JPH05265162A - Image receiving material for silver complex salt diffusion transfer - Google Patents

Abstract

PURPOSE:To obtain an image receiving material for silver complex salt diffusion transfer having high transmission density. CONSTITUTION:This image receiving material contains physical developing nuclei obtd. by adding silver ions to a colloidal dispersion of metallic palladium reduced with ascorbic acid in a hydrophilic colloidal soln. and further adding a reducing agent. When this image receiving material is used, higher transmission density than the conventional density can be obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver complex salt diffusion transfer material in which a light-sensitive material and an image receiving material are combined, and more particularly to a silver complex salt diffusion transfer transmission image receiving material having a high transmission density.

[0002]

The silver complex salt diffusion transfer method generally comprises a light-sensitive material having a silver halide emulsion layer as a light-sensitive layer formed on a support and an image-receiving material having an image-receiving layer containing physical development nuclei formed on the support. It is composed of a processing solution containing a silver halide solvent. The principle of the silver complex salt diffusion transfer method is that the silver halide in the exposed area of the exposed photosensitive layer is developed by the developing solution in the processing solution or the photosensitive material, and at the same time, the silver halide in the unexposed area becomes the halogen in the processing solution. It reacts with a silver halide solvent to form a soluble silver complex salt, diffuses into the image receiving material, and is deposited on physical development nuclei in the image receiving layer to form a silver image.

The silver complex salt diffusion transfer method based on such a principle is widely used for copy of documents, and further as a plate material for plate making work. As an important quality of the image receiving material used in the silver complex salt diffusion transfer method, the silver image density (reflection and transmission density) is high, the color tone (reflection and transmission) is good (generally blue-black tone is desired), and the diffusion transfer speed is fast. Furthermore, it is important that the image receiving layer has sufficient film strength. In particular, the silver image density (reflection and transmission density) is a very important quality, and it is said that a high image density is desirable for good reproduction of image quality (fine lines and halftone) when used as a block material. There is. However, the conventionally used physical development nuclei tend to be designed for a reflection image receiving material rather, and there is a drawback that the transmission density does not increase so much even if they are improved and used for a transmission image receiving material. .. Further, in the transmission image receiving material, the transmission color becomes reddish depending on how to select the physical development nuclei, and the ability to shield visible light is reduced, resulting in a reduction in transmission density.

[0004]

An object of the present invention is to provide a transmission image receiving material having a high transmission density.

[0005]

Examples of general physical development nuclei include heavy metals such as silver, platinum, palladium, copper, cadmium, lead, cobalt and nickel or their sulfides and selenides. These physical development nuclei materials reduce corresponding metal ions to form metal colloidal dispersions, or metal ion solutions and soluble sulfides,
It is obtained by mixing a selenide solution to form a water-insoluble metal sulfide, a colloidal dispersion of a metal selenide. It is known that physical development nuclei having different physical properties such as shape affect the density and transmitted color of a transferred silver image even if the same kind of metal, metal sulfide or selenide is prepared. ..

Japanese Unexamined Patent Publication No. 63-249845 discloses a structure in which two or more kinds of heavy metal sulfides are used as physical development nuclei, and at least one kind of heavy metal sulfide is attached to the surface of the heavy metal sulfide different from the former. It has been shown that an image receiving material containing the physical development nuclei thereof provides a diffusion transfer image with improved tone. However, when the physical development nuclei obtained under these conditions were applied to a transmission image receiving material, a satisfactory transmission density was not obtained. Moreover, JP-A-1-100
It is described in 545 that a transfer image with good image quality can be obtained by using metal palladium reduced by ascorbic acid in a hydrophilic colloid solution as a physical development nucleus. However, even when the physical development nuclei obtained under these conditions were applied to a transmission image receiving material, a similarly satisfactory transmission density could not be obtained. Therefore, as a result of further diligent research conducted by the present inventors with reference to these patents, a physical development nucleus having a structure in which another reduced metal nucleus is attached to the surface of one reduced metal nucleus is produced to produce a transmission image receiving material. When applied to, it succeeded in obtaining a high transmission density with a small amount of physical development nuclei.

