JPH01282551A - Reducing solution and reduction processing method of silver image - Google Patents

Abstract

PURPOSE:To obtain the reducing soln. having a good reducing property, i.e., large reducing range by incorporating a 1, 3-diamino propane tetraacetic ferric chelate compd. into the reducing soln. CONSTITUTION:The 1, 3-diamino propane tetraacetic ferric chelate compd. is incorporated into the image reducing soln. of a silver halide photosensitive material. While the content thereof varies with the kinds of the photosensitive materials to be used, the density of the silver images, etc., about 5-50g/l is preferred. Preservatives such as complexing agent, pH buffer and sulfite are used at need. A surface active agent and thickener are otherwise incorporated therein. This reducing soln. is effective in a 4-8 pH range. The effect of widening the reducing range is exhibited by using such reducing soln.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention corrects a silver image consisting of halftone dots and/or line drawings obtained by developing a silver halide photosensitive material, particularly a plate-making photosensitive material, after exposure. This relates to a force reduction treatment method. More specifically, it does not cause environmental pollution, has excellent storage stability,
The present invention also relates to a reducing solution that does not cause yellow staining of photosensitive materials after being processed.

(Prior Art) There are many documents and patents regarding the reduction of silver images, halftone dots or linear silver images formed on photosensitive materials for plate making.
Various types of reducing fluids have been used in the past.

In the past, Mr. Farmer's reducing solution, which mainly contains red blood salt, was common, but due to pollution issues, it has recently been replaced with cerium sulfate salt reducing solution and ferric ethylenediaminetetraacetic acid chelate reducing solution. liquid has come into use.

So-called lithium film has been mainly used as a photosensitive material for plate making, but recently new high-contrast photosensitive materials containing hydrazine compounds and tetrazolium compounds have been used, and the characteristics of the reducing liquid required have also changed. Things have changed.

Mr. Farmer's power reducing liquid is neutral and has good power reducing properties, but it has the drawbacks of pollution problems and poor liquid storage stability.

The cerium sulfate salt reducing solution has good storage stability and relatively good reducing suitability, but it is strongly acidic and difficult to handle, and it also has the disadvantage that it tends to leave yellow stains in non-image areas.

Ethylenediaminetetraacetic acid ferric chelate reducing solution is neutral and inexpensive, but its reducing properties are poor. In addition, in new high-contrast light-sensitive materials containing a large amount of silver iodide, a yellowish brown residue is produced at the periphery of the silver image, reducing the effective reduction width. There are drawbacks such as yellow stains remaining on the image area after power reduction.

Good suitability for reducing force means that the reduction in area of the silver image is large relative to the decrease in the density of the silver image, that is, the width of reducing force is large.

By the way, in JP-A-KOKAI No. 3370/3370, a reducing liquid using aminopolycarboxylic acid ferric chelate as an oxidizing agent is described, but none of the aminopolycarboxylic acids specifically described therein are However, the above problems could not be solved.

(Problems to be Solved by the Invention) Therefore, the first object of the invention is to provide a reducing fluid and a reducing force treatment method using the same that do not have these drawbacks. The second object is to provide a reducing liquid that is particularly suitable for the above-mentioned new high-contrast photosensitive materials.

(Means for Solving Problem 0!) After investigating a number of oxidizing agents, we found that the objective could be achieved using a reducing solution containing ferric chelate of 1,3-diaminopropanetetraacetic acid. .

The compounds of the present invention may be ammonium salts or alkali metal salts.

The amount of the compound of the present invention to be used varies depending on the desired reduction width, the type of photosensitive material used, the density of the silver image, etc.
/ to the solubility limit, preferably! From gr//! O
It is gr//.

The reducing solution of the present invention is basically an aqueous solution of the ferric 1,3-diaminopropanetetraacetic acid chelate, but if necessary, other additives such as complexing agents, pH buffers, sulfites, etc. Preservatives, halides, etc. may be added. As the complexing agent used in the reducing solution, well-known silver halide solvents such as sodium thiosulfate, ammonium thiosulfate, ammonium thiocyanate, thiourea, halides, and thioethers can be used.

The reducing liquid may contain a surfactant or a thickening agent, if necessary.

In the present invention, silver images are reduced in force by being immersed in a reducer. Reduction can also be achieved by contacting the silver image with a sheet impregnated in a hydrophilic binder such as the silver image and coated on the support.

In the present invention, prior to the force reduction treatment, sodium sulfate,
The effect can be further enhanced by pretreatment with a solution containing ammonium thiosulfate, sodium sulfite, sodium thiosulfate, or the like.

