JPH03241347A - Manufacture of image receiving material for silver complex salt diffusion transfer method - Google Patents

Abstract

PURPOSE:To inhibit occurrence of Newton's rings and to improve silver mirror by incorporating a hardener substantially not in a coating fluid for forming an image receiving layer but in that for forming a water-permeable hydrophilic colloidal layer. CONSTITUTION:The water-permeable hydrophilic colloidal layer containing no physically developing nucleus is formed on the image receiving layer containing the physically developing nuclei to obtain the image receiving material for the silver complex salt diffusion transfer method, and the hardener is incorporated not substantially in the coating fluid for forming the image receiving layer. It is preferred to use silver chloride, chlorobromide, chloroiodide, or chloroiodobromide containing >=90 mol% chloride for the silver halide of the silver halide emulsion of the photosensitive material to be used in order to rapidly form the silver complex salt by virtue of a silver halide solvent, thus permitting the Newton's rings not to occur and the silver mirror to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to an image-receiving material for silver complex diffusion transfer method (DTR method).

(B) Prior art and its problems The silver complex salt diffusion transfer method generally consists of a photosensitive material in which a silver halide emulsion layer is formed on a support as a photosensitive layer, and an image receiving layer containing physical development nuclei is formed on the support. It consists of a processing liquid containing an image-receiving material and a silver halide solvent. The principle of the silver complex diffusion transfer method is that the silver halide in the exposed areas of the exposed photosensitive layer is developed by a processing solution or a developing agent in the photosensitive material, and at the same time, the silver halide in the unexposed areas is developed by the halogen in the processing solution. It reacts with a silver oxide solvent to form a soluble silver complex salt, which diffuses into the image-receiving material and deposits on physical development nuclei in the image-receiving layer to form a silver image.

The DTR method has a wide range of possible applications. copies of documents;
For example, they are widely used for copies of printed matter, handwritten documents, blueprints, and as printing materials for plate making, and require faithful image reproduction of the original manuscript.

In addition, in the above DTR method, it is important to obtain a sharp, non-metallic glossy silver image with high optical density in the image-receiving material.

It is known that in order to obtain such a transferred silver image, a layer containing no physical development nuclei may be provided on the image-receiving layer of the image-receiving material.

That is, JP-A-1-94344 discloses that by using an image-receiving material in which the total solid coverage of the image-receiving layer and the water-permeable uppermost layer is 2 g/m or less, sharp nonmetallic lustrous silver can be produced within a short processing time and drying time. A method of forming an image is described.

However, in such an image-receiving material, when the image-receiving layer containing physical development nuclei is hardened by the hardening agent contained therein, a continuous silver image forms at the interface between the image-receiving layer and the colloidal layer that does not contain development nuclei. It was found that silver mirrors were formed, and due to the interference of light with the upper layer, so-called Newton rings were generated, which significantly reduced the quality of the image. .

(C) Object of the Invention An object of the present invention is to provide a method for producing an image-receiving material for a silver complex diffusion transfer method in which so-called Newton rings are not generated and the silver mirror is improved.

Another object of the present invention is to provide a method for producing an image-receiving material capable of obtaining non-metallic glossy silver images of high optical density.

(D) Structure of the Invention The object of the present invention is to provide an image-receiving material for a silver complex diffusion transfer method, which has at least one water-permeable hydrophilic colloid layer containing no development nuclei on an image-receiving layer containing physical development nuclei. Silver complex salt diffusion, characterized in that the image-receiving layer coating solution does not substantially contain a hardening agent, and the water-permeable hydrophilic colloid layer coating solution contains a hardening agent. This is achieved by a method for producing an image-receiving material for a transfer method.

In order to enable the rapid formation of silver complex salts with the aid of silver halide solvents, the silver halide of the silver halide emulsion of the light-sensitive material used according to the invention contains silver chloride, containing more than 90 mol % of chloride, It is preferable to use silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

Silver halide emulsions can also be spectrally sensitized in blue, green, and red. It can be a merocyanine, cyanine dye or other sensitizing dye.

Furthermore, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (e.g. hypo,
thiourea, unstable sulfur-containing gelatin), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts, iridium salts, rutium salts, etc.), US patents No. 2.518,
Polyalkylene polyamine compounds described in No. 698 etc.,
imino-amino-methanesulfonic acid as described in German Patent No. 1,208,864, reduction sensitizers (e.g.
tin, etc.) are advantageously used.