It is conventionally known to use a plurality of heavy metals as physical development nuclei. According to JP-A-63-249845, a method for producing physical development nuclei and its physical structure are described as follows. A method of obtaining a mixture of a metal sulfide colloidal dispersion by mixing a solution containing a plurality of metal ions with a solution containing a sulfiding agent. It is considered that the physical development nuclei prepared by the above method are in an aggregated state in which a plurality of metal sulfides are intricately formed, or are in a mixed state of each single metal sulfide. It is unlikely that a certain type of physical development nuclei (not limited to one type) may selectively form an aggregated structure on the surface of a different type of physical development nuclei. On the other hand, a first metal ion solution containing at least one metal ion and a solution containing an excess amount of a sulfiding agent with respect to all metal ions contained therein are mixed to once disperse the metal sulfide colloid. A metal sulfide colloidal dispersion obtained by mixing a second metal ion solution different from the first metal containing at least one metal to the place where the product is formed, or the first metal ion solution and it A solution containing all metal ions and an equivalent amount of a sulfiding agent is mixed to form a metal sulfide colloidal dispersion, and the second metal ion solution and a solution containing a sulfiding agent are mixed in the presence of this metal sulfide colloidal dispersion. The metal sulfide colloidal dispersion thus obtained is the surface of the metal sulfide produced by the metal ions contained in the first metal ion solution, and the gold contained in the second metal ion solution. Appears to be metal sulfides produced by ion is possible to explain that form the aggregate structure adheres. Because, the metal sulfide by the metal ions contained in the first metal ion solution has already been generated,
This is because it is sufficiently conceivable that the precipitation and growth of metal sulfides selectively occur due to the metal ions contained in the second metal ion solution with the surface of the metal sulfide particles as nuclei. Thus, it is considered that the description in JP-A-63-249845 can be applied not only to physical development nuclei by metal sulfides but also to reduced heavy metals. The physical development nuclei material prepared in this manner is the same as the physical development nuclei material prepared by the conventional method, or the physical development nuclei material obtained by separately preparing individual metals contained therein and then mixing them. Unlike the development nuclei, only the physical development nuclei of the present invention were able to obtain a high transmission density.

Preferable examples of the metal contained in the first metal ion solution used for preparing physical development nuclei of the present invention include palladium and silver, but other heavy metals such as zinc and tin may be used. Further, two or more of these metals may be used in combination, or the metals contained in the second metal ion solution may be combined. As a preferable example of the metal contained in the second metal ion solution, silver can be mentioned, but palladium, copper or the like can also be used. Moreover, you may use these together. Ascorbic acid is suitable as a reducing agent for reducing these metal ions, but, for example, NaBH ₄ or another metal ion having a different ionization tendency may be used. The molar ratio of the first metal ion and the second metal ion to the reducing agent is between 1: 1 and 1:10, but preferably between 1: 2 and 1: 4. A preferred example of the hydrophilic colloid used for preparing the physical development nuclei is poly-N-vinylpyrrolidone, but other commonly used hydrophilic colloid materials such as gelatin, carboxoxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, Polyacrylamide, acrylamide-vinylimidazole copolymer and the like can be used alone or in combination. As the hydrophilic colloid solution, a solution in which the solid content of the hydrophilic colloid material is 0.5 to 20% by weight is used.

The pH at the time of preparing physical development nuclei may be arbitrary,
It is preferably weakly acidic. The temperature is arbitrary between 10 ° C and 70 ° C, but is preferably between 30 ° C and 50 ° C.
After mixing the solution containing the first metal ion and the solution containing the reducing agent, the time required to generate the physical development nuclei substance varies depending on the temperature, but at 40 ° C., it takes 1 minute or more. Then, a solution containing the second metal is added, and it takes 1 minute or more at 40 ° C. The physical development nuclei contained in the image receiving layer are about 1 × 10 ⁻⁷ to about 1 × as the total amount of the first metal and the second metal.
The amount is in the range of 10 ⁻⁵ mol / m ² . Also, the molar ratio of the first metal to the second metal is between 1: 1 and 1:10, but preferably between 1: 2 and 1: 5.