Also, mercapto compounds such as those described in %Kaishojλ-61≠/R, and Komerkabutol.

J,! -) lyazole, λ-(kodimethelamineethyl)thio! -Mercaptothiadiazole can also be used in combination.

The reducing fluid of the present invention exhibits its effectiveness in the range of pi (r).

There is no particular restriction on the halogen composition of the silver halide photosensitive material to which the image reduction method of the present invention is applied. silver chlorobromide, silver chloride,
Silver iodobromide, silver iodobromochloride, or a mixture of two or more of these may be used, but a halogen composition containing silver iodide (preferably 0.0 to ! mol%, % to O01 mol%) The effect is particularly remarkable in the case of silver halide containing up to 3 mol of silver iodide.

The iron halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), A/7t4! J (December 1971), -2~
Page 23, “1. Emulsion pre
The method described in Haruka/17/l, (November 2007), page tttr, can be followed. US Patent No. ≠, Ko 3
Da, No. 226, No. 1. ≠32゜20 and Research Disclosure
Tabular grains such as those described in 2007 can also be used in the present invention.

Various photographic additives that can be used in the present invention include, for example, the aforementioned Research Disclosure A/72≠3, 13-
It is described on page 2r and Otsu 4tr-66/ of &/17/l. The types of these additives and their detailed description are shown below: Additive type RD/7611
3 I'LD/f7/4 chemical sensitizer 23
Page Sharpness Page Right Column Sensitivity Increaser
Spectral sensitizer as above, pages 23-2+', 6 hiro
Page right column ~ Super sensitizer A44
Negative right column whitening agent 24L tea kabushi prevention agent 2≠〜2! Page t≠ Negative right column and stabilizer light absorber, 7 21-Color page, right column ~ Ilter dye 610 left column UV absorber stain inhibitor λ, negative right column 6jO @ left ~ right column Hardener Page 2 Pages 1 and 11 Left column binder Page 26 Same as above Plasticizer, lubricant 27 Is, o Right column Coating aid, Table
26 to λ7 Negative Same as above Surface activator Static preventive Core negative Same as above Stop agent There is no particular restriction on the silver halide photosensitive material to which the force reduction method of the present invention can be applied, but it is preferably applied to photosensitive materials for plate making.

The force reduction method of the present invention can also be applied to photosensitive materials processed with a squirrel developer. The liquid (8) basically consists of ortho- or para-hydroxybenzene, an alkaline agent, a small amount of free sulfite, sulfite ion salts, etc. Practical examples of ortho- or para-hydroxybenzene as a developing agent include hydroquinone.

The force reduction method of the present invention can be effectively applied to ultra-high contrast sensitive materials containing hydrazine derivatives. Regarding such photosensitive materials, please refer to JP-A-Sho! 3-/142.1, same! 3-20? , No. 22, same! 3-Otsu No. 6732, U.S. Patent No. G, λ2≠, ii-.

No. 1, No. 'I, /1. lr, ri No. 77, same No. ≠, /6
A, No. 74'J, No. 41, 3/1, 71/, No. 'I, 272. tO4 issue, same issue '! ,2/1,1!
It is described in detail in the specifications of No. 7, Hiroshi No. 24'J, No. 7J, etc.

Also, Tokukai Showa f2-/13/7 issue, same! ! It is also effective for high-contrast sensitive materials containing tetrazolium salts described in No. 411p21 and No.j3-2j6-ta.

These new high-contrast photosensitive materials have the advantage of being able to obtain hard sea bream photographic characteristics with a developer that is even more stable than Lith's developer. The developer used here uses a dihydroxybenzene-based developing agent as the main developing agent, and a p-aminophenol-based or /-phenyl-3-pyrazolysine-based developing agent is used as an auxiliary developer. May be contained in the photosensitive material.Preservatives include sodium sulfite,
Potassium sulfite, sodium bisulfite, formaldehyde sodium bisulfite, etc.

The pn value of the developer is 10. It is set in the range of j-/2.3. For alkaline agents, ordinary water-soluble inorganic alkali metal salts (
For example, sodium hydroxide, potassium carbonate, tribasic potassium phosphate, etc.) can be used. U.S. Patent No. V, 26
Alternatively, alcatulamine described in the specification of Takota may also be used.

