JPS6057835A - Image receiving material - Google Patents

Abstract

PURPOSE:To enhance film strength, image density, and sharpness by incorporating gelatin specified in Ca concn. in a silver complex salt transfer diffusion material composed of a combination of a photosensitive material and an image receiving material. CONSTITUTION:Gelatin contg. <=1,000ppm is used as the binder of an image receiving layer. A hydrophilic synthetic resin, such as PVA, partially saponified polyvinyl acetate, maleic anhydride copolymer, the heat treated mixture of said copolymer and PVA, polyacrylamide, polyacrylic acid, poly-N-vinylpyrrolidone, and emulsion polymerized synthetic resins, can be used in combination with said gelatin, so long as the content of gelatin in the image receiving layer is lower than about 1,000ppm, and further, a nonsynthesized hydrophilic material, such as carboxymethyl cellulose, sodium alginate, dextran, gum arabic, agar, starch, and its derivs. may be used in combination, and they can be used together with usual gelatin. As a result, the obtained image receiving material can be enhanced in film strength, image density and sharpness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver complex diffusion transfer material that combines a light-sensitive material and an image-receiving material, and particularly relates to improvements in the image-receiving material. The silver complex diffusion transfer method generally uses a light-sensitive material in which a silver halide emulsion layer is formed on a support as a light-sensitive layer, an image-receiving material in which an image-receiving layer containing physical development nuclei is formed on a support, and a solvent for silver halide. It consists of a processing liquid containing 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 developer in the processing solution. The silver particles are absorbed into the image, diffuse into the image-receiving material, and deposit on physical development nuclei in the image-receiving layer to form a silver image. Based on this principle, the silver complex diffusion transfer method can be used to copy documents, such as printed materials, handwritten materials, and blueprints, as well as to handle plate material during platemaking. Image reproduction that is faithful to the original is required.

The important qualities of the image-receiving material used in the silver complex diffusion transfer method are high silver image density (reflection and transmission density) (good color tone (generally desired blue-black tone), fast diffusion transfer speed, and high image reception density). It is important that the layer has sufficient membrane strength.

In particular, silver image density (reflection and transmission density) is a very important quality. Copies are generally required to have high image clarity, and if the silver image density is high, copies with high clarity can be obtained. Furthermore, when used as a printing material, it is desirable that the silver image density be high in order to reproduce good image quality (fine lines and line quality).

It is not overconfident to say that the silver image density greatly influences the performance of the image-receiving material (although research and development in the industry has been intensively carried out to increase the silver image density of the image-receiving material).

In particular, in ordinary black-and-white photographic materials, the silver halide grains are developed to determine the silver image density, but in the silver complex diffusion transfer method, the environment in which the soluble silver complex is developed in the image-receiving layer is also silver. This is thought to have a large effect on image density.

Based on the above-mentioned idea, the present inventors conducted extensive research in order to improve the silver image density of the image-receiving material in the silver complex diffusion transfer method. As a result, the objective of the present invention of improving silver image density could be achieved.

A typical example of the present invention has a calcium content of 1.000
This image-receiving material uses gelatin of less than PPM as a binder for the image-receiving layer. In other words, gelatin is generally manufactured by solubilizing collagen, the main component of animal skin and bones, in hot water, but it is difficult to extract the raw material immediately into hot water. Now, add 1 to 3 ingredients to lime milk.
Collagen is partially hydrolyzed in advance by performing a long-term pretreatment called soaking for several months, ie, liming. The gelatin according to the present invention is made from bovine bones, and most of the inorganic components that account for more than half of the bovine bones, which are the main raw materials, are calcium phosphate. This is dissolved in dilute hydrochloric acid. Ossein is partially hydrolyzed by acid and lost, so hydrochloric acid treatment is carried out under efficient conditions, and long-term treatment to remove calcium phosphate will advance the necessary hydrolysis of ossein, so treatment should be carried out at the optimal location. is being carried out. Even in this case, gelatin extracted after lime treatment still contains a very high concentration of calcium and other inorganic salts. For example, if we look at calcium, commercially available photographic gelatin usually contains 3,000 PPM to 5.00 PPM.
(Contains PPM calcium. As a result of intensive research using gelatin from which these calcium salts and other inorganic salts have been removed, the inventors have found that calcium salts have an adverse effect on the transferred silver concentration. In addition, a high silver image density can be obtained by using an image-receiving material in which the calcium concentration in the gelatin of the image-receiving layer is about LOOOPPM or less.Preferably, the calcium concentration of the gelatin in the image-receiving layer is about 500 PPM or less. This is an image-receiving material made of

