this alkyl group includes those having a substituent. R ₃₂ represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an aryl group or an aralkyl group. Each group represented by R ₃₂ includes those having a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a thioether group, and a polyoxyalkyl ether group. It is done. R ₃₃ represents an alkylene group having 1 to 10 carbon atoms, a polyoxyalkylene group or a divalent aromatic group (for example, a phenylene group), and these include those having a substituent. R ₃₄ represents an alkyl group having 1 to 20 carbon atoms or an aryl group. Each group represented by R ₃₄ includes those having a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a thioether group, and a polyoxyalkylene ether group. Can be mentioned. n11, n12, n13 and n14 are the average number of moles of ethylene oxide added and are 2 to 50, particularly preferably 5 to 30. n13 and n14 may be the same or different. N15 is also the average number of moles of ethylene oxide added and is a number from 1 to 100. m is an integer of 2 to 50, m11 and m12 are each an integer of 0 to 20, and p is an integer of 0 to 30. These compounds are disclosed in U.S. Pat. Nos. 2,982,651, 3,428,456, 3,457,076, 3,454,625, 3,552,972, 3, No. 655,387, Japanese Patent Publication No. 51-9610, Japanese Patent Publication No. 53-29715, Japanese Patent Publication No. 54-89626, Japanese Patent Application No. 57-85764, Japanese Patent Application No. 57-90909, Hiroshi Horiguchi, “New Interface Activator "(Sankyo Publishing, 1975) and the like. Among the nonionic surfactants represented by the general formulas (W-II) to (W-VII), those preferably used are sorbitan ester compounds represented by (W-II) and (W-III). . Next, specific examples of the nonionic surfactant preferably used in the present invention will be shown, but the present invention is not limited thereto.

The addition amount of these surfactants is not particularly limited, but is preferably 1 × 10 ⁻⁵ g / m ² to 1 g / m ² , and preferably 1 × 10 ⁻⁴ g / m ² to 1 × 10 ^−1. g / m ² is more preferable, and 1 × 10 ⁻³ g / m ² to 1 × 10 ⁻² g / m ² is particularly preferable.

The non-photosensitive silver precipitation nuclei of the present invention will be described in detail below.
Specific examples of the non-photosensitive silver precipitation nuclei of the present invention include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, or noble metals such as gold, silver (including microcolloidal silver), There are platinum and palladium. Also, heavy metal and noble metal sulfide salts, selenide salts such as copper, aluminum, zinc, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum, palladium and the like, Alternatively, selenide salts such as lead, zinc, antimony and nickel can also be preferably used. Further, the silver halide grains previously fogged are reduced by development and can be preferably used as silver precipitation nuclei as metallic silver.
The amount of precipitation nuclei present invention is preferably 1 g / ^{m 2} from ^{1 × 10 -6 g / m 2} , 1 × 10 -5 g / m more preferably 0.1 g / ^{m 2} from ^2, 1 × 10 ^- Particularly preferred is ⁴ g / m ² to 1 × 10 ⁻² g / m ² . When the amount is less than this, the metal silver does not sufficiently precipitate on the precipitation nucleus, and when the amount is more than this, the effect of speeding up the thin layer, which is the object of the present invention, is not sufficient.

  A water-soluble binder can be used as the binder for the silver precipitation nuclei of the present invention. Gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl A variety of synthetic hydrophilic polymer materials such as a single or copolymer such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid and polyacrylamide can be used. When PdS is used as a silver precipitation nucleus, it is effective to use cellulose diacetate as a binder because a silver precipitation nucleus of PdS is easily generated. During the treatment, cellulose diacetate undergoes hydrolysis to become cellulose.

The silver halide solvent of the present invention is described in detail below.
The silver halide solvent used in the present invention may be any compound that forms a water-soluble complex ion with Ag ⁺ ions. In the case of an ionic compound, a compound in which a dissociated anion forms a complex salt with an Ag ⁺ ion may be used.
The compounds preferably used as the silver halide solvent in the present invention are cyclic imides represented by uracil and its derivatives, thiosulfates, nitrogen-containing bases, thioether compounds and rings described in Japanese Patent Application No. 3-99107. A combination of the formula imide and a nitrogen base, 1,1-bissulfonylalkane and its derivatives, and the like. As the cyclic imide, a compound represented by formula (I) is preferable.

Here, Z is an atomic group forming a 5- to 6-membered cyclic imide, the cyclic imide contains 1 to 3 nitrogen atoms, and the remaining atoms are carbon atoms. Each atom may be substituted, and examples of the substituent include an amino group, an aromatic group, an aliphatic group having 1 to 4 carbon atoms, and a halogen atom. Moreover, when the atom which forms cyclic imide is a carbon atom, you may couple | bond with an oxygen atom with a double bond, and may form a ketone.
Typical cyclic imide mother nuclei used in the present invention include uracil, triazine, barbitalate, urazole, hydantoin, glutarimide, glutaconimide, succinimide, maleimide and the like.
Although the example of a compound represented with general formula (I) below is described, this invention is not limited to this.

  Examples of the thiosulfate used in the present invention include sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, calcium thiosulfate, and barium thiosulfate.

The nitrogen-containing base used in the present invention will be described. The nitrogen-containing base must be soluble in an alkaline aqueous solution, and preferred compounds include ammonia, amine, hydroxylamine, hydroxylamine substituted with an aliphatic group, hydrazine, hydrazine substituted with an aliphatic group, and the like. It is done.
Although the compound example is described about a nitrogen-containing base below, this invention is not limited to this.

