JPH0273248A - Reducing solution and reduction processing method for silver picture - Google Patents

Abstract

PURPOSE:To improve the reducing aptitude and the preservation stability of the reduction solution, and to reduce the yellow stain of a photosensitive material after processing it by using a prescribed chelating agent and a specified reducing promoter in combination for the subject reducing solution. CONSTITUTION:A ferric chelating compd. of aminopolycarboxylic acid such as 1,3-propane diamine tetraacetic acid and the reducing promoter shown by formula I are incorporated in the reducing solution. In the formula, A<1> and A<2> are each a group shown by formula II or a nitrogen contg. heterocyclic ring residual group, R<1>-R<3> are each hydrogen atom or alkyl (q) is 0 or 1, B<1> is alkylene or arylene, etc., (h) is 0 or 1, Z<1> is an anion, (i) is 0-2. The promoter shown by the formula is composed of a compd. shown by formula III. A silver picture formed by exposing a process silver halide photosensitive material and then developing it, is subjected to reduction processing with the reducing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application J) The present invention relates to a method for modifying 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. It is related to force processing methods.

More specifically, the present invention relates to a reducing solution that has good reducing suitability, excellent storage stability, and does not cause yellow staining of photographic materials after being processed.

(Prior Art) There are many documents and patents regarding the reduction of strength of silver images, especially halftone or linear silver images formed on photosensitive materials for plate making, and various kinds of reduction liquids have been used heretofore.

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 come into use, and the characteristics of the reducing liquid required have also improved. Things have changed.

Mr. Farmer's power reducing fluid is neutral and has good power reducing properties, but it has drawbacks such as 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 drawback of easily leaving yellow stains in non-image areas.

Ethylenediaminetetraacetic acid ferric chelate reducing solution is neutral and inexpensive, but its reducing properties are poor. In new high-contrast light-sensitive materials containing a large amount of silver iodide, a yellow-brown residue is produced at the periphery of the silver image, reducing the effective reduction width.

There are drawbacks such as yellow staining remaining on the image area after power reduction.

Good reduction performance means that the reduction in the area of the silver image is large relative to the reduction in the density of the silver image, that is, the reduction width is large.

By the way, JP-A No. 33701 describes a reducing solution that uses aminopolycarboxylic acid ferric chelate as an oxidizing agent, but all of the aminopolycarboxylic acids described therein are However, it was not possible to solve the above problems alone.

In general, aminopolycarboxylic acid ferric chelate has a weak oxidizing power, so compared to cerium sulfate salt, red blood salt, etc., it has a low oxidation rate (oxidation rate), and it is difficult to make it into a practical reducing solution. Even if these compounds are used to reduce power for a long time, especially when used in combination with the new high-contrast light-sensitive materials mentioned above, the halftone dot density will be greatly reduced, and the image area after the reduction will be yellowed, and the area around the halftone dots will be significantly reduced. There was a problem that yellowish brown residue was likely to remain on the parts.

In addition, JP-A Shoj Co. TRμl No. 1 describes the use of a heterocyclic mercapto compound in a reducing fluid, particularly in combination with ferric ethylenediaminetetraacetic acid chelate, but this combination also has the above-mentioned problems. It was not something that could 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 method that do not have these drawbacks.

The second object is to provide a reducing liquid and a reducing method that are particularly suitable for the new high-contrast photosensitive materials.

(!Means for solving the problem J) As a result of examining many oxidizing agents and accelerators, we found a ferric chelate of aminopolycarboxylic acid and the general formula (
It has been found that the purpose can be achieved by using a reducing liquid containing the compound represented by 1).

Examples of chelating agents used in 8A of the present invention include iminodiacetic acid (IDA), glycol ether tetraacetic acid (GEDTA), /63-propanediaminetetraacetic acid (i
, J-PDTAJ, and ethylenediamine with slightly weak oxidizing power [11(EDTA>, l, cordiaminobro/<
There are ferric iron chelates such as 74 vinegar rR (Me-EDTA), corn chlorohexanediaminetetraacetic acid (Cy-DTA). The former chelate is preferred.

The chelate compound of the present invention may be an ammonium salt or an alkali metal salt.

