JPS62222250A - Silver complex diffusion transfer process - Google Patents

Abstract

PURPOSE:To improve reproduction of continuous tone picture image by obtg. a photosensitive material for silver complex diffusion transfer process by coating a silver halide emulsion layer and an overcoat layer successively on a base body, and incorporating a specified amt. of hydrophilic colloid and silver halide therein. CONSTITUTION:A photosensitive material for silver complex diffusion transfer process is prepd. by the process described hereunder. In the first stage, a silver halide emulsion layer contg. silver chloride, silver bromide, or silver iodide, etc., and an overcoat layer are coated successively on a base body. At most 6g/m<2> hydrophilic colloid such as gelatin, etc., is incorporated into the layer comprising the silver halide emulsion layer and the overcoat layer. The content of the hydrophilic colloid in the silver halide emulsion layer is at most 5g/m<2>, and the content of silver halide expressed in terms of AgNO3 is at most 1.4g/m<2>. o-Dihydroxybenzene compd., 3-pyrazolidone compd., and p-dihydroxybenzene compd. are added to the photosensitive material. Since the amt. of the hydrophilic colloid and silver salt are reduced, running property of the photosensitive material is improved and the material is made more suitable for reproduction.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a silver complex diffusion transfer method for reproducing continuous tone image remains.

(B) Prior art and its problems The principle of silver complex diffusion transfer method (hereinafter referred to as DTR method) is as follows:
It is described in US Pat. No. 2,352,014 and is well known.

In the DTR method, an imagewise exposed silver halide emulsion layer is brought into contact with an image-receiving layer in the presence of a developing agent and a silver halide complexing agent. In the exposed parts of the silver halide emulsion layer, the silver halide is developed to silver (chemical development) and therefore it cannot be dissolved or diffused any further. In the unexposed areas, the silver halides are converted to soluble silver complexes, which are transferred to the image-receiving layer, where they form a silver image, usually in the presence of physical development nuclei.

The advantage of the DTR method is that by superimposing the light-sensitive material for diffusion transfer and the image receiving material in a DTR processing solution using a simple processor, ultra-high contrast and halftone dot reproducibility comparable to commercially available Lith film can be obtained. Moreover, it is easier to manage the processing liquid than the Squirrel system.

The DTR method is used for reproducing documents, creating block copies in the field of plate making, and the like. In the DTR method used in this field, DTR materials are designed to increase the contrast, resolution and sharpness obtained on the image-receiving layer, and such materials are required to reproduce continuous tone images. Not suitable.

In order to reproduce a continuous tone image, it must be designed to obtain soft tone photographic characteristics.
The methods described in Japanese Patent Application Laid-open No. 99436 and Japanese Patent Application Laid-open No. 57-33775 have been proposed. Unexamined Japanese Patent Publication 1973
99436, the weight ratio of hydrophilic colloid to silver halide is about 3:1 to about 10:1, and 'O-dihydroxybenzene compound and 3-
On the other hand, in JP-A-57-33775, it is disclosed that [the weight ratio of hydrophilic colloid to silver halide is 3.5:1 to 7.8:1]. and specifying that the halogen composition of the silver halide emulsion should contain 90 mol% or more of chloride.'' however,
Even with this method, for the purpose of reproducing continuous tone images,
It wasn't enough.

Further, a drawback of such a method is poor running performance. That is, when processing with a diffusion transfer processing liquid and allowing time to pass, as the number of days elapses increases, a decrease in pH is observed, and therefore, images obtained by diffusion transfer processing become defective.

The weight ratio of hydrophilic colloid to silver halide is described in JP-A-54-99436 and JP-A-57-33775.
It was revealed that when the process was carried out as described in the specification, the amount of hydrophilic colloid increased, and under this condition, the above-mentioned running properties were significantly reduced.

(C) Object of the Invention An object of the invention is to provide a silver complex diffusion transfer method for reproducing continuous tone images with improved running properties.

The object of the present invention will become clear from the following description of the specification.

(D) Structure of the Invention In order to improve the running performance of the silver complex diffusion transfer method for reproducing continuous tone images, the present inventors have conducted various studies and have developed a photosensitive material for silver complex diffusion transfer. We have discovered that running performance can be greatly improved by designing the configuration as shown below.

That is, a. The light-sensitive material for silver complex diffusion transfer is one in which a silver halide emulsion layer and an overlayer are sequentially coated on a support, and b. The silver halide emulsion layer and the overlayer consist of a total of Containing at most 6 g/m of hydrophilic colloid, c, the silver halide emulsion layer is at most 59/m of hydrophilic colloid and silver nitrate, at most 1.4! The method is to use a photosensitive material for silver complex diffusion transfer containing silver halide of J/m.