The preferred coverage of silver halide in g of silver nitrate per 1 d is in the range 1 to 5 g. The binder for the silver halide emulsion layer is preferably gelatin. However, instead of or in addition to gelatin, one or more other natural and/or synthetic hydrophilic colloids may be used, such as albumin, casein, zein, polyvinyl alcohol, alginic acid or its salts, cellulose derivatives (such as carboxymethyl cellulose, modified gelatin). ) etc. can also be used.

The weight ratio of hydrophilic colloid to silver halide in terms of silver nitrate in the silver halide emulsion layer of the photosensitive material is 0.3.
-5, preferably 0.5-3.

In addition to the binder and silver halide, the photosensitive material contains any type of commonly used compounds in the silver halide emulsion layer and/or in one or more layers in water permeable relationship thereto. can.

For example, mercapto compounds, anti-capri agents or stabilizers such as tetraazaindene, saponins as surfactants, sodium alkylbenzene sulfonates, sulfosuccinic acid ester salts, and alkylaryl sulfonates as described in U.S. Pat. No. 2,600,831. In addition, wax polyol compounds, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, N-guanyl bitrazone compounds, etc. , quaternary onium compounds, mordants such as tertiary amine compounds, diacetyl cellulose, styrene-perfluoroalkylene sodium maleate copolymers, reaction products of styrene-maleic anhydride copolymers and p-aminebenzenesulfonic acid. Antistatic agents such as alkali salts, polymethacrylic esters, polystyrene, matting agents such as colloidal silicon oxide, acrylic esters, film property improvers such as various latexes, styrene-maleic acid copolymers,
Thickeners and antioxidants such as those disclosed in Japanese Patent Publication No. 36-21574,
A developing agent and a pH adjuster can be used.

The silver halide emulsion layer can be hardened with a suitable hardener, and specific examples of hardeners include aldehyde compounds such as formaldehyde and geltaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, Bis(2-chloroethylurea)-2-hydroxy-4,6-
Dichloro-L3.5-triazine, U.S. Patent No. 3. 2
88. No. 775, compounds with reactive halogens, divinyl sulfone, U.S. Pat. 635°7 (compounds with reactive olefins as described in No. 8,
N-methylol compounds such as those described in U.S. Pat. No. 2,732,316; 103°437, U.S. Pat. No. 3,017,280
No. 2. 983. aziridine compounds as described in No. 611, carbodiimide compounds as described in U.S. Pat. No. 3,100,704, U.S. Pat. No. 3,09↓,
Examples include epoxy compounds as described in No. 537, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chromium alum, potassium alum, and zirconium sulfate.
These can be used alone or in combination of two or more.

As the support for the photosensitive material used in the present invention, plastic films such as polystyrene, polycarbonate film, cellulose triacetate and polyethylene terephthalate, polyethylene laminated paper coated with polyethylene, baryta paper, etc. are used.

The back layer desirably provided on the back side of the support contains a hydrophilic colloid in an amount necessary to maintain curl balance with the photosensitive layer side. The amount depends on the total amount of hydrophilic colloid on the photosensitive layer side, the amount of white inorganic pigment, etc.

The image-receiving layer of the image-receiving material used according to the invention can be coated on an opaque or transparent support, which can be one of the supports mentioned above for photosensitive materials.

Physical development nuclei include silver, gold, platinum, palladium, copper,
Metals such as cadmium, lead, cobalt, nickel, or their sulfides, selenides, etc. can be used. These are preferably colloidal.

One or more layers of non-photosensitive materials, including the image-receiving layer, may include surfactants, matting agents, fluorescent dyes, anti-tarnish agents, toning agents, developing agents (e.g. hydroquinone and its derivatives, 1-phenyl-3-pyrazolidone). and its derivatives), silver halide solvents (for example, 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.

The image-receiving layer and the water-permeable hydrophilic colloid layer provided above the image-receiving layer are comprised of any of the binders described above for the silver halide emulsion layer. Gelatin is the preferred binder for the image receiving layer and the hydrophilic colloid layer.

In the present invention, the thickness of the image-receiving layer is generally preferably 0.1 to 3.0 μm, and more preferably 0.4 to 5 μm.

The thickness of the water-permeable colloid layer provided on the image-receiving layer is:
0.4-2.0 pm is preferable, and 0.8-1.5 pm is more preferable.

The water-permeable hydrophilic colloid layer also contains a suitable hardener as described for the silver halide emulsion layer. Preferred are low molecular weight diffusible hardeners, particularly aldehyde-based, triazine-based, and vinylsulfone-based hardeners.