The machine for using the chelate compound of the present invention has a target force reduction width,
It varies depending on the quality of the photosensitive material used, the density of the silver image, etc., but 0
, 39/l to the solubility limit, preferably from 1i// to 709/l.

In the present invention, one or more types of compounds represented by the following general formula (1) are used as the force reduction promoter used in combination with the chelating agent.

General formula +1) A' (B1)h A2 (represents Z'Ji or a saturated or unsaturated heterocyclic residue containing at least one nitrogen atom. AI and A2 may be the same or different. .RR2 and R3 each represent a hydrogen atom or an alkyl group (including substituted alkyl groups), and R1, R2, and R3 may be the same or different. Examples of the li1 group include a hydroxy group, a carboxyne group, a sulfo group, and an alkoxy group. group, aryl group, amino group, alkyl-substituted amino group, alkyl group, halogen atom, etc.The number of carbon atoms in the alkyl group is 1.
Karahiro is preferred. q represents θ or l. The nitrogen atom of the heterocyclic residue may be quaternized. The heterocycle may contain an oxygen atom or a sulfur atom, and is preferably a j-A membered ring, specifically μ, an imidazolyl group, a thiazolyl group, a thiazolinyl group, an oxasilyl group, a triazolyl group, a pyridyl group, a bilibidinyl group, a Examples include a lysinyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a lysyl group for py, a radinyl group for py, a morpholinyl group, and the like. The pKa of the conjugate acid of these heterocycles is preferably V-10. Particularly preferred are pyridyl group and imidazolinyl group. Heterocycles include those having a #xia group.

The substituents are the same as those listed for R1 and R2R3.

B' U, alkylene, alkenylene, arylene, -
5o2-1-8O-1-S--O-aryl group] is a covalent organic group composed of a single combination of 5o2-1-8O-1-S--O-aryl groups. A preferred sequence is alkylene at 81, -5-1
A monovalent organic group constituted by -〇- alone or in combination can be mentioned. If -8- is included - or more,
Particularly preferred.

h is O or l.

It represents Z'H anions (chloride ion, bromide ion, nitrate ion, sulfate ion, p-toluenesulfocate, oxalate, etc.).

i is O17 or ko.

Specific compound examples of the compound represented by general formula (I) are listed below, but the present invention is not limited thereto.

(Il − (5) λαe (!n1 (6) (11−+2) Kocl!e 2C1θ λαθ (Il−(91 (Il−01 +11−C9) (1)−Qυ (11−C1”Z) − C1l tr+-αyu2 koHα ko(cooH)2 JC/!θ Among the above reduction accelerators, particularly preferred compounds Ul-/, ■-
Ko, (-3, ■-ta, 1-10.j-/l.

The usage of the compound represented by the general formula (I) of the present invention is as follows:
It depends on the desired reduction width, the type of photosensitive material used, etc., but it is 0.00/-3, OfH//l"'CO.

oi-o and zi/l are preferred. They may be used alone or in combination.

It is preferable to use 2 to 9 g of the reducing solution of the present invention for 9 days.

The reducing solution of the present invention is basically an aqueous solution of ferric chelate of aminocarboxylic acid/compound of general formula (1) of the present invention/complexing agent, but if necessary, other additives such as pH Buffers, preservatives such as sulfites, 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, a thickener, and a dye, if necessary.

In the present invention, silver images are reduced in force by being immersed in a reducer solution. Reduction can also be achieved by contacting the silver image with a sheet impregnated in hydrophilic pine f 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, thorium thiosulfite, sodium thiosulfate, or the like.

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,
Although silver iodobromide, silver chloride, or a mixture of two or more of these may be used, a halogen composition containing silver iodide is particularly effective.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure Y-
(RDJ16/7tlA3 (/971/, year/month.22
-23 pages 01. Emulsion preparation
ration and types
The method described in the r'yit (1972//month) tar page can be followed. U.S. Patent Department, 4t3 Hiro, Coco No. ≠, ≠ 32. ! Tabular grains such as those described in No. 20 and Research Disclosure 716 λ2-3 (January 2003) can also be used in the present invention.

