JPH052976B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver complex diffusion transfer method (DTR method) and an image receiving element used therein. In the DTR process, silver complex salts are imagewise transferred by diffusion from a silver halide emulsion layer to an image-receiving layer, and they are converted into a silver image, often in the presence of physical development nuclei. For this purpose, an imagewise exposed silver halide emulsion layer is brought into contact with an image receiving element in the presence of a developing agent and a silver halide complexing agent to solubilize the unexposed silver halide. Convert to silver complex salt. In the exposed parts of the silver halide emulsion layer, the silver halide is developed to silver (chemical development);
Therefore, it cannot be dissolved or diffused any further. In the unexposed portions of the silver halide emulsion layer, the silver halide is converted to soluble silver complex salts which are transferred to the received image where they form a silver image, usually in the presence of development nuclei. In a direct positive silver halide emulsion, the exposed and unexposed areas have opposite effects. The DTR method has a wide range of possible applications. JP-A-50-34523 describes that continuous tone images can be obtained by modifying the silver halide emulsion layer. However, the silver images obtained by this method suffer from a marked brown to yellowish brown color, and even with the use of well-known blackening agents such as 1-phenyl-5-mercaptotetrazole, there is little problem. It is enough. JP-A-54-99436 describes that the color tone of silver images can be improved by using catechol and 3-pyrazolidinone, but this is still insufficient. In particular, since it is a continuous tone image, from low to high density areas,
This makes it difficult to obtain a neutral gray transferred silver image. The purpose of the present invention is to be able to obtain neutral gray continuous tone images.
An object of the present invention is to provide a DTR method and an image receiving element used therein. The above-mentioned object of the present invention is to have a silver halide emulsion layer of silver chloroiodide or silver chloroiodobromide, and the amount of the hydrophilic colloid binder in the emulsion layer or in the emulsion layer and the layer above the silver halide is A method for forming a recorded image using a photosensitive element having an amount of about 3 times or more by weight relative to the amount of silver and an image receiving element having a layer containing physical development nuclei dispersed in a hydrophilic colloid binder, the method comprising: This was achieved using a silver complex diffusion transfer method in which the sexual colloid binder is a synthetic polymer having a group that is hydrophilic to physical development nuclei. This will be explained in more detail below. As the physical development nucleus, metals such as silver, gold, platinum, palladium, copper, cadmium, lead, cobalt, nickel, or their sulfides, selenides, etc. can be used. These are preferably colloidal. The inventors of the present invention have attempted various improvements in the deterioration of the color tone of silver images caused by the method of forming continuous tone images as described above, and have found that although the high density areas become neutral, the low density areas are brownish. Or, when a somewhat satisfactory neutral color was obtained, the maximum density was significantly lowered, making it impossible to obtain a fully satisfactory result. However, as a result of further intensive research, we found that the type of hydrophilic colloid binder used in producing physical development nuclei is important for improving color tone, and the presence of groups that have hydrophilic properties for the core particles is important. I found it to be essential. It seems possible to explain that a group having hydrophilicity toward the nucleus is a group that has an adsorption effect on the core particles such as metals or their sulfides, and has a tendency to aggregate the core particles. It will be done. This is because it is consistent with the fact that a hydrosol core without binder is highly cohesive but can obtain neutral colors. However, the image-receiving element using the synthetic polymer of the present invention was able to form a neutral color continuous tone silver image with less loss in maximum density. Examples of synthetic polymers that are hydrophilic to physical development nuclei include those described in Japanese Patent Application Laid-Open No. 53-21602. That is, the polymer is a polymer containing at least a monomer having a functional group A generally represented by the following formula. A is a group having an affinity for physical development nuclei, and includes groups corresponding to the following () to (). () A 5- or 6-membered heterocycle containing one or more atoms selected from N, O, and S. These rings may be two or more condensed rings, or they may be condensed with a benzene ring or naphthalene ring. It may be something you did. () Thioether group, thiol group, thioxo group () Amino group, guanidino group B is a hydrophilic group such as hydroxyl group, carboxyl group, sulfonic acid group, amide group, X ₁ and X ₂ are functional groups A,