In the present invention, various silver halide solvents can be used in combination as the silver halide solvent. In this case, the same type of silver solvent may be used in combination, or another type of silver solvent may be used in combination.
The amount of silver halide solvent of the present invention, when the expansion process, the coating amount of the diffusion transfer film unit is preferably ^{0.05g / m 2 ~15g / m 2} , more preferably 0.1 g / ^{m 2} ~10g / m ^2, particularly preferably from ^{0.5g / m 2 ~5g / m 2} .
If the amount is less than this, the silver halide emulsion between the white light diffusion layer and the light shielding layer cannot be sufficiently dissolved. If the amount is more than this, the halogen in the silver halide emulsion layer combined with the dye image-forming substance Dissolves silver halide emulsion.

Hereinafter, I.I. Photosensitive sheet, II. Transparent cover sheet and III. The alkali treatment composition will be described.
I. Photosensitive sheet A) White light diffusing layer The white light diffusing layer of the photosensitive sheet used in the present invention may form a white background of a color image, but usually contains a white pigment and a hydrophilic binder.
As the white pigment for the white light diffusion layer, barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, alumina, zirconium oxide, zirconium zirconium sulfate, kaolin, mica, titanium dioxide, and the like are used. Furthermore, non-film-forming polymer particles made of styrene or the like are also used. Moreover, these may be used independently and can also be mixed and used in the range in which the preferable reflectance is obtained.
The white pigment is preferably titanium dioxide.

The whiteness of the white light diffusion layer varies depending on the type of pigment, the mixing ratio of the pigment and the binder, and the coating amount of the pigment, but the light reflectance is preferably 70% or more.
When using titanium dioxide as a white pigment, 5 to 40 g / m ² of titanium dioxide, preferably 10 to 25 g / m ² was applied, white light reflectance has a 78 to 85% with light having a wavelength of 540nm A diffusion layer is preferred. Titanium dioxide can be selected from various commercially available brands.
Of these, rutile type titanium dioxide is particularly preferred. Most of the commercially available products are surface-treated with alumina, silica, zinc oxide or the like, and in order to obtain a high reflectance, a surface treatment amount of 5% or more is preferable. Examples of commercially available titanium dioxide include those described in Research Disclosure Magazine No. 15162 in addition to Ti-pure R931 (trade name) manufactured by DuPont.

As the white light diffusion layer, an alkali-permeable polymer matrix such as gelatin, polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose can be used. When gelatin is used as the binder, the mass ratio of the white pigment to gelatin is 1/1 to 20/1, preferably 5/1 to 10/1.
In the white light diffusing layer, it is preferable to incorporate an anti-fading agent such as Japanese Patent Publication Nos. 62-30620 and 62-30621.

B) Light Shielding Layer A light shielding layer containing a light shielding agent and a hydrophilic binder is provided between the white light diffusing layer and the following photosensitive layer. As the light shielding agent, any material having a light shielding function is used, but carbon black is preferably used. Further, degradable dyes described in US Pat. No. 4,615,966 may be used. The binder for coating the light-shielding agent may be any one that can disperse carbon black, and is preferably gelatin. As the carbon black raw material, for example, any method such as a channel method, a thermal method and a furnace method as described in Donnel Voet “Carbon Black” Marcel Dekker, Inc. (1976) can be used. The particle size of carbon black is not particularly limited, but is preferably 90 to 1800 mm. The addition amount of the black pigment as the light shielding agent may be adjusted according to the sensitivity of the photosensitive material to be shielded from light, but is preferably about 5 to 10 in terms of optical density.
The thickness of the light shielding layer used in the present invention is not particularly limited.
C) Support The support of the photosensitive sheet used in the present invention is any smooth transparent support that is usually used for photographic light-sensitive materials, and cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc. are used, and an undercoat layer is used. (Undercoat layer) is preferably provided. In general, the support preferably contains a trace amount of a dye or a pigment such as titanium oxide in order to prevent light piping. The thickness of the support of the photosensitive sheet is 25 to 350 μm, preferably 50 to 210 μm, more preferably 70 to 150 μm. If necessary, a layer for curling balance or an oxygen barrier layer described in JP-A-56-78833 can be provided on the back side of the support.

D) Image receiving layer The image receiving layer (dye image receiving layer) of the photosensitive sheet used in the present invention includes a mordant contained in a hydrophilic colloid. This may be a single layer or a multilayer structure in which mordants having different mordant powers are applied in layers. These are described in JP-A-61-252551. As the mordant, a polymer mordant is preferable.
The polymer mordant is a polymer containing secondary and tertiary amino groups, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation, etc., having a molecular weight of 5,000 or more, particularly preferably 10,000 or more. Is. The coating amount of the mordant is generally 0.5 to 10 g / m ^2, preferably 1.0 to 5.0 g / m ^2, particularly preferably ² to 4 g / m ² .

As the hydrophilic colloid used for the image receiving layer of the photosensitive sheet, gelatin, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone and the like are used, and gelatin is preferred.
In the image receiving layer, anti-fading agents described in JP-A Nos. 62-30620, 62-30621, and 62-215272 can be incorporated.
The thickness of the image receiving layer used in the present invention is not particularly limited.

E) Photosensitive layer In the present invention, a photosensitive layer comprising at least one silver halide emulsion layer combined with a dye image forming substance (dye image forming compound) is provided adjacent to the light shielding layer. The components will be described below.

(1) Dye Image Forming Compound Specific examples of the dye image forming compound are described in the following documents.
Examples of yellow dyes:
U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139 No. 4,383, No. 4,195,992, No. 4,148,641, No. 4,148,643, No. 4,336,322, JP-A No. 51-114930, No. 56-71072, Research Disclosure 17630 (1978), and 16475 (1977).