As described in the exemplary embodiment of the present invention, such low concentration calcium salt image receiving layers are made possible by the use of gelatin as the sole binder, with a calcium concentration of about 1,000 PPM or less. However, as long as the calcium concentration in the gelatin of the image-receiving layer is as low as about 1,000 PPM, hydrophilic synthetic resins such as polyvinyl alcohol, partially saponified polyvinyl alcohol, maleic anhydride copolymers (such as styrene- Maleic anhydride copolymer, ethylene-maleic anhydride copolymer, inbutylene-maleic anhydride copolymer, Vinyl J Kirneyko J Shi-4RF 7leg 1 noic acid copolymer, vinyl acetate-maleic anhydride copolymers, etc.), and heat-processed products of these maleic anhydride coheavy metals and polyvinyl alcohol,
Polyacrylamide, polyacrylic acid, poly-N-vinylpyrrolidone, emulsion polymerized synthetic resins (for example, polyacrylic ester, polyacrylic acid, polymethacrylic acid, polymethacrylic ester, polystyrene polybutadiene, etc.) or copolymers, etc.) Furthermore, carboxymethyl cellulose, hydroxylethyl cellulose,
It can be used in combination with sodium alginate, dextran, gum arabic, agar, starch and its derivatives, and can also be used in combination with ordinary gelatin.

Gelatin travels 1/// of the total binder amount in the image-receiving layer,
Preferably it is about 24 or more.

The image-receiving layer of the image-receiving material can be hardened with a suitable hardening agent. Specific examples of the hardening agent include aldehyde compounds such as formaldehyde and geltaraldehyde, ketone compounds such as diacetyl and cyclobentanedione, and (2
-chloroethylurea)-2-hydroxy-4,6-dichloro-1,3,5) riazine, U.S. Pat. No. 3,288,
Compounds having reactive halogens as described in No. 775,
Divinyl sulfone, compounds with reactive olefins as described in U.S. Pat. No. 3,635,718, N-methylonyl compounds as described in U.S. Pat. No. 2,732,316, and N-methylonyl compounds as described in U.S. Pat. No. 3,103,437. Incyanates such as U.S. Patent Nos. 3,017,280 and 2,9
aziridine compounds as described in US Pat. No. 83,611, carbodiimide compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. - Logenocarboxaldehydes, dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chromium alum, potassium alum, zirconium sulfate, etc., and these can be used singly or in combination of two or more.

Physical development nuclei used in the image-receiving layer of the image-receiving material according to the present invention include noble metals such as silver, gold, platinum, palladium, copper, cadmium, lead, cobalt, and nickel, or their sulfides;
Selenide etc. can be used. These are preferably colloidal.

The image-receiving layer contains surfactants (for example, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkyl amines, quaternary ammonium salts, pyridine and other heterocycles, Cationic surfactants such as sulfoniums, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols Amphoteric surfactants such as fluorine-containing 7)
thread anions and amphoteric surfactants, etc.), cloak agents, fluorescent dyes, anti-tarnishing agents, color toning agents (typical examples include 1-phenyl-5-mercapto-tetrazole, and other materials published by Focal Press, Photographic. Color toning agents (described on page 61 of Silver Halide Siffusion Process), developing agents (e.g., hydroquinone and its derivatives, 1-pheny/l/-3-pyrazolidone and its derivatives, etc.), silver halide solvents (e.g., thio sodium sulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc.). Furthermore, an overlayer (for example, an overlayer using lime-treated gelatin, acid-treated gelatin, hydroxyethyl cellulose, carboxylmethyl cellulose, pullulan, sodium alginate, etc.) on the image-receiving layer, a neutralizing layer below, and a support layer. A subbing layer may be provided to improve adhesion.

The method for applying the image-receiving layer in the production of the image-receiving material of the present invention is as follows:
A commonly used coating method (eg, air knife method, extrusion method, curtain method, etc.) is used. Regarding drying of the applied coating layer, the drying conditions (temperature, dew point temperature, etc.) are not particularly strictly limited, but
It is preferable to set the gelatin at a temperature of 20° C. or lower and then dry it.

The silver halide emulsion used in the photosensitive layer of the photosensitive material for silver complex diffusion transfer according to the present invention is an emulsion commonly used for diffusion transfer, and there are no strict regulations on the composition of this emulsion.
It is sufficient that the silver salt has the ability to develop and diffuse in the exposed and unexposed areas at the speed required for the diffusion transfer method, such as silver bromide, silver iodide, silver chloride, silver chlorobromide, Mention may be made of silver iodobromide, silver chloroiodide and mixtures thereof. Moreover, they can be subjected to chemical sensitization and spectral sensitization, which are commonly performed. The binder of the photosensitive layer is usually a polymeric substance used in the production of silver halide emulsions, such as
Lime-processed gelatin, acid-processed gelatin, phthalated gelatin, acylated gelatin, phenylcarbamylated gelatin,
Polyvinyl alcohol, partially saponified polyvinyl alcohol to polyacrylamide, poly N-vinylpyrrolidone, hydroxyethyl cellulose, carpoquin methyl ses/l/C7-s, polyvinyl alcohol and anhydrous maleic copolymer (e.g. styrene-maleic anhydride) Synthetic resins subjected to emulsion polymerization (e.g., polyacrylic acid x 7.
(alone or copolymers of polymethacrylate, acrylic acid, methacrylic acid, polystyrene, polybutadiene, etc.) can be used.

