JPS63138350A - Method for processing silver halide color photographic sensitive material excellent in rapid processing - Google Patents

Abstract

PURPOSE:To enable rapid processing by exposing a silver halide color photographic sensitive material having a photographic constituting layer contg. a specific silver halide emulsion layer, followed by recessing the obtd. material with a color developer and a processing solution having specific bleach-fixing ability. CONSTITUTION:The silver iodide content of silver halide contd. in the silver halide emulsion layer is >=0.5mol% and the total dry film thickness of the whole photographic constituting layer of the silver halide emulsion layer provided on a carrier is <=25mum. And, the processing solution having bleach-fixing ability has pH of 3.0-6.8, and contains at least one compd. selected from a ferric complex salt contg. a compd. shown by formula (I) as a ligand, and polyethylene amine and a compd. shown by formula (II). In formulas, R1 is hydrogen atom, etc., R2 is 2-6C hydroxyalkyl group, R3 and R4 are each hydrogen atom or 1-6C alkyl group, etc., Thus, the bleach-fix bath does not deposit a bleaching agent at a low temperature, and the obtd. coloring image is controlled the reduction of desilvering ability, and the generation of a defective recoloring, and the rapid processing of the titled material is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which can be applied to a light-sensitive material for M-Award and can be coupled with rapid processing.

[Background of the Invention] Currently, in the desilvering process of photographic materials using high-sensitivity silver iodobromide emulsions containing silver iodide of a specific m or more, the bleaching process and the fixing process are carried out separately. .

In order to simplify and speed up the desilvering process of the photographic light-sensitive materials, the present inventors have investigated a bleach-fixing process in which bleaching and fixing are performed in one bath.

In the course of this study, it has been considered that it is advantageous to use the above bleach-fix solution in a region with a high C1 (C1) from the viewpoint of solution storage stability and the occurrence of poor color restoration of the obtained dye image. As a result of searching for bleaching agents with excellent desilvering ability in the high l1JH region, the present inventors found that among various aminopolycarboxylic acid iron complexes, diethylenetriaminepentaacetic acid ferric complex salt (DTPA-Fe complex salt) has the highest desilvering rate. , has been proposed as one that satisfies the recoloring properties of the resulting dye image and the storage stability over time of the bleach-fix solution.
No. 4238, No. 60-130738 No. 60-1367
44, etc.) The above-mentioned DTPA-FeiI salt can satisfy the above characteristics in a high pH range, specifically in the range of about DH7 to 9, but ammonia gas is likely to be generated in such a pH range. However, it has disadvantages in terms of working environment when developing processing is carried out in a narrow room. Roughly speaking, over time when photosensitive materials are processed over a long period of time,
It has been found that a decrease in desilvering ability and poor color restoration occur, which are thought to be caused by the accumulation of ferrous ions in the bleach-fix solution.

As a result of a detailed study of the above drawbacks, we found that the accumulation of ferrous ions is highly dependent on the IIH of the bleach-fix solution, and that above a certain oH, over time during processing, the accumulation of ferrous ions is not normally used as a bleach. This problem was found to be common to iron complex salts of aminopolycarboxylic acids.

In order to solve the above-mentioned problems, the present inventors investigated the practical application of a bleach-fix solution in a low pH range and found that it has sufficient bleaching ability even when used as a bleach-fix solution for high-sensitivity photographic materials. We found a specific bleaching agent that has
It has become clear that when these specific bleaching agents are used at low pH, they have the disadvantage that precipitation of the bleaching agents is particularly likely to occur at low temperatures. This phenomenon of low-temperature precipitation becomes extremely likely to occur when the concentration of the bleaching agent is increased to increase the bleaching rate, or when the concentration of the replenisher is increased to reduce the amount of replenisher.

As a result of repeated studies in order to solve the problem of low-temperature precipitation of specific bleaching agents in low 1)H as described above, the present inventors have found that by using specific alkanolamines and polyalkyleneimines, the above-mentioned Although the problem could be solved, it became clear that the use of these compounds had a serious drawback in that the poor color restoration became even more obvious.

