JPS622307B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver complex diffusion transfer material that combines a photosensitive 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 in the processing solution. It reacts with the silver halide 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 silver diffusion transfer method, which is based on this principle, is widely used for copying documents, such as copies of printed materials, handwritten documents, and blueprints, as well as for printing materials used in platemaking, and is used to create copies that are faithful to the original manuscript. Image reproduction is required. Silver image density (reflection and transmission density) is an important quality of the image receiving material used in the silver complex diffusion transfer method.
It is important that the color tone is high and the color tone is good (blue-black tone is generally desired), and that the image-receiving layer has sufficient film strength (the image-receiving layer is resistant to scratches when it contains processing liquid and water). It is. Usually, the image-receiving layer contains gelatin, phthalated gelatin, acylated gelatin, phenylcarbamylated gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl alcohol and maleic anhydride as binders. Acid copolymers (e.g. styrene-
maleic anhydride, ethylene-maleic anhydride, etc.)
heated processed products, polyacrylamide, poly-N
-A water-soluble polymer compound such as vinylpyrrolidone is used, and a hardening agent is added to obtain sufficient film strength. Generally, there is a contradictory relationship between the film strength of the image-receiving layer and the silver image density, and the stronger the film strength using a hardening agent, the more difficult it becomes for the image-receiving layer to absorb processing liquid, which hinders the progress of physical development. As a result, the silver image density tends to decrease. However, the decrease in silver image density is not necessarily caused only by film strength, and the hardening agent itself may have an adverse effect on physical development. Typical hardening agents for water-soluble polymer compounds that have been conventionally used include aldehydes, active vinyl compounds, carbodiimide compounds, and methylol compounds. However, it significantly reduces silver image density. Therefore, it has been desired to develop a hardening agent for use in the image-receiving layer of an image-receiving material that provides sufficient film strength and reduces the reduction in silver image density. An object of the present invention is to provide an image-receiving material having sufficient film strength and high silver image density in a silver complex diffusion transfer method in which a photosensitive material and an image-receiving material are combined. While investigating various hardening agents, the present inventor found that by using a modified polyamide-formaldehyde resin as a hardening agent for an image-receiving layer that uses a water-soluble polymer compound as a binder, it was possible to obtain sufficient film strength and It has been found that an image-receiving material with high silver image density can be obtained. The modified polyamide-formaldehyde resin of the present invention is a formalin-modified condensation resin based on high molecular weight polyamide, and is manufactured by Deik Hercules Co., Ltd. under the trade name "EPINOXP-".
9007Y". Modified polyamide-formaldehyde resins are described in Paper and Pulp Technology Times, Vol. 13, No. 2. One method for synthesizing the modified polyamide-formaldehyde resin of the present invention is to condense a dibasic carboxylic acid (e.g. adipic acid) and an amine (e.g. ethylenediamine) by heating to form a polyamide, and then -NH -There is a method of reacting the part with urea to remove ammonia, and then reacting with formalin. This modified polyamide-formaldehyde resin is easily dissolved in water. The amount of the modified polyamide-formaldehyde resin of the present invention to be used is 0.1 to 20% based on the solid content of the water-soluble polymer compound that is the binder of the image-receiving layer. The amount used may be adjusted appropriately depending on the type and amount of the compound, and is usually used in the range of 0.5 to 5%. Methods for incorporating the modified polyamide-formaldehyde resin of the present invention into the image-receiving layer include a method in which an aqueous solution of the modified polyamide-formaldehyde resin is added to a coating solution containing a water-soluble polymer compound forming the image-receiving layer, and a method in which the modified polyamide-formaldehyde resin is applied in advance. There are methods such as applying a modified polyamide-formaldehyde resin aqueous solution to the image-receiving layer, but the method is not limited to these methods.
In the former method, the modified polyamide of the present invention
Even when an aqueous formaldehyde resin solution is added to a coating solution, there is no change in pH or increase in viscosity of the coating solution, which is often seen when adding a hardening agent. Furthermore, there is no change in pH or viscosity of the coating solution over time, and the effects of the modified polyamide-formaldehyde resin of the present invention as referred to in the present invention are not impaired at all. There is no particular limit to the pH of the coating solution when it is added, and it can be applied over a wide range.
Can be used in PH range. Also, in our industry,
It is known that a hardening agent and a polyhydric alcohol (e.g., glycerin, ethylene, glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, etc.) are used in combination as a method of increasing the hardening speed. Similarly, polyamide-formalin resin can be used in combination with a polyhydric alcohol to increase the hardening speed. When polyhydric alcohol is used in combination, the amount of modified polyamide-formaldehyde resin used can be reduced. Further, the hardening speed of the modified polyamide-formaldehyde resin of the present invention becomes faster by heat treatment. Therefore, in the actual manufacturing process, it is advantageous for the image-receiving layer containing the modified polyamide-formaldehyde resin of the present invention to be heat-treated after coating and drying, or to have a sufficiently high drying temperature (for example, 100° C. or higher). As the binder for the image receiving layer of the image receiving material for silver complex diffusion transfer according to the present invention, 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-vinyl Water-soluble polymer compounds such as pyrrolidone and latexes (for example, polyacrylic esters, polymethacrylic esters, polystyrene, polybutadiene, etc. alone or in copolymers) can be used alone or in combination. As the physical development nucleus, heavy 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 image-receiving layer contains a surfactant, a matting agent, a fluorescent dye, a discoloration inhibitor, a toning agent (for example, 1-phenyl-5-mercapto-tetrazole), and a developing agent (for example,
Hydroquinone and its derivatives, 1-phenyl-
3-pyrazolidone 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. 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. silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, as long as they have the ability to develop and diffuse in the exposed and non-exposed areas, respectively, at the speed required for the diffusion transfer method. , 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 gelatin, phthalated gelatin,
Acylated gelatin, phenylcarbamylated gelatin, polyvinyl alcohol, partially saponified polyvinyl alcohol, polyacrylamide, polyN-vinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol and anhydrous maleic copolymer (e.g. (styrene-maleic anhydride, ethylene-maleic anhydride, etc.), latexes (e.g., polyacrylic esters, polymethacrylic esters, polystyrene, polybutadiene, etc. alone or copolymers, etc.), etc. I can do it. Further, the photosensitive layer can be hardened using a suitable hardening agent. Typical hardeners include aldehydes, active vinyl compounds, carbodiide compounds, and the like. Furthermore, the photosensitive layer contains additives generally used in silver halide photosensitive materials, such as surfactants, antifoggants, matting agents, fluorescent dyes, hydroquinone and its derivatives, 1-phenyl-3-
It may contain a developing agent such as pyrazolidone and its derivatives. The photosensitive material for silver complex diffusion transfer according to the present invention may be provided with an antihalation layer and a subbing layer for improving adhesion to a support under the photosensitive layer. 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, developing agents for developing exposed silver halide, such as hydroquinone and its derivatives, 1-phenyl-3-pyrazolidone and its derivatives, solvents for undeveloped silver halide, such as sodium thiosulfate, ammonium thiosulfate,
Sodium thiocyanate, potassium thiocyanate, etc.
It may contain additives such as sodium sulfite as a preservative, potassium bromide as a development inhibitor, and 1-phenyl-5-mercapto-tetrazole as a toning agent. As the support for the light-sensitive material for silver complex diffusion transfer and image-receiving material according to the present invention, plastic films such as cellulose triacetate and polyethylene terephthalate, polyethylene laminate paper coated with polyethylene, baryta paper, etc. are used. The support may be subjected to corona discharge treatment to improve adhesion to the photosensitive layer or image-receiving layer. The present invention will be explained in detail below with reference to Examples. In addition, in the Examples, in order to explain the technology of the present invention in detail in comparison with known technology, comparative compounds are selected and studied. Example 1 The image-receiving material was produced using polyvinyl alcohol and ethylene as shown in Japanese Patent Application Publication No. 1986-96946.
A heated product of maleic anhydride copolymer was used as a binder for the image-receiving layer. That is, 800 g of a 10% aqueous solution of polyvinyl alcohol (average degree of polymerization, 1000, degree of saponification 98% or more) and 200 g of a 10% aqueous solution of ethylene/maleic anhydride copolymer (average molecular weight, 100000).
1000g of 5% gelatin aqueous solution was added to the heat-processed product obtained by heat-reacting 100g of gelatin at 80℃ or higher for 3 hours, and 40ml of colloidal cobalt sulfide physical development nuclear solution (5mM/concentration) was added to this as a binder. Add water to 3000g. Next, divide this liquid into 8 equal parts,
A coating solution was prepared by adding the hardener of the present invention, comparative hardener A, and comparative hardener B as shown in Table 1. This coating solution was coated to a thickness of 2 μm on 90 g/m ² polyethylene laminate paper and polyethylene terephthalate film that had been previously treated with corona discharge and dried. The resulting sample was conditioned at 70%RH for 24 hours and then heated at 40°C for 7 days. Comparative hardener A; Formalin Comparative hardener B;