Generally, the developer contains a pH buffer such as boric acid,
Development inhibitors such as potassium bromide and potassium iodide, organic solvents such as triethylene glycol and ethanol, antifoggants such as penztriazole compounds such as j-methylbenztriazole, and indazole compounds such as j-nitroindazole. Alternatively, it may contain a black spot preventive agent, and may further contain a color toning agent, a surfactant, a water softener, etc. depending on the membership fee.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixer contains a water-soluble aluminum salt, such as aluminum sulfate, as a hardening agent.
It may also include light bread, etc. Here, the amount of water-soluble aluminum salt is usually O~3.01! kl/l. In addition, as an oxidizing agent, ethylenecyabanetetraacetic acid Fe (Ill
) Complex salts may also be used.

The processing temperature is usually selected between /r'c and jOoC, but it may also be lower than /Ir0C or above 100c.

The present invention will be explained in more detail with reference to Examples below.

Example 14 1 mole of silver in an aqueous solution kept at to'c≠X1
In the presence of 0 moles of potassium iridium chloride and ammonia, an aqueous solution of silver nitrate, potassium iodide, and potassium bromide were simultaneously added over 60 minutes, during which the pAg was reduced to 7.
．． By keeping it at 1, the average particle size O, tμ,
A cubic monodisperse emulsion with an average silver iodide content of 0.3 mol.
I did it. This emulsion was desalted by the 70 curation method, and then inert gelatin of uOgr per mole of silver was added and kept at 0c to serve as a sensitizing dye! .

! -Cyclorotorethyl-3,3-bis-(3-sulfoprobyl)oxacarbocyanine and a 1 mol silver to 10 mol KI bath solution were added, and the mixture was allowed to stand for lj minutes, and then the temperature was lowered. This emulsion was redissolved and 0.0.2 mol of methylhydroquinone per mol of silver and 1 mol of the following sensitizing dye (1) and hydrazine derivative (2) were added at 4°C.
．． x 10 mol/Ag mol, and the following additives (a
), Z-methylbe.

ndstriazole, ≠-Hydroxy-1, J, Ja.

7-Chitrazaindene, the following accelerator (≠), (-1)
A dispersion of polyethyl acrylate and a hardening agent were added thereto, and the mixture was coated on a polyethylene terephthalate film.

To the film thus obtained/! After exposure through a sensitometric wedge using a 0-line contact screen, the film was developed with a developer having the following composition for 3≠00.30 seconds, fixed, washed with water, and dried.

Elephant liquid ethylenediamine/tetraacetic acid tetrasodium salt 7g Sodium hydroxide lIrgIr potassium ! jg! -Sulfo-ruchilic acid Boric acid
15g potassium sulfite /
10gn-methyldiethanolamine l! gN-
Methyl-p-aminephenol//λ sulfate 0,1 g Hydroquino:/ 3 j g! −
Methylbenztriazole o, rg Sodium bromide 3 Add water
/L (pH/1,z) fixer is GRF-/(
(manufactured by Fuji Film Co., Ltd.) was used.

The obtained halftone silver image (area ratio jO%) was subjected to a reduction treatment using the following reduction liquid.

Silver image before reduction processing @ degree (4/L, AO or higher) - degree Ko,! The rate at which the halftone dot area decreased until it reached 0, i.e., the change from pto%, was determined, and the residue was examined to obtain the results shown in Part 1.

"As is clear from Table 7, the force reduction liquid according to the present invention has a significantly wide range of force reduction and is free from residue.

Example.

10 mole silver chloride, /ri,! Morch's silver bromide and 0. j
A silver halide emulsion consisting of Morch's silver iodide was gold-sensitized and iodine-sensitized, and a spectral sensitizer (1), development accelerator (2), hardener (3), and latex were added in sequence. after,
Coated on polyethylene terephthalate.

(1) 3-carboxymethyl-5-(z-(J-ethyltheazolinidene) eteldene) rhodanine (2) yt?lJ oxyethylene nonylphenyl ether (ethylene oxide group 10) (3) Mucochloric acid After exposing the material through a magenta contact screen, it was developed with H8-1 (manufactured by Fuji Photo Film Co., Ltd.) at 32°C% for 1 minute, and then reduced with the following reducing solution. It is shown in Table 2.

Table 2 shows that the force reduction liquid of the present invention is excellent in both force reduction width and residue.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (2)

[Claims] (1) A reduction liquid characterized by containing a ferric chelate compound of 1,3-diaminopropanetetraacetic acid. (2) A silver image formed by exposing and developing a silver halide photosensitive material and subjecting it to a reduction treatment in the presence of a ferric chelate compound of 1,3-diaminopropanetetraacetic acid. Power reduction treatment method.