The light-sensitive material for silver complex diffusion transfer according to the present invention is one in which a silver halide emulsion layer and an overlayer are sequentially coated on a support. Specific examples of the support include paper supports such as baryta paper and polyethylene laminated paper, and film supports such as polyethylene terephthalate.

The hydrophilic colloid content in the silver halide emulsion layer and the overlayer of the light-sensitive material for silver complex diffusion transfer according to the present invention is at most 6j/m. When it exceeds 69/m, running performance deteriorates.

In the present invention, the amount of hydrophilic colloid in the silver halide emulsion layer is at most 5 g/m. When the amount exceeds 5 g/hip, running performance deteriorates.

In the present invention, the amount of silver in the silver halide emulsion layer is at most 1.49/min in terms of silver nitrate.

If it is more than 149/m in terms of silver nitrate, the contrast will be too high and it will not be suitable for reproduction of continuous tone images.

In the present invention, in the photosensitive material for silver complex diffusion transfer, O
It is preferable to contain a -dihydroxybenzene compound and a 3-pyrazolidone compound.

Specific examples of the O-dihydroxybenzene compound used in the present invention include catechol and methylcatechol. In the present invention, 0.2C is added to the silver halide emulsion layer.
It is preferable to use J/m or more, and if it is less than 0.29/m, it is not suitable for continuous tone image reproduction.

Specific examples of the 3-pyrazolidone compound used in the present invention include 1-phenyl-3-pyrazolidone (Phenidone), 1-phenyl-4-methyl-3-pyrazolidone (Phenidone Z), 1-phenyl-4,4- dimethyl-3-
These include pyrazolidone (Dimezone), 1-phenyl-4-methylol-3-pyrazolidone (Dimezone S), etc.It is also possible to use these 3-pyrazolidone compounds in combination, but these 3-pyrazolidone compounds It is preferably used in an amount equal to or less than the molar amount of the compound.

In the present invention, it is preferable to use a p-dihydroxybenzene compound in addition to the above two compounds. Specific examples of p-dihydroxybenzene compounds include hydroquinone, methylhydroquinone, and chlorohydroquinone. In the present invention, the amount of the p-dihydroxybenzene compound added is preferably at most 10% in molar ratio relative to the O-dihydroxybenzene compound.

Hydrophilic colloids that are advantageously used for preparing light-sensitive emulsions include lime-treated gelatin, acid-treated gelatin, and gelatin derivatives (for example, Japanese Patent Publication No. 38-48-54, 1973).
-5514, 1972-12237@, 1972-2
63458, U.S. Pat. No. 2,525.753, U.S. Pat.
．． 594.293, 2.614,928, 2,763,639, 3.118,766, 3.132,945, 3.186,846,
No. 3,312,553, British Patent No. 861,414
No. 1,033,189), proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, poly-N - Synthetic hydrophilic binders such as vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof, and partial hydrolysates, etc., and these hydrophilic colloids can be used alone or in combination. .

In addition, these hydrophilic colloids can be used in antihalation layers,
It is also advantageously used to create non-photosensitive layers such as overlayers, backing layers or image-receiving layers.

The hydrophilic colloid in the silver halide emulsion layer is used in a weight ratio of 1 to 6 based on silver halide converted to silver nitrate.

The silver halide may be any one such as silver chloride, silver bromide, silver chlorobromide, or a combination thereof with silver iodide.

The present invention is not limited to ``specifying that the chloride content in the halogen composition of the silver halide emulsion is 90 mol % or more'' as described in JP-A-57-33775.

Rather, it contains more than 10 mol% bromide and 90% chloride.
When the amount is less than mol%, softer photographic characteristics can be obtained.

Silver halide emulsions can also be spectrally sensitized in blue, green, and red. It can be 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, gelatin containing labile sulfur, etc.), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts, iridium salt, rutinium salt, etc.), U.S. Patent No. 2,51
Polyalkylene polyamine compounds described in German Patent No. 8.698, imino-amino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (for example, stannous chloride, etc.), etc. are advantageously used. .

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

The silver halide emulsion layer of the present invention can improve image reproducibility when combined with an antihalation layer containing a black pigment.

Further, when the silver halide emulsion layer of the present invention is combined with an antihalation layer containing a white pigment, image reproducibility can be improved.

Furthermore, image reproducibility can also be improved when combined with an antihalation layer containing the above-mentioned black pigment and white pigment.

However, the amount of hydrophilic colloid in the antihalation layer needs to be set to 1'i/rrI or less, which is preferable for improving running properties. Also,
When combined with the silver halide emulsion layer and overlayer of the present invention, the amount of hydrophilic colloid in these three layers is 6 g/
It is preferable that the Tr is below 1g.