Examples of magenta dyes:
U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954 No. 4,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104, 4,287,292, JP-A-52-106727, 53-23628, 55-36804, 56-73057, 56-71060, 55-134 , JP-A-7-120901, 8-286343, 8-286344, and 8-292537.

Examples of cyan dyes:
U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220, 4,242 , 435, 4,142,891, 4,195,994, 4,147,544, 4,148,642; British Patent 1,551,138 Japanese Patent Laid-Open Nos. 54-99431, 52-8827, 53-47823, 53-143323, 54-99431, 56-71061; European Patent (EP) 53,037, 53,040; Research Disclosure 17,630 (1978) and 16,475 (1977).

A dye image forming compound that forms a dye by coupling can also be used. For example, they are described in JP-A-8-286340, JP-A-9-152705, JP-A-8-357190, JP-A-8-357191, JP-A-9-117529, and the like.
A positive type dye image forming compound can also be used. In this case, a negative silver halide emulsion may be used as the silver halide emulsion. Examples thereof include JP-A-4-156542, JP-A-4-155332, JP-A-4-172344, JP-A-4-172450, JP-A-4-318844, JP-A-356046, and JP-A-5-45824. Gazette, 5-45825 gazette, 5-53279 gazette, 5-107710 gazette, 5-241302 gazette, 5-107708 gazette, 5-232659 gazette, and U.S. Pat. No. 192,649.

  These compounds can be dispersed by the method described in JP-A-62-215272, pages 144-146. These dispersions may contain the compounds described in JP-A-62-215272, pages 137 to 144. Specific examples of these dye image forming compounds include the following compounds. Dye in the following compounds represents a dye group, a dye group temporarily shortened in wavelength, or a dye precursor group.

(2) Silver halide emulsion in a silver halide emulsion layer combined with a dye image-forming substance Silver halide emulsion in a silver halide emulsion layer combined with a dye image-forming substance used in the present invention (hereinafter simply referred to as halogen) For example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. In particular, silver chlorobromide, silver bromide, Silver iodobromide and silver chloroiodobromide are preferred. Further, negative type silver halide emulsions that mainly form a latent image on the surface of silver halide grains, or internal latent image type direct positive emulsions that form a latent image inside silver halide grains are preferred.

  The negative type emulsion that forms a latent image on the surface of the silver halide grain may be a so-called core-shell emulsion having a phase different from that of the inside of the grain and the surface of the grain, and silver halides having different compositions are joined by epitaxial joining. May be. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167743 and 4-223463 is also used.

  The crystal habit of silver halide grains has regular crystals such as cubes, octahedrons, tetradecahedrons, spherical crystals, irregular crystal systems such as high aspect ratio flat plates, twins Any of those having a crystal defect such as a plane, a composite system thereof, or the like may be used.

  Specifically, US Pat. No. 4,500,626, column 50, 4,628,021, Research Disclosure Journal (hereinafter abbreviated as RD) No. 17, 029 (1978), ibid. 17, 643 (December 1978) 22-23, the same No. 18, 716 (November 1979) 648, ibid. 307, 105 (November 1989) 863-865, JP-A-62-253159, JP-A-64-13546, JP-A-2-236546, JP-A-3-110555, and Grafkide, "Photograph Physics and Chemistry". Published by Paul Monte (P. Glafkides, Chemie et Pisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), Halogens prepared using the method described in “Production and coating of photographic emulsions” by Zelikman et al., Published by Focal Press (V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964), etc. Any silver halide emulsion can be used.

  In the process of preparing a photosensitive silver halide emulsion, it is preferable to perform so-called desalting to remove excess salt. As a means for this, a Nudell water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid) Sodium), or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. A sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain, for example, heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount added depends on the purpose of use, but is generally about 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide. Moreover, when making it contain, you may put in a particle | grain uniformly and you may make it local in the inside and surface of particle | grains. Specifically, emulsions described in JP-A Nos. 2-236542, 1-116637, and 5-181246 are preferably used.

  In the grain forming stage of the photosensitive silver halide emulsion, rhodan salts, ammonia, tetrasubstituted thioether compounds, organic thioether derivatives described in JP-B-47-11386 or JP-A-53-144319 are described as silver halide solvents. Sulfur-containing compounds that have been used can be used.

  Other conditions are described in the above-mentioned Graffkide, "Photo Physics and Chemistry" published by Paul Monte (P. Glafkides, Chemie et Pisique Photographique, Paul Montel, 1967), Duffin's "Photo Emulsion Chemistry", Focal Press ( GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), “Production and Coating of Photographic Emulsions” by Zerikman et al., Published by Focal Press (V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press , 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A backmixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is generated is kept constant can be used.

  In order to accelerate grain growth, the addition concentration, addition amount, and addition rate of silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open Nos. 55-142329, 55-158124, US Pat. No. 3,650,757). Gazette). Furthermore, the stirring method of the reaction solution may be any conventional stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner according to the purpose. A preferred pH range is 2.3 to 8.5, more preferably 2.5 to 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion.
For chemical sensitization of light-sensitive silver halide emulsions, known emulsions for light-sensitive materials include known sulfur sensitizing methods, selenium sensitizing methods, chalcogen sensitizing methods such as tellurium sensitizing methods, gold, platinum, palladium, etc. The noble metal sensitizing method and the reduction sensitizing method to be used can be used alone or in combination (for example, JP-A-3-110555 and JP-A-5-241267). These chemical sensitizations can also be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). In particular, the nitrogen-containing heterocyclic compound having a mercapto group described in JP-A No. 62-40446 is preferably added at the end of chemical sensitization. An antifoggant can be added after the chemical sensitization. Specifically, the methods described in JP-A Nos. 5-45833 and 62-40446 can be used. The antifoggant represented by formula (A) used in the present invention is preferably added at the end of chemical sensitization.