As the binder of the image receiving layer, 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 (for example, styrene-maleic anhydride, ethylene-maleic anhydride, etc.), polyacrylamide, poly-N
Water-soluble polymer compounds such as vinylpyrrolidone and latexes (for example, homopolymers or copolymers of polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polybutadiene, etc.) can be used alone or in combination.

The image-receiving layer can be hardened with an appropriate hardener, and specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, Bis (2-chloroethylurea) -2-hydroxy-4,6-
Dichloro-1,3,5 triazine, US Pat. No. 3,28
Reactive halogen-containing compounds as described in US Pat. No. 8,775, divinyl sulfone, US Pat. No. 3,635,718.
Compounds having reactive olefins as described in US Pat. No. 2,732,316, N-methylol compounds as described in US Pat. No. 3,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. No. 3,017. , 280 and 2,983,611, and aziridine compounds,
Carbodiimide compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum. Inorganic hardeners such as potassium alum, zirconium sulfate, etc. can be used alone or in combination of two or more.

The image-receiving layer is a surface active agent (for example, a natural surface active agent such as saponin, alkylene oxide type, glycerin type, glycidol type nonionic surface active agent, higher alkylamines, quaternary ammonium salts, pyridine, etc. Of heterocyclic compounds, cationic surfactants such as sulfonium compounds, anionic surfactants containing an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester group, phosphoric acid ester group, amino acids, aminosulfonic acids, amino alcohols Amphoteric surfactants such as sulfuric acid or phosphoric acid esters, fluorine-based anions and amphoteric surfactants), matting agents,
Fluorescent dye, anti-tarnish agent, toning agent (for example, 1-phenyl-5-mercaptotetrazole as a typical one, other toning agents described on page 61 of Photographic Silver Halide Diffusion Process issued by Focal Press Co., Ltd.), development Main agent (eg hydroloquinone and its derivative, 1-phenyl-3-pyrazolidone and its derivative etc.), silver halide solvent (eg sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate etc.) it can. Further, an over layer may be provided on the image receiving layer, a neutralizing layer may be provided below, and an undercoat layer for improving adhesion to the support may be provided.

The silver halide emulsion used in the light-sensitive layer of the silver complex salt diffusion transfer light-sensitive material according to the present invention is preferably a silver chloride-based emulsion as described above, but is not limited thereto. Instead of an emulsion commonly used for diffusion transfer, the silver complex salt may have the ability to develop and diffuse in the exposed and unexposed areas at the speeds required for the diffusion transfer method, respectively. Mention may be made of silver iodide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodide, silver chloroiodobromide and mixtures thereof.

The silver halide emulsion can be sensitized in various ways as it is manufactured or coated. It may be chemically sensitized by methods well known in the art, for example with sodium thiosulfate, alkyl thioureas, or with gold compounds such as gold rhodanide, gold chloride, or a combination of both. Further, the spectral sensitization that is usually performed can be performed.

As the binder of the photosensitive layer, a polymer substance usually used in the production of silver halide emulsion, for example, the binder described in the image receiving layer can be used. The photosensitive layer can be hardened with an appropriate hardener described in the image receiving layer. Further, the light-sensitive layer contains additives generally used in silver halide light-sensitive materials such as surfactants, antifoggants, matting agents, fluorescent dyes, developing agents (such as hydroquinone and its derivatives, 1-phenyl-3- Pyrazolidone and its derivatives) are used. Further, in addition to the photosensitive layer, an auxiliary layer such as an undercoat layer, an intermediate layer, a protective layer and a peeling layer may be provided if necessary.

The support of the image receiving material according to the present invention is any transparent support which is usually used. Glass, a film such as a cellulose acetate film, a polyvinyl acetal film, a polystyrene film, or a polyethylene phthalate film can be used for this.