A group that connects B, such as -O-, -CH ₂ -, -
CH ₂ −, −CH ₂ −,

It shows groups such as [Formula], and it is not necessary to have these groups. n is 1 mol% or more, preferably 5 to 50 mol%,
m is generally (100-n) mol%, but other structural units may be copolymerized. The average degree of polymerization is about 100 to about 3000. Specific examples of the functional heterocycle represented by A are shown below, but these may have a substituent. For example, imidazole, imidazoline, imidazolidine, benzimidazole, imidazolone, imidazolidone, pyrazolidone, pyrazolene, pyrazolidine, pyrazoline, pyrazole, imidazole, oxazolidone, oxazolone, oxazole, benzoxazole, thiazolidone, thiazolone, thiazolidine, thiazoline, thiazole, benzothiazole, Examples include pyrrolidone, pyrrolidine, pyrroline, pyrrole, indole, thiophene, benzothiophene, oxazine, thiazine, piperidine, pyridine, quinoline, pyrimidine, quinazoline, pyridazine, piperazine, pyrazine, quinoxazine, triazole, benztriazole, triazine, tetrazole, purine, etc. However, it is not necessarily limited to these. Further, as the hydrophilic group represented by B, a hydroxyl group, a carboxyl group, an amide group, a sulfonic acid group, etc. are suitable. The synthetic polymer used in the present invention is not only a copolymer represented by the above formula, but also a polymer having a functional group A or a blend thereof with a polymer having a functional group B. It can also be used in Furthermore, it can also be combined with other arbitrary polymers. The image-receiving layer contains a surfactant, a matting agent, a fluorescent dye, a discoloration inhibitor, a toning agent (e.g., 1-phenyl-5-mercapto-tetrazole), a developing agent (e.g.,
Hydroquinone and its derivatives, 1-phenyl-
3-pyridridone and its derivatives), silver halide solvents (eg, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc.), and the like.
Furthermore, a neutralizing layer and a subbing layer for improving adhesion to the support may be provided below the image-receiving layer. A typical photosensitive material for DTR is composed of at least one silver halide emulsion layer provided on a support, and the amount of silver halide, calculated as silver nitrate, is generally coated in the range of 0.5 g to 3.5 g/m ² be done. In addition to this silver halide emulsion layer, auxiliary layers such as an undercoat layer, an intermediate layer, a protective layer, and a release layer are provided as necessary. As mentioned above, the image-receiving element of the present invention uses a silver halide of silver chloroiodide or silver chloroiodobromide with a high content of silver chloride, as described in JP-A-50-34523, and the halogen It is used in a method of forming continuous tone images using a light-sensitive material in which the emulsion layer (and its upper layer) contains a polymer binder with a high ratio of silver oxide. Silver chloride is approximately 80 mol% or more, silver iodide is approximately
It is silver chloroiodide or silver chloroiodobromide containing 0.1 mol% or more. Hydrophilic colloid binders for photosensitive materials include gelatin, phthalated gelatin, acylated gelatin, phenylcarbamylated gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol,
Partially saponified polyvinyl alcohol, heat processed products of polyvinyl alcohol and maleic anhydride copolymers (e.g. styrene-maleic anhydride, ethylene-maleic anhydride, etc.), polyacrylamide, poly-N-vinylpyrrolidone, latex Water-soluble polymer compounds such as polyacrylic esters, polymethacrylic esters, polystyrene, polybutadiene, etc. alone or in combination can be used alone or in combination. The binder is used in such a manner that the total amount in the emulsion layer or in the emulsion layer and a layer above it (for example, a protective layer) is about 3 times or more the weight of the silver halide. Silver halide emulsions can be sensitized in a variety of ways when they are manufactured or coated. It may be chemically sensitized by methods well known in the art, for example with sodium thiosulfate, alkylthioureas, or with gold compounds such as rhodan gold, gold chloride, or a combination of both. good. The emulsion is about 530 more.
It is usually sensitized to a range of ˜560, but can also be bankro sensitized. The silver halide emulsion layer and/or the image-receiving layer may contain any compound commonly used for carrying out the silver complex diffusion transfer method. These compounds can include, for example, capri inhibitors such as tetrazaindene and mercapto compounds, coating aids such as saponins and polyalkylene oxides, hardeners such as formalin and chrome alum, plasticizers, and the like. The support used for the photosensitive material or image-receiving material is any commonly used support.