The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9 .0. The coating amount of the photosensitive silver halide used in the present invention is in the range of terms of silver 1 mg to 10 g / m ^2, preferably a 10mg~10g / m ^2.

  In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity, and blue sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. Moreover, you may give infrared-sensitive spectral sensitization as needed.

  The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, sensitization described in U.S. Pat. No. 4,617,257, JP-A-59-180,550, JP-A-64-13546, JP-A-5-45828, JP-A-5-45834, and the like. Pigments. These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization.

In addition to the sensitizing dye, a dye that does not itself have spectral sensitizing action or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion before or after chemical ripening, or before and after nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. But you can. These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant solution. The amount added is generally about 10 ⁻⁸ to 10 ⁻² mole per mole of silver halide.

  Internal latent image type direct positive emulsions include, for example, so-called “conversion type” emulsions made by utilizing the difference in solubility of silver halide, metal ions doped, chemically sensitized, or both. There is a “core / shell type” emulsion in which at least the photosensitive sites of the inner core (core) grains of the silver halide applied are coated with an outer shell (shell) of silver halide. 592,250, 3,206,313, British Patent 1,027,146, US Patents 3,761,276, 3,935,014, 3,447,927, 2, 297,875, 2,563,785, 3,551,662, 4,395,478, German Patent 2,728,108, US Pat. No. 4,431,730, etc. Been That.

  When an internal latent image type direct positive emulsion is used, it is necessary to give surface fog nuclei using light or a nucleating agent after image exposure. As the nucleating agent therefor, hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982, hydrazines and hydrazones described in US Pat. No. 3,227,552, UK Patent 1,283,835, JP-A-52-69613, US Patent 3,615,615, 3,719,494, 3,734,738, 4,094,683, Heterocyclic quaternary salt compounds described in US Pat. No. 4,115,122 and the like, sensitizing dyes having a nucleating substituent described in US Pat. No. 3,718,470 in dye molecules, US Patents 4,030,925, 4,031,127, 4,245,037, 4,255,511, 4,266,013, 4,276,364, British patents No. 2,012,443 Thiourea-linked acyl hydrazine compounds described in US Pat. No. 4,080,270, US Pat. No. 4,278,748, British Patent 2,011,391B, and the like. An acyl hydrazine-based compound in which a heterocyclic group such as is bonded as an adsorbing group is used.

  In the present invention, a spectral sensitizing dye can be used in combination with these negative emulsion and internal latent image type direct positive emulsion. Specific examples thereof include JP-A-59-180550, JP-A-60-140335, Research Disclosure (RD) 17029, U.S. Pat. No. 1,846,300, JP-A-2,078,233, JP-A-2,089, No. 129, No. 2,165,338, No. 2,231,658, No. 2,917,516, No. 3,352,857, No. 3,411,916, No. 2,295,276 2,481,698, 2,688,545, 2,921,067, 3,282,933, 3,397,060, 3,660,103, 3,335,010, 3,352,680, 3,384,486, 3,623,881, 3,718,470, 4,025,349, etc. Has been.

(3) Structure of photosensitive layer The above-described dye image-forming compound which provides a dye having a selective spectral absorption in the same wavelength range as that of the emulsion spectrally sensitized by the spectral sensitizing dye for reproducing a natural color by the subtractive color method And a photosensitive layer comprising at least two of the combinations.
The emulsion and the dye image-forming compound may be applied as separate layers, or may be mixed and applied as a single layer. When the dye image-forming compound is coated and has absorption in the spectral sensitivity range of the emulsion combined therewith, a separate layer is preferred. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image forming compound layer. For example, a layer containing a nucleation development accelerator described in JP-A-60-173541, a partition layer described in JP-B-60-15267 is provided to increase the color image density, or a reflective layer is formed. The sensitivity of the provided photosensitive element can also be increased.

Such a light diffusion layer is a layer containing a white pigment and a hydrophilic binder. Preferably, the white pigment is titanium oxide and the hydrophilic binder is gelatin. The coating amount of titanium oxide ^{0.1g / m 2 ~8g / m 2} , and preferably from ^{0.2g / m 2 ~4g / m 2} . An example of the light diffusion layer is described in JP-A-60-91354.

In the multilayer structure of the photosensitive layer in the present invention, it is preferable that the combination unit of the blue-sensitive emulsion, the combination unit of the green-sensitive emulsion, and the combination unit of the red-sensitive emulsion are sequentially arranged from the exposure side. Arbitrary layers can be provided between the respective emulsion layer units as required. In particular, it is preferable to provide an intermediate layer in order to prevent the undesired influence of the development effect of a certain emulsion layer on other emulsion layer units.
In the present invention, an irradiation prevention layer, a UV absorber layer, a protective layer and the like are coated as necessary.
The thickness of the photosensitive layer in the present invention is not particularly limited.

II. Transparent cover sheet In the color diffusion transfer film unit of the present invention, it is preferable to have a neutralizing function on the transparent cover sheet.
F) Support The support of the cover sheet used in the present invention may be any smooth transparent support that is usually used for photographic materials, and cellulose acetate, polystyrene, polyethylene terephthalate, polycarbonate, etc. are used, and an undercoat is used. It is preferred to provide a layer. The support preferably contains a trace amount of dye to prevent light piping.