Various photographic additives that can be used in the present invention include, for example, the above-mentioned Research Disclosure 4/7A4 (j, 2
J-21 Sada and 16/f7/A (71 Hiro r-61
/ page. The types of these additives and their detailed locations are shown below: Chemical sensitizers Sensitivity enhancers Spectral sensitizers Super sensitizers Brighteners Antifoggants and stabilizers Original absorbers, filter dyes UV absorber Anti-stain agent Hardener Binder Plasticizer, lubricant Coating aid, Surface active agent Static inhibitor 13 pages 23-2tI pages 2≠ pages, 1-2t pages, 2! -Page 25 Page right column 26 Page 26 Page 27 Page 26-27 Core page 6 Reference Page r Right column Same as above t μr Page Right column tμ Column AjO Page Left to Right Column 61/Page Left Column Same as Above tro Page Right Column Same as Above Same as Above 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 applicable to photosensitive materials for plate making. is preferable. The force reduction method U of the present invention can also be applied to photosensitive materials processed with a lithographic developer. Risugen 1 bathing liquid basically consists of dihydroxybenzene, an alkaline agent, a small amount of sulfite, sulfite buffer, etc.

Is the force reduction method of the present invention particularly applicable to hydrazine derivatives? It can be effectively applied to ultra-high contrast photosensitive materials containing the same.

Regarding such photosensitive materials, please refer to JP-A-Sho! 3-/BU No. 423, J3-20 Octopus No. 2, DOJ 3-6T 732, U.S. Patent Department, 21≠.

ttoi No. 1I, /6Ir, No. 977, No. ≠.

For details, refer to the specifications of No. 166.7172, No. a, 3ii, Yri, No. 272.404, No. ≠, Co//, No. 1j7, No. ≠, λ≠ 3,732 Are listed.

In addition, this ultra-high contrast photosensitive material uses JP-A-Sho-t as a nucleation accelerator.
3-/ko≠O≠! Issue, JP-A-63-/33/Hiroshi! It may also contain compounds described in this issue.

Also, JP-A No. 121/13/7, same! 3-Tayo 62r,
It is also effective for high-contrast light-sensitive materials containing tetrazolium salts as described in Mukai J3-ta No. 162.

These new high-contrast photosensitive materials are also easy to use with Lithium developer.
1i! It has the advantage of being able to obtain high-contrast photographic characteristics with a suitable developer.

Gen@ used here! A liquid hydroxybenzene-based developing agent is used as the main developing agent, and a p-aminephenol-based or/
- A phenyl-3-pyrazolysine type developer is used as an auxiliary developer. The developer can be used even if it is contained in the photosensitive material.

Preservatives include sodium sulfite, potassium sulfite, sodium bisulfite, formaldehyde sodium bisulfite, and the like.

pHIIftx of developer / 0, /-/ 2, 3
'D range is set. As an alkaline agent, use the usual water-based inorganic alkali metal salts (fila: sodium hydroxide, potassium carbonate, tribasic potassium phosphate, etc.) f:! :: Can be used. The alkanolamines described in U.S. Pat. No. 44.2 and 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, ethanol, etc.
! - It may also contain an antifoggant or a black splatter agent such as a penztriazole compound such as methylbent IJ azole, or an indazole compound such as nitroindazole, and if necessary, a color toning agent, a surfactant, and a water softener. It may also contain agents.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, Miso sulfur compounds, which are 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 is usually 0 to 3.0 Elkl/it in terms of a nium salt.

Ethylenediaminetetraacetic acid Fe (I[l
) Complex salts may also be used.

The processing temperature is usually selected between 1"C and 70C, but it may also be lower than 11C or above ROOC.

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

Example 1! per mole of silver (1×
/ 0 mol of potassium iridium chloride In the presence of ammonia, a silver nitrate water bath solution and an aqueous solution of potassium iodide and potassium bromide were prepared simultaneously for 60 minutes, and the pAg during that time was
By keeping 7.1, the average particle size o, 2r
A cubic monodisperse emulsion with an average silver iodide content of 0,000 μm was prepared. This emulsion was desalted by the 70-kV curing method, and after adding Hiroshi Og of inert gelatin per mole of silver, the emulsion was kept at a temperature of 70 kV and used as a sensitizing dye. ,
ta'-cyclorotaethyl-3,3'-bis-(3-
A solution of 1 io mole of sulfoglovir J oxacarbonanine per mole of silver was added, and the temperature was lowered after 75 minutes. This emulsion was redissolved and 0002 mol of methylhydroquinone per 1 mol of silver and the following sensitizing dye (1) and hydrazine visiting conductor L2)'\/
, co×10 mol/Ag mol, and the following additives (3
),! -Methylbenztriazole, Hiro-Hydroquine-
6-Methyl-/, 3.3a, 7-chitrazaindene, the following nucleation accelerator (≠, 5), and a polyethyl acrylate dispersion were added to a hardener klf5 and applied to a polyethylene terephthalate film.

l.