The silver complex salt diffusion transfer treatment liquid used in the present invention may have an ordinary silver complex salt diffusion transfer treatment liquid composition. That is, a developing agent for developing exposed silver halide, such as hydroquinone and its derivatives, 1-
Solvents of undeveloped silver halide, such as phenyl-3-pyrazolidone and its derivatives, such as sodium thiosulfate,
Ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc., sodium sulfite as a preservative, potassium bromide as a development inhibitor, additives such as 1-phenyl-5-mercaptotetrazole as a toning agent, an alkaline substance,
For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, a thickening agent such as carboxymethyl cellulose, hydroxyethyl cellulose and the like can be contained.

[0018]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Comparative Example 5 ml of a 0.05 mol / l aqueous solution of palladium chloride (dissolved by adding sodium chloride) and 0.1 ml of L-ascorbic acid in 30 ml of a 3% aqueous solution of poly-N-vinylpyrrolidone.
A physical development nucleus for comparison was prepared by mixing 5 ml of a 5 mol / l aqueous solution with vigorous stirring and reacting at 40 ° C. for 10 minutes. Example 4 In a 30% aqueous solution of 3% poly-N-vinylpyrrolidone, 4 ml of a 0.05 mol / l aqueous solution of palladium chloride (dissolved by adding salt) and 0.1 ml of L-ascorbic acid.
A 5 mol / l aqueous solution (4 ml) was mixed with vigorous stirring, and the mixture was reacted at 40 ° C. for 10 minutes.
1 ml of 5 mol / l aqueous solution was added, and 1 ml of 0.15 mol / l aqueous solution of L-ascorbic acid was further added to prepare physical development nuclei of the present invention. Both were added to an aqueous gelatin solution of appropriate concentration and pre-subbed to a thickness of 100.
An image receiving material of the present invention was prepared by making a gelatin image receiving layer containing 1 × 10 ⁻⁶ mol / m ² of palladium on one side of a polyethylene terephthalate film support of μm so that the dry weight of the hydrophilic colloid was 2 g / m ² . ..

The light-sensitive material was provided with an undercoat layer containing carbon black for preventing halation on polyethylene laminated paper, and an ortho-sensitized silver chlorobromide (silver bromide 5 (Mol%) converted to silver nitrate, 1.5 g / m ² , further 0. It was prepared by providing a gelatin silver halide emulsion layer containing ² g / m ² of 1-phenyl-3-pyrazolidone, 0.7 g / m ² of hydroquinone and 4 g / m ² of gelatin. The silver halide emulsion layer is hardened by including a hardening agent so as not to hinder diffusion transfer.

The diffusion transfer treatment liquid used had the following composition.

Water 800 ml Sodium hydroxide 25 g Anhydrous sodium sulfite 100 g Hydroquinone 20 g 1-Phenyl-3-pyrazolidone 1 g Potassium bromide 3 g Sodium thiosulfate 30 g 1-Phenyl-5-mercaptotetrazole 0.1 g Water is added to make 1000 ml.

The light-sensitive material produced as described above is appropriately exposed by a plate-making camera with a manuscript having an appropriately black portion, and the emulsion surface of the light-sensitive material and the image-receiving surface of the image-receiving material are overlapped to each other, and Both materials were peeled off one minute after exiting the squeezing roller by passing through a processor with an squeezing roller inside. The image receiving material was washed with water for about 30 seconds and then dried, and the transmission density of the black portion was measured with a Macbeth TD504 transmission densitometer.

[0023]

[Table 1]

[0024]

As is clear from the examples, the image-receiving material according to the present invention has a high transmission density.

Claims (1)

[Claims] 1. A physical development nucleus in a silver complex salt diffusion transfer material, which comprises two or more types of reduced heavy metals as physical development nuclei, and has a structure in which at least one type of heavy metal is attached with a metal different from the former. A transmission image receiving material characterized by containing.