These include paper, glass, films such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, etc.; metal supports coated on both sides with paper; paper supports coated on one or both sides with an alpha-olefin polymer such as polyethylene; You can also use your body. The developing solution used in the DTR method contains alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and tribasic sodium phosphate. Preservatives such as sodium sulfite, thickening agents such as carboxymethyl cellulose, hydroxyethyl cellulose, antifoggants such as potassium bromide,
silver halide solvents, such as sodium thiosulfate,
Toning agents, such as 1-phenyl-5-mercapto-
tetrazole, development modifiers such as polyoxyalkylene compounds, onium moieties, developing agents such as those described in GB 1001558, and if necessary developing agents such as catechol, hydroquinone, 1-phenyl- Contains 3-pyrazolidone, hydroxylamine, etc. The pH of the processing solution is the pH that activates development, usually about 10~
14, preferably about 12-14. a certain
The optimum pH in the DTR method varies depending on the photographic element used, the desired image, the type and amount of various compounds used in the processing liquid composition, etc. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited in any way. Example 1 Physical development nuclei consisting of nickel sulfide and silver sulfide were prepared in a 1% gelatin aqueous solution by reacting equimolar amounts of nickel nitrate, silver nitrate, and sodium sulfide. On one side of a 110 g/m ² paper support coated on both sides with polyethylene, a gelatin image-receiving layer containing 5 x 10 ^-5 mol/m ² of the above-mentioned nuclei was applied with a dry weight of 3 ml of hydrophilic colloid.
Comparative image-receiving material A was prepared by providing the film at a concentration of 1.2 g/m ² . On the other hand, on the same paper support as the image-receiving material, carbon black and 1
A gelatin subbing layer (gelatin 3 g/m ² ) containing hydroquinone (g/m ² ) and 1-phenyl-4-methyl-3-pyraridone (0.3/ml) is applied, and silver chloroiodobromide (silver bromide) is applied thereon. The gelatin-silver halide milk layer (silver nitrate: gelatin) is ortho-sensitized and contains 1.8 g/m ² of silver nitrate (7 mol %, silver iodide 1 mol %), and further contains 0.15 g/m ² of hydroquinone (silver nitrate:gelatin). =
1:2.7) and a protective layer (gelatin 1.3 g/m ² ) to prepare a photosensitive material. The emulsion surface of the photosensitive material exposed for sensitometry and the image receiving surface of the image receiving material are superimposed, passed through a normal processor containing the following developing processing solution 1, and 30 seconds after exiting the squeegee roller, both materials are separated. I peeled it off. The processing liquid temperature was 20°C. <Diffusion transfer developer> Water 800ml Anhydrous sodium sulfite 40g Sodium triphosphate (12-hydrate) 75g Sodium hydroxide 5g Sodium thiosulfate (pentahydrate) 20g N-methyl-aminoethanol 10ml 1-phenyl-5-mercaptotetrazole
50 mg Potassium bromide 1 g A silver image with sufficient gradation to reproduce the continuous tone original was formed on image-receiving material A, but the image was a brownish color with a marked reddish tinge. On the other hand, the 1% aqueous gelatin solution used for the production of the core was mixed with AM-VI (acrylamide-vinylimidazole copolymer having 20 mol% vinylimidazole), CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose),
An image receiving material was prepared and tested in the same manner except that PVA (polyvinyl alcohol) and PAM (polyacrylamide) were used. All of these image-receiving materials had continuous tone properties and maximum densities comparable to those of comparative image-receiving material A. However, samples other than samples using AM-VI tend to improve the color tone in high concentration areas to neutral colors, but cannot change the color tone from low concentration areas to high concentration areas to neutral colors. On the other hand, the AM-VI image-receiving material showed good neutral color over the entire density range. Example 2 The core of Example 1 was produced using the vinyl copolymer shown in the table below at a concentration of 7%, and mixed with gelatin of the image-receiving layer at a ratio of 5% by weight to prepare an image-receiving material. Values represent mol%.

[Table] All were good continuous tone original images and good neutral color silver images. Example 3 Example 2 was repeated. A photosensitive material produced in exactly the same manner as in Example 1 was used, except that catechol was used instead of hydroquinone in the undercoat layer. It was a silver image with good continuous gradation and a more neutral color.

Claims (1)

[Claims] 1 It has a silver halide emulsion layer of silver chloroiodide or silver chloroiodobromide, and the amount of hydrophilic colloid binder in the emulsion layer or in the emulsion layer and the layer above it is about 3% relative to the above amount of silver halide. A method of forming a recorded image on an image-receiving element using a photosensitive element whose weight is more than double the weight of the photosensitive element, the method comprising:
A silver complex salt diffusion transfer method, wherein the hydrophilic colloid binder of the image receiving element is a synthetic polymer having a group having hydrophilicity toward physical development nuclei.