Conventionally, it has been known to add various compounds such as organic amines as solubilizers to bleaching solutions or bleach-fixing solutions (Japanese Patent Laid-Open Publication No. 49-84652, etc.).
, However, the present invention provides that specific alkanolamines or alkylene imines are used to reduce the low-temperature reaction that occurs when the specific bleaching agent of the present invention is used in the bleach-fix solution having the specific l)H region of the present invention. This achievement was achieved by discovering that, in addition to solving the problem of precipitation, the problem of poor color reproduction, which becomes even more apparent due to the use of the compounds of the present invention, can be solved by processing the color photosensitive material having the specific film thickness of the present invention. Conventionally known solubilizing agents other than the alkanolamines or alkyleneimines of the present invention are those that occur when the bleaching agent of the present invention is used in the bleach-fix solution having the specific pH range of the present invention. Not only does it not necessarily have a sufficient effect on low-temperature precipitation, but even if it does have some effect, the problem of poor color recovery can be further solved by using the color photosensitive material of the present invention having a specific film thickness. Can not.

[Object of the Invention] Therefore, the object of the present invention is to prevent precipitation of bleach at low temperatures in a bleach-fix solution, to suppress a decrease in desilvering ability and to suppress occurrence of defective color recovery in the obtained dye image, and An object of the present invention is to provide a method for processing silver halide color photographic materials that enables rapid processing.

The above-mentioned object of the present invention is to perform at least color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support. In a method for processing a silver halide color photographic light-sensitive material in which the silver halide color photographic material is processed with a processing solution and a processing solution having bleach-fixing ability, the silver iodide content of the silver halide contained in the silver halide emulsion layer is 0.5 mol% or more. The total dry film thickness of all the photographic constituent layers on the side having the silver halide emulsion layer on the support is 25 μm or less, and the PL-1 of the processing solution, which roughly determines the bleach-fixing ability, is 30 ~6.8 and selected from ferric complex salts having a compound represented by the following general formula [I] as a ligand, poly(alkylene imine), and a compound represented by the following general formula [T[ ] It is coupled by a method for processing a silver halide color photographic light-sensitive material containing at least one of them.

General formula [I] In the formula, R1 represents a hydrogen atom or a lower alkyl group,
nl, n2 and n3 each represent an integer from O to 3. However, the sum of nl, n2 and 1)3 is an integer from 2 to 4, and the sum of the numbers is 2 or more. ] General formula [II] [wherein R2 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R3 and R4 are each a hydrogen atom, a furkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or an integer of the formula;
6 alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms. ] [Specific Structure of the Invention] The silver halide color photographic light-sensitive material used in the processing of the present invention contains silver iodide in at least 0.5 mol %, preferably 3 to 10 mol %, of silver iodide in at least one of the silver halide emulsion layers. %, more preferably 5 to 8 mol %.

The above-mentioned silver halide grains containing 0.5 mol% or more of silver iodide have an average silver halide composition of 0.5 mol % or more.
There is no particular restriction as long as the content is mol % or more, but in the present invention, core-shell type silver halide grains and tabular silver halide grains are preferred.

In the present invention, at least one layer of the silver halide emulsion layer contains silver halide grains having a silver iodide content of 0.5 mol% or more (a preferred embodiment of the silver halide grains is a core-shell type silver halide grain as described above). A silver halide emulsion containing silver halide grains having a silver iodide content of 0.05 mol % or more, which can be applied to all silver halide color photographic light-sensitive materials containing silver halide grains and/or tabular silver halide grains. The layer may be all or one layer of silver halide emulsion on the support.

The silver halide color photographic light-sensitive material used in the present invention having silver halide grains having a silver iodide content of 0.5 mol % or more has the entire photographic structure on the side having the silver halide emulsion layer on the support. The total dry film thickness of the layers is 25 μm or less. In the present invention, the dry film thickness of all photographic constituent layers means the photographic constituent layers excluding the support, that is, silver halide emulsion M (at least 3 layers in the case of a full-color photographic light-sensitive material),
Undercoat layer, antihalation layer formed as necessary,
This is the total thickness of all hydrophilic colloid layers such as the intermediate layer, filter layer, protective layer, etc., and is the thickness of the dried photographic constituent layers. Gelatin is often used as the hydrophilic colloid, and in this case, the film thickness can be referred to as the gelatin film thickness.