C2L"i5 S V.

(t)CsHxx 　2H5 j.

The film thus obtained was exposed to light through a sensitometric wedge using an ltQ-ray contact screen, developed for 30 seconds with a developer having the composition shown below, fixed, washed with water, and dried.

Current Article 11 (Liquid Ethyleneaminetetraacetic acid tetratetate lamb salt Sodium hydroxide ! -Sulfosalicylic acid potassium sulfite n-glytyljetanolamine N-methyl-p-aminepheno L/cosulfate hydroquinone 2-Merukabutbenzuizudashi monolunarsulfuric acid ! -(!-Merukabutoteto 2zo Sodium benzenesulfonate thorium Toluenesulfone er thorium ! -Methylbenztriazole sodium bromide add water ! ,09 o, rg og l liter (pH//, t) The fixer is GR-F/(manufactured by Fuji Photo Film). 7g 1g r! i 110g zg 0.3g oy O, 39 0.2fl was used.

The obtained halftone silver image (area ratio! O-tin) was subjected to a reduction treatment using the following reduction liquid.

The reduction speed is the dot area ratio after processing to seconds, and the reduction suitability is 10.
h Density after reduction (silver image density before reduction≠).

60 or higher), and the residue was examined with the results shown in Table 1.

Table 1 The unit is g/l p) i is according to Hiroshi.

As is clear from Table 1, by using the force reduction accelerator of the present invention, the force reduction speed is faster, the force reduction width is significantly wider, and there is no residue.

Example 2! θmolti silver chloride, /ri,! Morch's silver bromide and O0t
A silver halide emulsion consisting of Morch's silver iodide was gold-sensitized and sulfur-sensitized, and a spectral sensitizer (1), a development accelerator (co), a hardener (3), and latex were added in this order. after,
Coated on polyethylene terephthalate.

C 3-carboxymethyl-! -(co(3-ditylthiazolinidene)ethylidene) rhodaninco, holoxyethylene nonylphenyl ether (10 ethylene oxide groups) 3. Mucochloric acid After exposing this photosensitive material through a magenta contact screen, H3-t (Fuji After developing at 32°C/min with a photographic film (manufactured by ``Photographic Film''), the strength was reduced using the following reducing solution, and the results are shown in Table 2.

Table 2 Table 2 shows that the force reducing fluid of the present invention is excellent in both force reducing speed and speed.

reduction width

Claims (2)

[Claims] (1) A reducing liquid characterized by containing a ferric chelate compound of aminopolycarboxylic acid and a compound represented by the following general formula (I). General formula (I) A^1-(B^1)_h-A^2(Z^1)_i (In the formula, A^1 and A^2 are each ▲a mathematical formula, a chemical formula, a table, etc.▼, or , represents a saturated or unsaturated heterocyclic residue containing at least one nitrogen atom.A^1, A^
2 may be the same or different. R^1, R^2, R^3
represent a hydrogen atom and an alkyl group, respectively. R^1, R
^2 and R^3 may be the same or different. q is 0 or 1. The nitrogen atom of the heterocyclic residue may be quaternized, and the heterocyclic ring may contain an oxygen atom or a sulfur atom. B^1 is alkylene, alkenylene, arylene,
-SO_2-, -SO-, -S-, -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R^4 is a hydrogen atom, an alkyl group, an aryl group ] represents a divalent organic group composed of either alone or in combination. h is 0 or 1. Z^1 represents an anion. i is 0, 1 or 2. ) (2) A method for reducing force on a silver image, which comprises subjecting a silver image formed by exposing and developing a silver halide photosensitive material to light using the reducing liquid according to claim 1.