In the present invention, it is preferable to use a water-soluble halide. Specific examples of water-soluble halides include chlorides such as sodium chloride and chloride, and bromides such as sodium bromide and potassium bromide.

Various additives may be contained in the constituent elements of the diffusion transfer material according to the present invention.

For example, mercapto compounds, antifoggants or stabilizers such as tetraazaindene, saponins as surfactants, sodium alkylbenzene sulfone, sulfosuccinic acid ester salts, and alkylaryl sulfonates as described in U.S. Pat. No. 2,600,831. In addition, waxes, polyol compounds, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, N-guanyl hydrazone compounds, etc. , quaternary onium compounds, mordants such as tertiary amine compounds, diacetyl cellulose, styrene-fluoroalkylene sodium maleate copolymers, reaction products of styrene maleic anhydride copolymers and p-aminobenzenesulfonic 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, antioxidants, such as those specified by Special Publication No. 36-21574@
A developing agent, l) H adjuster, etc. can be used.

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 an alkaline substance such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., a silver halide solvent such as sodium thiosulfate, ammonium thiothianate, a cyclic imide compound, Preservatives such as thiosalicylic acid, such as sodium sulfite, thickening agents such as hydroxyethylcellulose, carboxymethylcellulose, antifoggants such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., developer modifiers such as polyester, etc. Oxyalkylene compounds, onium compounds, developing agents such as hydroquinone, catechol, 1-phenyl-3-pyrazolidone, alkanolamines, etc. can be included.

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 developing agent is included in the DTP material, i.e. in the silver halide emulsion layer and/or in the hydrophilic colloid layer in water-permeable relationship therewith. The method can largely avoid that drawback.

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, 1977-30856, 1977-43778
You can refer to the specifications of .

In the present invention, the mechanism of action of the silver complex salt on the running properties of the light-sensitive material for diffusion transfer is estimated as follows. That is,
In the silver complex diffusion transfer method for reproducing continuous tone images, Q-dihydroxybenzene compounds and 3-pyrazolidone compounds are often used as developing agents. In the silver complex diffusion transfer method used for document reproduction and block preparation,
A p-dihydroxybenzene compound and a 3-pyrazolidone compound are used, and these exhibit superadditivity and tend to produce high contrast. On the other hand, an O-dihydroxybenzene compound and
The 3-pyrazolidone compound does not show superadditivity, has a soft tone, and seems to have poor developability. In addition, materials for silver complex diffusion transfer for the reproduction of continuous tone images (conventionally, materials for high contrast images have been developed by increasing the amount of hydrophilic colloid and lengthening the diffusion distance of the silver complex produced by the dissolution of silver halide). By controlling the diffusion rate of the silver complex into the image-receiving material, soft contrast has been imparted to the image-receiving material.However, the increase in the amount of hydrophilic colloid is due to
resulting in an increased neutralization reaction with the buffer, resulting in
This causes a decrease in p] in the film during diffusion transfer processing, resulting in a decrease in developability. In the present invention, the neutralization reaction with the 4-alkaline buffer is suppressed by reducing the amount of hydrophilic colloid, thereby preventing a decrease in the pH within the film, preventing a decrease in developability, and improving running properties. . However, this results in an increase in the diffusion rate of the silver complex, making it difficult to reproduce continuous tone images. In order to overcome this difficulty, in the present invention, an overlayer is used to lengthen the diffusion distance, and at the same time, it is possible to not only control the diffusion rate of the silver complex, but also to soften the tone by reducing the amount of silver complex. This is what we are trying to do.

The present invention will be explained below using examples.

(E) Examples Example 1 A breast milk preparation was prepared based on the following prescription.

While keeping the A solution at 50'C and stirring, add the B solution over 2 minutes, ripen for 20 minutes, and reduce the DH by 3.5 degrees with sulfuric acid.
4, added Na2SO4, precipitated, and washed with water.

Next, gelatin was added and redissolved in this breast milk, and sulfur sensitization and gold sensitization were performed using sodium thiosulfate and potassium chloroaurate. The emulsion thus prepared was ortho-sensitized by adding a sensitizing dye, divided into portions at pH=4.5, gelatin was added to give the gelatin coverage as shown in Table 1, and catechol was added at 0°6 cJ/ TIt11-phenyl-
4,4-dimethyl-3-pyrazolidone 0.2 q/
m, add a hardening agent and a surfactant,
I put on make-up.