The dry film thickness in the present invention means the film thickness measured at 23°C and 55% humidity. Further, regarding the thickness of each layer, the cross section of the dried sample is photographed under magnification using a scanning electron microscope, and the thickness of each layer is measured. The lower limit of the total dry film thickness of all the hydrophilic colloid layers on the side having the emulsion layer is determined by the volume occupied by the silver halide emulsion, oil agents such as couplers, additives, binders such as gelatin, etc. contained therein. Dry film thickness is 2
The total dry film thickness may be 5 μm or less, but the total dry film thickness is preferably 22 μm or less, particularly 20 μm or less, and more preferably 18 μm or less. In terms of photographic performance, the lower limit is 8 μm.
It is preferable that it is above.

The above silver halide color photographic light-sensitive material for image forming according to the present invention comprises a ferric complex salt having a compound represented by the general formula [I] as a ligand, a poly(alkylene imine) and a compound represented by the general formula [II]. It is processed with a processing solution containing at least one compound selected from the following and having a bleach-fixing ability with p+ in the range of 3.0 to 6.8.

Hereinafter, the processing solution having bleach-fixing ability of the present invention, that is, the bleach-fix solution of the present invention will be explained.

The bleach-fix solution of the present invention uses a ferric complex salt having a compound represented by the general formula M as a ligand.

In general formula [I], R1 is preferably a hydrogen atom. Further, the total number of carbon atoms in +CH2 古廿C)I-sufCt-hi is most preferably 3.

Preferred specific examples of the compound represented by the general formula [g] are shown below.

Exemplary Compound A compound represented by the above general formula [I] as a ligand.
The iron complex salt (hereinafter referred to as the ferric complex salt of the present invention) is also used as a free acid (hydrogen salt), but as a counter temperature, it can be used as an alkali metal salt such as sodium salt, potassium salt, lithium salt, or ammonium salt. Alternatively, it can also be used as a water-soluble amine salt, such as a triethanolamine salt.

Preferably potassium, sodium and ammonium salts are used. These ferric complex salts of the present invention may be used in small amounts (one kind may be used, but two or more kinds can be used in combination. Furthermore, they can be used in combination with ferric complex salts other than the present invention.

Among the ferric complex salts of the present invention exemplified above, ferric m salts using exemplified compounds (I-1), (I-2) and (I-3) as ligands are preferred. Further, among the exemplified compounds No., (I-1), (I-2) and (I-3), it is particularly preferable to use (I-1) and (Nie 2) from the viewpoint of male dissolubility, and the present invention Considering various points such as the desired effect, it is most preferable to use (I-1) in the present invention.

The ferric complex salt of the present invention can be used in any amount as long as it obtains the effect of the present invention in the bleach-fix solution of the present invention, but if the concentration of the ferric complex salt becomes too high, the shelf life of the bleach-fix solution may be On the other hand, if the concentration of the ferric complex salt is too low, the desilvering performance and color recovery performance will deteriorate. Therefore, usually 0.02 to 1.3
It is preferable to use it in the range of 0 mol/2, and from 0.10 to
It is more preferable to use it in a range of 1.20 mol/2.

In particular, when used in the range of 0.20 to 0.80 mol/2, the desilvering property and color recovery performance can be improved more efficiently without significantly deteriorating the bleaching agent precipitation at low temperatures.

The bleach-fix solution used in the present invention has the general formula [■]
It contains at least one compound selected from poly(alkyleneimine) and a compound represented by the general formula [I] together with the compound represented by the formula [I].

Below, poly(alkyleneimine) R used in the present invention
3 and the compound represented by the general formula [I[] will be explained.

The poly(alkylene imines) used in the present invention consist of substituted or unsubstituted repeating alkylene chain units connected to each other via nitrogen atoms. These are well known commercially available materials. Typical poly(alkyleneimine) has the following general formula [
FAI].