G) Layer having a neutralization function The layer having a neutralization function (neutralization layer) used in the present invention contains an acidic substance in an amount sufficient to neutralize the alkali introduced from the alkali treatment composition described later. It may be a layer having a multilayer structure composed of layers such as a neutralization rate adjusting layer (neutralization timing layer) and an adhesion reinforcing layer, if necessary.
A preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group that gives such an acidic group by hydrolysis), more preferably olein described in US Pat. No. 2,983,606. Higher fatty acids such as acids, polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or acid anhydrides as disclosed in US Pat. No. 3,362,819; French Patent 2,290 Copolymer of acrylic acid and acrylate ester as disclosed in US Pat. No. 4,699; Research Disclosure No. 4,139,383 and Research Disclosure No. Mention may be made of latex-type acidic polymers as disclosed in US Pat. No. 16102 (1977). In addition, U.S. Pat. No. 4,088,493, JP-A-52-153739, 53-1023, 53-4540, 53-4541, 53-4542, etc. Mention may also be made of the disclosed acidic substances.

  Specific examples of the acidic polymer (polymer acid) as the acidic substance include a copolymer of vinyl monomer such as ethylene, vinyl acetate, vinyl methyl ether, and maleic anhydride, and an n-butyl ester, butyl acrylate, and acrylic. Examples thereof include a copolymer with an acid, cellulose, and acetate / hydrodiene phthalate.

The acidic polymer can be used as a mixture with a hydrophilic polymer. Examples of such hydrophilic polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether, and the like. Of these, polyvinyl alcohol is preferred.
Further, a polymer other than the hydrophilic polymer such as cellulose acetate may be mixed with the acidic polymer.

  The coating amount of the polymer acid is adjusted by the amount of alkali in the alkali treatment composition described later. The equivalent ratio of polymer acid to alkali per unit area is preferably 0.9 to 2.0. If the amount of the polymer acid is too small, the hue of the transfer dye changes or stains are produced in the white background, and if it is too much, problems such as a change in hue or a decrease in light resistance occur. A more preferred equivalent ratio is 1.0 to 1.3. If the amount of the hydrophilic polymer to be mixed is too large or too small, the quality of the photograph is deteriorated. The mass ratio of the hydrophilic polymer to the polymer acid is 0.01 to 10, preferably 0.1 to 3.0.

  Additives can be incorporated into the layer having a neutralizing function in the present invention for various purposes. For example, hardeners well known to those skilled in the art to harden this layer, or polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc., can be added to improve the brittleness of the film. In addition, an antioxidant, a fluorescent brightening agent, a development inhibitor, and a precursor thereof can be added as necessary.

  In the present invention, the neutralization timing layer used in combination with the neutralization layer is, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, or the like. Polymers that lower alkali permeability; latex polymers that are made by copolymerizing a small amount of a hydrophilic comonomer such as an acrylic acid monomer and that increase the activation energy of alkali permeation; polymers that have a lactone ring are useful.

  Of these, cellulose acetate disclosed in JP-A-54-136328, U.S. Pat. No. 4,267,262, U.S. Pat. No. 4,009,030, U.S. Pat. Timing layer: JP-A-54-128335, JP-A-56-69629, JP-A-57-6843, US Pat. Nos. 4,056,394, 4,061,496, 4,199, No. 362, No. 4,250,243, No. 4,256,827, No. 4,268,604, etc. are copolymerized with a small amount of a hydrophilic comonomer such as acrylic acid. Latex polymer prepared; polymer having monoacrylic acid ester or monomethacrylic acid ester of polyhydric alcohol disclosed in JP-A-11-2890 Polymers having a lactone ring disclosed in U.S. Pat. No. 4,229,516; other JP-A-56-25735, JP-A-56-97346, JP-A-57-6842, European Patent (EP) 31, The polymers disclosed in 957A1, 37,724A1, 48,412A1, etc. are particularly useful.

In addition, those described in the following documents can also be used.
U.S. Pat. Nos. 3,421,893, 3,455,686, 3,575,701, 3,778,265, 3,785,815, 3,847 No. 4,615, No. 4,088,493, No. 4,123,275, No. 4,148,653, No. 4,201,587, No. 4,288,523, No. 4,297,431, West German Patent Application (OLS) No. 1,622,936, No. 2,162,277, Research Disclosure 15162, no. 151 (1976).
The neutralization timing layer using these materials can be used as a single layer or as a combination of two or more layers.

  Further, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,913,164, US Pat. 54-155837, 55-138745, etc., development inhibitors and / or precursors thereof, hydroquinone precursors disclosed in US Pat. No. 4,201,578, and other useful photographs. It is also possible to incorporate additives for use or precursors thereof. Furthermore, providing a neutralizing layer as described in JP-A Nos. 63-168648 and 63-168649 as the layer having the neutralizing function reduces the change in transfer density over time after processing. This is effective.

H) Others The cover sheet in the present invention may have a back layer, a protective layer, a filter dye layer, and the like as a layer having an auxiliary function in addition to the layer having a neutralizing function.
The back layer is provided for adjusting curl and imparting slipperiness. Filter dyes may be added to this layer.
The protective layer is mainly used to prevent adhesion to the cover sheet back surface and adhesion to the photosensitive material protective layer when the photosensitive material and the cover sheet are overlapped. The sensitivity of the photosensitive layer can be adjusted by incorporating a dye into the cover sheet.
The filter dye may be added directly to the support of the cover sheet or the layer having a neutralizing function, and further to the back layer, protective layer, capture mordant layer, etc., or a single layer may be provided. .