Further, the photosensitive layer can be hardened using a suitable hardening agent as described for the image-receiving layer. Furthermore, the photosensitive layer contains additives generally used in silver halide photosensitive materials, such as surfactants, anti-capri agents, matting agents, fluorescent dyes, and developing agents (e.g., hydroquinone and its derivatives, 1-phenyl-3-
pyrazolidone and its derivatives).

Furthermore, there is an overlayer (for example, lime-treated gelatin) on the photosensitive layer.
(e.g., an overlayer using e-treated gelatin, hydroxyl cellulose A/rose, carboxymethyl cellulose, glulan, sodium alginate, etc.), an antihalation layer may be provided underneath.

Generally, the silver complex diffusion transfer method is a so-called "mono-sheet method" in which a photosensitive material and an image-receiving material are formed on the same support.
In this method, the photosensitive material and the image-receiving material are formed on separate supports, and when used, the two materials are overlapped and pressed together with a roller to perform diffusion transfer, and then peeled off.
The present invention is applicable to both of these methods.

The treatment liquid for silver complex diffusion transfer in the present invention can have a composition of a usual silver complex diffusion transfer treatment liquid. That is, a developing agent for developing exposed silver halide, such as hydroquinone and its derivatives, 1-phenyl-3
- Pyrazolidones and their derivatives, etc., solvents for undeveloped silver halide, such as sttrium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc., sodium sulfite as a preservative, potassium bromide as a development inhibitor, It may contain additives such as 1-phenyl-5-mercapto-tetrazole as a color toner.

As the support for the photosensitive material and image-receiving material for silver complex diffusion transfer according to the present invention, plastic films such as polystyrene, polycarbonate film, cellulose triacetate, and polyethylene terephthalate, polyethylene laminate paper coated with polyethylene, baryta paper, etc. are used. be done.

The present invention will be explained in detail by way of examples below.

Example 1 For an image-receiving material, the following coating solution was prepared, and the coating solution was coated on 9011/d polyethylene laminate paper, which had been previously treated with corona discharge, to a gelatin concentration of 29/d, and dried. The obtained sample was conditioned at 70% RH for 24 hours and then heated at 40° C. for 7 days.

Gelatin A is lime-treated gelatin with a calcium concentration of 4,100 PPM, and this gelatin A is desalted to have a calcium concentration of 1,800 PPM (Gelatin B).
, 740ppix (gelatin O), and 270ppm (gelatin D) were prepared, and an image-receiving material was produced in the same manner except that gelatin A was used in place of the above-mentioned gelatin A. The photosensitive material was placed on polyethylene laminated paper/for prevention of invasion. An undercoat layer containing carbon black is provided, and a 0.3μ
Ortho-sensitized silver chlorobromide (silver bromide 5 mol %) with an average particle size of 1.511/lrl in terms of silver nitrate, and 0.217 m' of 1-phenyl-3-pyrazolidone and 0.2 m' of 1-phenyl-3-pyrazolidone were added. It was manufactured by providing a gelatin silver halide emulsion layer containing hydroquinone of 711/rl and gelatin of 41/d.

The silver halide emulsion layer is
The material is hardened by adding a hardening agent to it.

The processing solution for diffusion transfer was manufactured as described above using the following composition. 7'C A manuscript with moderately dark areas was given appropriate exposure using a plate-making camera, and the emulsion surface of the light-sensitive material and image-receiving material were The image-receiving surfaces of the materials were placed one on top of the other, and the materials were passed through a processor having a squeeze roller containing the above-mentioned diffusion transfer treatment liquid, and after 30 seconds after exiting the squeeze roller, both materials were peeled off.

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.

Example 2 Except for applying the coating liquid for the image-receiving material of Example 1 to the polyethylene terephthalate film, all the treatments were carried out using an image-receiving material prepared in the same manner.The results measured with a Macbeth TD504 transmittance meter are shown below. .

From the results of Examples 1 and 2, it was found that both the reflection density and the transmission density were improved without reducing the calcium concentration;
．． It can be seen that it is remarkable when it becomes less than OOOPPM.

Example 3 The following image-receiving layer coating solution was applied to the supports of Examples 1 and 2.

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Claims (1)

[Claims] (1) An image-receiving material characterized by containing gelatin having a calcium concentration of about LOOOPPM or less.