The amount of hardening agent used should be calculated based on the total amount of gelatin, and should be the minimum amount that achieves the required hardening level, and can be freely selected depending on the purpose, but approximately per gram of gelatin. , the addition amount may be about 0.02 to 0.2mM.

In the present invention, "the image-receiving layer coating liquid does not substantially contain a hardening agent" does not mean not only that it does not contain a hardening agent at all, but also that it is used in a small amount within a range that does not impair the achievement of the purpose of the present invention. should be understood as inclusive.

A plurality of hydrophilic colloid layers can be applied in several parts, or can be applied in multiple layers simultaneously. The coating method may be any known method and is not limited.

The processing liquid used in the diffusion transfer method contains alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., silver chloride solvents such as sodium thiosulfate, ammonium thiocyanate, etc.
Cyclic imide compounds, thiosalicylic acid, etc., preservatives, such as sodium sulfite, thickening agents, such as hydroxyethyl cellulose, carboxymethyl cellulose, antifoggants, such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., development modification. agents such as polyoxyalkylene compounds, onium compounds, developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone, hydroxylamine, and the like.

However, in a highly alkaline processing solution containing this developing agent,
The developing agent has the disadvantage of being deactivated by air oxidation, and therefore, the method of incorporating the developing agent into the DTR material, that is, into the silver halide emulsion layer and/or the hydrophilic colloid layer which is in a water-permeable relationship therewith, is effective. Its shortcomings can be largely avoided.

In diffusion transfer materials containing such a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used.

The DTR method using an alkaline activated liquid was developed by the Japanese Patent Publication Publication No. 39-27
568, opening/closing 47-30856, opening/closing 51-43778
You can refer to the specifications of .

(E) Examples The present invention will be explained below using Examples, but the present invention is not limited in any way.

The photosensitive material is a polyethylene laminated paper with an undercoat layer containing carbon black for antihalation, and on top of that an ortho-sensitized silver chlorobromide (silver bromide 5 mol%) with an average particle size of 0.3μ. ) converted to silver nitrate is 1.5
g/rd, plus 0.2 g/rd of 1-phenyl-
3-pyrazolidone and 0°7 g/rd hydroquinone,
It was produced with a gelatin silver halide emulsion layer containing 4 g/i of gelatin.

The silver halide emulsion layer is hardened by containing a hardening agent so as not to interfere with diffusion transfer processing.

For the image-receiving material, the following coating solution was prepared, and the solid content was 0.8 g/rr! It was coated and dried.

It was applied so that the mold crushing amount was 1.2 g/rd.

The obtained sample was conditioned at 70% RH for 2 hours and then heated to 40°C.
It was heated for 7 days.

The diffusion transfer treatment liquid used had the following composition.

Apply the following coating solution to the dried image-receiving layer in a dry state.

(Left below) The photosensitive material produced as described above is exposed according to the image, the emulsion surface of the photosensitive material and the image receiving surface of the image receiving material are overlapped, and the process is carried out in a processor having an aperture roller containing the above-mentioned diffusion transfer processing liquid. After passing through and exiting the squeeze roller, both materials were peeled off 30 seconds later.

The image-receiving material was washed with water for about 30 seconds, dried, and the reflection density of the black area was measured using a Macbeth RD519 reflection densitometer.

The size of the silver mirror and Newton's ring interference fringes in the transferred image was evaluated by observing with the naked eye.

The production of transferred images using the above materials was repeated several times in the same manner except that the binders and hardeners in the image-receiving layer and the water-permeable hydrophilic colloid layer were changed as shown in Table 1 below. Hardener A is 2,4-dichloro-6-hydroxy-s-triazine sodium salt (5% aqueous solution), and hardener B is formalin (5% aqueous solution Table 1. The measurement results obtained are shown in Table 2 below. show.

Table 2 It is clear from Table 2 that the image-receiving materials 4 to 6 of the present invention exhibit excellent photographic performance.

Claims (1)

[Claims] 1. In the method for producing an image-receiving material for a silver complex diffusion transfer method having at least one water-permeable hydrophilic colloid layer containing no development nuclei on an image-receiving layer containing physical development nuclei, a hardener is added to the image-receiving layer coating solution. A method for producing an image-receiving material for a silver complex diffusion transfer method, characterized in that the coating solution for the water-permeable hydrophilic colloid layer contains a hardening agent.