III. Alkaline Processing Composition In the present invention, the alkali processing composition is uniformly spread on the photosensitive element after exposure of the photosensitive sheet (photosensitive element), and is (A) the back side of the support or the side opposite to the processing solution in the photosensitive layer. The photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed with the components contained therein. For this purpose, the composition contains an alkali, a thickener, a light-shielding agent, a developer, a development accelerator for controlling development, a development inhibitor, and an antioxidant for preventing deterioration of the developer. Etc. A light-shielding agent is always included in the composition for light-shielding.

These alkali processing compositions are preferably developed on the photosensitive element with a development thickness (a processing liquid amount per m ² after transferring the processing liquid) of 10 μm to 200 μm. The processing temperature when processing the photosensitive element is preferably 0 to 50 ° C, more preferably 0 to 40 ° C.

  The alkali is sufficient to adjust the pH of the liquid to 12 or more, such as an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide), an alkali metal phosphate (for example, potassium phosphate). , Guanidines and hydroxides of quaternary amines (for example, tetramethylammonium hydroxide), among which potassium hydroxide and sodium hydroxide are preferable.

  The thickener is necessary to uniformly develop the processing composition and to maintain adhesion between the photosensitive layer / cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose, or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment or a combination thereof may be used as long as it does not diffuse to the dye image-receiving layer and produce stain. A typical example is carbon black.

  As the preferred developer, any developer can be used as long as it cross-oxidizes the dye image-forming compound and does not substantially produce stain even when oxidized. Such developing agents may be used alone or in combination of two or more, or may be used in the form of a precursor. These developing agents may be contained in an appropriate layer of the photosensitive sheet or in the alkaline processing composition. Specific examples of the compound include aminophenols and pyrazolidinones. Among them, pyrazolidinones are particularly preferable because they generate less stain. For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1- (3′-methyl-phenyl) -4-methyl-4-hydroxymethyl-3-pyrazolidinone 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, and the like.

A development accelerator described in JP-A-62-215272, pages 72 to 91, a hardener described in pages 146 to 155, or a surfactant described in pages 201 to 210, in any one of a photosensitive sheet, a cover sheet and an alkali processing composition. A fluorine-containing compound described on pages 210-222, a thickener described on pages 225-227, an antistatic agent described on pages 227-230, a polymer latex described on pages 230-239, a matting agent described on page 240, and the like. Can do. Further, tertiary amine latexes described in JP-A-6-273907, JP-A-7-134386, JP-A-7-175193, and JP-A-7-287372 can be included.
The thickness of the diffusion transfer film unit of the present invention is not particularly limited.

  For details of the heat-developable color light-sensitive material (dye-fixing element) in which the dye image-forming compound of the present invention is used and the exposure and heating method and apparatus to be applied, refer to, for example, JP-A-7-219180 [0128] to [0159]. 〕It is described in. A preferred exposure method is a method in which exposure is performed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.
Example 1

1. Preparation of photosensitive sheet First, photosensitive elements (photosensitive sheet-101) having the compositions shown in Tables 1 to 4 below were prepared. The emulsions in the table were prepared by the method shown in Table 5.

  The compounds used for the emulsion preparation are summarized below.

  The compound used for preparation of the photosensitive element (Photosensitive sheet-101) is shown below.

2. Production of Cover Sheet A 75 um thick polyethylene terephthalate transparent support was applied with a layer structure as shown in Table 6 to produce a cover sheet 101.

  The chemical structural formulas and the like of the compounds used in the cover sheet are shown below.

3. Production of Alkali Treatment Composition Next, an alkali treatment composition (treatment liquid-101) having the following composition was produced.
Carbon black (manufactured by Dainichi Seika Co., Ltd.) 224.3g
Additive (23) 12.1 g
Carboxymethylcellulose Na salt 43.0g
Potassium sulfite (anhydrous) 1.90 g
13.6 g of 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone
Potassium hydroxide 52.7g
Zinc nitrate 0.60g
Water was added in a total amount of 1 kg. 0.3 g of the treatment liquid having the above composition was filled into a container that could be broken by pressure.

  A photosensitive sheet 102 similar to the photosensitive sheet 101 was prepared except that the third layer was changed to the layer shown in Table 7 below. The silver halide emulsion X has the characteristics shown in Table 8.

  A method for preparing silver halide emulsion X is shown below.

Preparation of silver halide emulsion X High silver chloride cubic grains were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, K ₂ [IrCl ₆ ] was added from the time point when the addition of silver nitrate was 70% to 90%. Furthermore, when 100% of the addition of silver nitrate was completed, Additive A was added so as to be 1 × 10 ⁻³ mol per mol of the finished silver halide. The obtained emulsion grains were monodisperse cubic silver chloride grains having a side length of 0.07 μm and a coefficient of variation of 18.5%. This emulsion was subjected to sedimentation and desalting treatment, and gelatin and calcium nitrate were added and redispersed.

  A photosensitive sheet 103 similar to the photosensitive sheet 101 was prepared except that the third layer was changed to the two layers shown in Table 9 below.

A photosensitive sheet 104 was prepared in the same manner as the photosensitive sheet 101 except that the third layer was changed to the layer shown in Table 10 below.

A treatment liquid similar to the treatment liquid-101 except that the following compounds were added in the amounts shown below,
Treatment liquid-102 was prepared.

Uracil-1 17g
11g uracil-2
Uracil-3 7g
0.8g potassium thiosulfate
However, the amount of water was adjusted so that the total amount of the treatment liquid was 1 kg.