【formula】

[Table] The photosensitive material is a polyethylene laminated paper with an uncoated layer containing carbon black to prevent halation, and on top of that an ortho-sensitized silver chlorobromide (silver bromide 5 mol%) with an average particle size of 0.3μ. ) contains 1.5g/ ^m2 in terms of silver nitrate, and further contains 0.2g/m2.
m ² of 1-phenyl-3-pyrazolidone and 0.7 g/
A light-sensitive material was prepared by providing a gelatin silver halide emulsion layer containing m ² of hydroquinone and 4 g/m ² of gelatin. A diffusion transfer treatment solution having the following composition was used. Water 800ml Potassium hydroxide 1.5g Tertiary sodium phosphate dodecahydrate 60g Anhydrous sodium sulfite 40g Potassium bromide 0.5g Hypo 20g Make 1 with water. The emulsion surface of the photosensitive material produced as described above and the image receiving surface of the image receiving material are superimposed, passed through a processor having a squeeze roller containing the above-mentioned diffusion transfer processing solution, and 30 seconds after exiting from the squeeze roller. After peeling off both materials, the image-receiving material was washed with water for about 10 minutes, and then its hardness was measured, and after drying, its reflection density and transmission density were measured. The degree of hardness was determined by measuring the scratch strength in water at 20°C.
To measure the scratch strength, a load was applied to a stainless steel needle with a tip of about 0.5 mm, and the sample was scratched, and the limit load that caused scratches was determined. Table 2 shows the quality of the image-receiving materials (Samples 1 to 8) produced in Examples.

[Table] As shown in Table 2, comparative hardeners A and B (sample
Nos. 2 to 5) increase the scratch strength, that is, the hardness, but significantly reduce the reflection and transmission density. In comparison, the modified polyamide-formaldehyde resins of the present invention (Samples Nos. 6 to 8) are excellent hardeners that increase scratch strength and cause little reduction in reflection and transmission density.

Claims (1)

[Claims] 1. A silver complex diffusion transfer image-receiving material comprising a modified polyamide-formaldehyde resin, which is an image-receiving material used in a silver complex diffusion transfer method in which a photosensitive material and an image-receiving material are combined.