The emulsion thus prepared was coated so that the coating amount was 5 silver and the amount of gelatin coated was as shown in Table 1. Next, gelatin 1V
For comparison, the overlayer was applied so that the amount of catechol 0.27/Trt, 1-)12-4,4-dimethyl-3-pyrazolidone was 0.08 g/m. Examples (B) and (C) Two types of silver halide emulsion single layer systems were prepared. At this time, catechol was 0.8y/buttocks was 1
-Phenyl-4,4'-dimethyl-3-pyrazolidone 0
．． A sample was prepared to contain 2EEJ/m.

Two of the following compositions were applied onto a polyethylene-coated paper support.
It was coated with a coating amount of 0m/butt and used as a monthly fee.

Next, these samples were exposed in the same way to form the image receiving material (
They were passed through Mitsubishi Paper Mills' One Step Activator ACII (processing solution) together with the receiver), overlapped, and peeled off one minute in diameter. The treatment temperature was 23°C. The product thus obtained was sensimetered and the results are shown in Table 1.

In the table, S represents the relative sensitivity, and L represents the logarithm of the relative exposure amount of the minimum density Dmin plus 0.05 and 90% of the maximum density.
Dmax represents the maximum density.

(The following is a blank space) As is clear from Table 1, Samples 1 to 3, which are embodiments of the present invention, and Comparative Example C showed favorable characteristics for continuous tone image reproduction, but Comparative Examples A and B Both had continuous tone reproduction performance, but OmaX was low and the resulting images were poor.

Next, after treating 100 sets of Mitsubishi One Step 03-NE and 08-IP using the aforementioned treatment liquid ACII,
When the running properties of Samples 1 to 3 and A to C were examined after being left for 2 days, Samples 1 to 3 had good characteristics for continuous tone reproduction, whereas Samples A to C is omax
was 1.0 or less, and a poor result was obtained.

As is clear from the above, the silver salt diffusion transfer method for reproducing continuous tone images of the present invention has been found to have excellent running properties.

Example 2 A silver nitrate aqueous solution containing 1 mol of silver nitrate was stirred into an aqueous gelatin solution containing 42.59 mol of inert gelatin, 1.2 mol of sodium chloride, 0.25 mol of potassium bromide, and 0.04 mol of potassium iodide. , added over 3 minutes, 50
The mixture was aged for 30 minutes at 'C' and an emulsion was prepared in the same manner as in Example 1.

At this time, gelatin was added so that the gelatin coating amount was as shown in Table 2, and sodium chloride Q, 'l 5 mole/mole
leAg, catechol 0.6 q/but, 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.15 g/m
, hydroquinone was processed so that it became 0.02 CJ/Td.

The emulsions thus prepared were coated so that the amounts of coated silver and gelatin coated were as shown in Table 2. Next, gelatin 1.
3g/TIl, catechol 0.29/m, 1-phenyl-4-methyl-4-methylol-3-pyrazolidone O,
An over layer was applied to give a coating thickness of 15 y/m.

Thereafter, it was treated and sensitometry was performed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

(Left below) As is clear from Table 2, as the amount of silver increases, the contrast becomes sharper, and Samples 4 to 6, which are actual IM embodiments of the present invention, showed favorable characteristics for continuous tone image reproduction. For example, the contrast was too high, and the reproduction of the details of the continuous tone original was extremely poor.

Next, running properties were examined in the same manner as in Example 1, and all were found to be good.

As is clear from the above, the actual M aspect of the present invention has excellent running properties and is suitable for reproducing continuous tone images.

Claims (3)

[Claims] (1) A light-sensitive material for silver complex diffusion transfer containing a silver halide emulsion layer is exposed to a continuous tone original image, passed through a processing solution for silver complex diffusion transfer together with the image receiving material, overlapped, and diffuse transferred. In the silver complex diffusion transfer method for reproducing images, a. the light-sensitive material for silver complex diffusion transfer has a silver halide emulsion layer and an overlayer sequentially coated on a support; b. the silver halide The emulsion layer and the overlayer contain in total at most 6 g/m^2 of hydrophilic colloid; c. the silver halide emulsion layer contains at most 5 g/m^2 of hydrophilic colloid and silver nitrate; Converting to 1.4g/m at most
A silver complex diffusion transfer method for reproducing continuous tone images, characterized in that a photosensitive material for silver complex diffusion transfer containing silver halide of ^2 is used. (2) The silver complex diffusion transfer method according to claim 1, wherein the light-sensitive material for silver complex diffusion transfer contains an 0-dihydroxybenzene compound and a 3-pyrazolidone compound. (3) In addition to the 0-dihydroxybenzene compound and the 3-pyrazolidone compound in the silver complex salt diffusion transfer photosensitive material, p- The silver complex diffusion transfer method according to claim 1, characterized in that a dihydroxybenzene compound is also added.