  Using the photosensitive sheets 101 to 104, the cover sheet 101, the processing solution 101, and the processing solution 102, a color diffusion transfer photographic unit shown in Table 11 below by the method described in JP-A-7-159931 -A to H were prepared. After this color diffusion transfer photographic unit was loaded into the camera, it was exposed from the cover sheet side and developed with a pressure roller adjusted so that the processing liquid had a thickness of 55 μm between both materials. Exposure and development were performed. The treatment was performed at 25 ° C., and the reflection density one day after the development treatment was measured with a color densitometer to obtain the highest density and the lowest density.

Samples 102 ′ to 104 ′ were prepared by adjusting the coating amount of the second layer of the photosensitive sheets 102 to 104 so that the minimum density was the same as that of the unit-A under the processing conditions.
Color diffusion units B ′ to D ′ and F ′ to I ′ were prepared using the prepared photosensitive sheet, the cover sheet 101 and the processing solutions 101 and 102 in the same manner as described above. The prepared sample was subjected to exposure with white light and processed in the same manner as the above processing method (concentration adjustment was performed by measurement with green light, which is the region with the highest specific visual sensitivity). The yellow density of each unit after processing was measured over time, and the time when the yellow density exceeded 1.6 was examined. Table 12 shows the ratio of the coating amount of the second layer of 102 ′ to 104 ′ to the coating amount of 101, and the time when the yellow density exceeds 1.6.

  From Table 12, by using an alkali treatment composition containing a silver halide emulsion and a silver precipitation nucleus and containing a silver halide solvent between the white light diffusion layer and the light shielding layer as in the present invention. It was found that the white color of the unexposed area can be maintained. Further, it was found that the transfer progress can be accelerated while maintaining the same white background.

Example 2
In the color diffusion transfer photographic unit production method of Example 1, the photosensitive element was changed to the photosensitive sheet-201, and a unit in which the developed thickness of the processing solution was changed was produced, and the effect was evaluated.

  First, photosensitive elements (photosensitive sheet-201) having the compositions shown in Tables 13 to 17 below were prepared.

  The compound used for preparation of the photosensitive element (Photosensitive sheet-101) is shown below.

  Three types of silver halide emulsions, surface latent image type emulsions -J, K, and L, were prepared by the following preparation method and used. Table 12 summarizes the results.

Emulsion-K:
In 0.7 liter of gelatin aqueous solution containing 1.1 g of low molecular weight gelatin having 0.005 mol of potassium bromide and an average molecular weight of 20,000 or less, 26.5 ml of silver nitrate aqueous solution having a concentration of 0.58 mol / liter and 0.42 mol of potassium bromide 46.4 ml of an aqueous solution containing 1.5% by weight of a low molecular weight gelatin having an average molecular weight of 20,000 or less was mixed at the same time by virtue of the double jet method over 1 minute (first addition). During this time, the gelatin aqueous solution was kept at 35 ° C. After adding 0.5 g of potassium bromide, the temperature was raised to 75 ° C. with a gradient of 1.5 ° C. per minute.
After reaching a temperature of 75 ° C., 0.16 liters of gelatin solution containing 16% by mass of deionized gelatin having a Ca content of 100 ppm or less (first addition) and 5 ml of 4.9% sulfuric acid aqueous solution were added. Subsequently, a double jet of an aqueous silver nitrate solution with a concentration of 1.88 mol / liter and an aqueous potassium bromide solution with a concentration of 1.88 mol / liter at an accelerated flow rate (the flow rate at the end is 3.5 times the flow rate at the start). (The second addition, the amount of silver nitrate aqueous solution used was 366 ml, and the amount of potassium bromide aqueous solution was 375 ml).

  Next, 0.08 liter of gelatin solution containing 14% by mass of deionized gelatin having a Ca content of 100 ppm or less (second addition) and 2 mg of sodium benzenethiosulfate were added. Subsequently, an aqueous solution of silver nitrate with a concentration of 1.88 mol / liter and an aqueous solution of potassium bromide with a concentration of 1.88 mol / liter are double jetted at an accelerated flow rate (the flow rate at the end is 1.2 times the flow rate at the start). (Added for the third time, the amount of silver nitrate aqueous solution used was 157 ml, and the amount of potassium bromide aqueous solution was 163 ml).

After adding 4.6 g of potassium bromide, it was washed with water by a conventional flocculation method, deionized gelatin, 2-phenoxyethanol and methyl p-hydroxybenzoate were added, and then adjusted to pH 5.8 and pAg 8.8. The emulsion was adjusted to contain 1.35 mol of silver and 84 g of gelatin per 1 kg of the emulsion. 0.74 kg of the emulsion thus prepared was dissolved by heating and heated to 55 ° C., then 0.5 g of potassium iodide, 4.2 × 10 ⁻⁴ mol of sensitizing dye (6), and sensitizing dye. 5.4 × 10 ⁻⁴ mol of (7) was added and aging was performed for 30 minutes. Next, 5.0 × 10 ⁻⁴ mol of potassium thiocyanate, 1.4 × 10 ⁻⁵ mol of potassium tetrachloroaurate, and 1.2 × 10 ⁻⁵ mol of sodium thiosulfate were added and aged for 60 minutes. Emulsion preparation was completed by adding 1.0 × 10 ⁻³ mol of Compound E-4 and further adding 3.2 × 10 ⁻⁴ mol of Compound E-5 at the end of ripening.

  The diameter of a circle having an area equal to the projected area when viewed from the main plane direction of each particle is called a circle equivalent diameter. As a result of observation by an electron microscope, the average value of the particle thickness hi (= Σhi × ni / Σni) was 0.135 μm, and the average value of the equivalent circle diameter Di of the particles (= ΣDi × ni / Σni) was 1.15 μm. The average aspect ratio defined by the average value of the equivalent circle diameter Di / the average value of the particle thickness hi was 8.5.

Emulsion-J:
Emulsion-J was prepared by adding 9.2 × 10 ⁻⁴ mol of sensitizing dye (9) instead of sensitizing dye (6) and sensitizing dye (7) in the preparation method of emulsion-K. .

Emulsion-L:
In the preparation method of Emulsion-K, sensitizing dye (1) is 8.4 × 10 ⁻⁴ mol instead of sensitizing dye (6) and sensitizing dye (7), and sensitizing dye (2) is 2.6. Emulsion-L was prepared by adding .times.10.sup.- ⁵ mol and sensitizing dye (3) to 1.7.times.10.sup.- ⁴ mol.

  The compounds used for the emulsion preparation are summarized below.

  A photosensitive sheet 202 was prepared in the same manner as the photosensitive sheet 201 except that the third layer was changed to the layer shown in Table 7.

  A photosensitive sheet 203 was prepared in the same manner as the photosensitive sheet-201 except that the third layer was changed to the two layers shown in Table 9 above.

  A photosensitive sheet 204 similar to the photosensitive sheet 201 was prepared except that the third layer was changed to the layer shown in Table 10 above.

A treatment liquid similar to the treatment liquid 101 except that the following compounds were added in the following amounts:
Treatment liquid 202 was prepared.

Uracil-1 25g
Uracil-2 16g
Uracil-3 10g
Potassium thiosulfate 1.2g
However, the amount of water was adjusted so that the total amount of the treatment liquid was 1 kg.

  A color diffusion transfer photographic unit-I shown in Table 19 below using the photosensitive sheets 201-204, the cover sheet-101, the processing solution-101, and the processing solution-202 by the method described in JP-A-7-159931. ~ P was made. This color diffusion transfer photographic unit was subjected from exposure to development processing with an exposure development processing machine incorporating a three-color LED exposure machine of blue, green and red. After loading the color diffusion transfer photographic units -I to P into the exposure developing processor, the LED is exposed from the cover sheet side using an LED as a light source, and a pressure roller adjusted so that the processing liquid has a thickness of 38 μm between both materials. The unit-I to P were exposed and developed. The treatment was performed at 25 ° C., and after 5 minutes from the development treatment, the reflection density after 1 day was measured with a color densitometer to obtain the maximum density and the minimum density.

Sample photosensitive sheets 202 ′ to 204 ′ were prepared by adjusting the coating amount of the second layer of the photosensitive sheet 202204 so that the minimum density was the same as that of the unit-I under the processing conditions.
Color diffusion units J ′ to L ′ and N ′ to P ′ were prepared using the prepared photosensitive sheet, the cover sheet 101 and the processing solutions 101 and 202 in the same manner as described above. The prepared sample was exposed to white light and processed in the same manner as the above processing method (concentration adjustment was performed by measurement with green light, which is the region with the highest specific visual sensitivity). The yellow density of each unit after processing was measured over time, and the time when the yellow density exceeded 1.6 was examined. Table 20 shows the ratio of the coating amount of the second layer 201 ′ to 204 ′ to the coating amount of 201 and the time when the yellow density exceeds 1.6.

  From Table 20, even when the negative type silver halide emulsion is used and the exposure is performed using an exposure head having different light sources that emit light in a plurality of specific wavelength ranges, the white light diffusion layer and the light-shielding layer are separated as in the present invention. It was found that the white color of the unexposed area can be maintained by coating the silver halide emulsion and silver precipitation nuclei and using an alkali treatment composition containing a silver halide solvent. Further, it was found that the transfer progress can be accelerated while maintaining the same white background.

Claims (5)

A photosensitive sheet (i) provided with a silver halide emulsion layer combined with an image-receiving layer, a white light diffusion layer, a light-shielding layer, and a dye image-forming substance on the side of the transparent cover sheet of the transparent support;
A transparent cover sheet (ii) provided with a neutralization layer and a neutralization timing layer on the side surface of the photosensitive sheet of a transparent support different from the above; and carbon black developed between the photosensitive sheet and the transparent cover sheet A white light diffusing layer in the photosensitive sheet, comprising the alkaline processing composition (iii), and (i) to (iii) arranged to be exposed through the transparent cover sheet. A diffusion transfer film unit comprising a silver halide emulsion and a non-photosensitive silver precipitation nucleus between the light-shielding layer and the light-shielding layer, wherein the alkali treatment composition contains a silver halide solvent.   2. The diffusion transfer film unit according to claim 1, wherein the average grain size of the silver halide emulsion between the white light diffusion layer and the light shielding layer is 0.5 [mu] m or less.   3. The diffusion transfer film unit according to claim 1, wherein a silver halide emulsion other than the silver halide emulsion in the diffusion transfer film unit photosensitive sheet and between the white light diffusion layer and the light shielding layer is provided. A diffusion transfer film unit characterized by being a negative type silver halide emulsion.   3. The diffusion transfer film unit according to claim 1, wherein a silver halide emulsion other than the silver halide emulsion in the diffusion transfer film unit photosensitive sheet and between the white light diffusion layer and the light shielding layer is provided. A diffusion transfer film unit characterized by being an internal latent image type direct positive silver halide emulsion.   6. The diffusion transfer film unit according to claim 1, wherein exposure is performed using an exposure head having different light sources that emit light in a plurality of specific wavelength regions. Characteristic diffusion transfer film unit.