General formula [FAI] 1→R+ -N-Narua (in the formula, R1 represents an alkylene group having 1 to 6 carbon atoms, R2 represents an alkyl group, and n is 500 to 20,0
Represents an integer of 00. ) The alkylene group having 1 to 6 carbon atoms represented by R1 above may be linear or branched, and is preferably an alkylene group having 2 to 4 carbon atoms, such as ethylene group, propylene group, butene group, isobutyne group, dimethylethylene group. group, ethylethylene group, etc. R2
The alkyl group represented by preferably has 1 to 4 carbon atoms.
It is an alkyl group such as a methyl group, an ethyl group, a propyl group, etc., and also includes those having a substituent (for example, a hydroxyl group). n represents the number of repeating units in the polymer chain and is an integer from 500 to 20,000, preferably from 501 to 2,000. Most preferred for purposes of this invention are poly(ethyleneimines) in which R1 is an ethylene group.

Examples of poly(alkyleneimine) used in the bleach-fix solution of the present invention are shown below, but the present invention is not limited thereto.

“Exemplary Compounds FAI-1 Poly(ethyleneimine) PAI-2 Poly(propyleneimine) FAI-3 Poly(buteneimine) PAI-4 Poly(isobutyneimine) FAI-5 Poly(N-methylethyleneimine) FAI-
6 poly(N-β-hydroxyethylethyleneimine) PAI-7 poly(2,2-dimethylethyleneimine) FAI-8 poly(2-ethylethyleneimine) FAI-
9 In the poly(2-methylethyleneimine) general formula [II], R2 is a hydroxyalkyl group having 2 to 6 carbon atoms, R3 and R4 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 2 to 6 carbon atoms, respectively. ~6 hydroxyalkyl group, benzyl group, or an integer in the formula, X and Z are each hydrogen atom, carbon number 1 ~
6 alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms.

Among the compounds represented by the general formula [II], compounds represented by the following general formula [■'] are particularly preferably used.

General formula [■'] (In the formula, R5 represents a hydroxyalkyl group having 2 to 4 carbon atoms, and R6 and R7 each represent an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.) Preferred specific examples of the compound represented by the general formula [II] are as follows.

Ethanolamine, jetanolamine, triethanolamine, di-isopropanolamine, 2-methylamineethanol, 2-ethylamineethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamine-2-propanol, 3 -diethylamine-1-propanol, 3-dimethylamino-
1゛-propertool, isopropylamine ethanol,
3-amino-1-propatol, 2-amino-2-methyl-1,3-propanediol, ethylenecyamine titreitsbrobanol, benzyljetanolamine, 2
-Amino-2-(hydroxymethyl)-1,3-propanediol.

The poly(alkylene imine) used in the present invention, 1
At least one compound selected from compounds represented by formula [12] and general formula [II] can be optionally used in the bleach-fix solution of the present invention, but generally the bleach-fix solution 12
preferably 0.1 to 500q, more preferably 0
．． It is used in a range of 5g to 300g.

The bleach-fix solution of the present invention has a DH range of pH 3.0 to
6.8, and any l)H can be used within this pH range, but in addition to desilvering and recoloring properties, it also has the solubility of various iron salts at low temperatures, and is generated from @sulfite ions. Considering the odor of sulfur dioxide gas, it is preferable to use it at a pH of 4, Q to 6.1, most preferably at a pH of 5.0 to 6.5.

The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount of 5 g/12 or more, preferably 50 g/4 or more, more preferably 70 a/1 or more.

The bleach-fix solution of the present invention can contain various additives. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like.

The bleach-fix solution of the present invention includes Imm, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
pHM consisting of various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
Shocking agents can be contained alone or in combination of two or more. The powder may also contain various optical brighteners, antifoaming agents, surfactants, and antifungal agents.

In addition, organic chelating agents such as acetyl aretone, phosphocarboxylic acid, polyphosphoric acid, oxidized phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid, and aminopolycarboxylic acid, or nitroalcohol, nitrate M salt, etc. A stabilizer, a solubilizing agent such as an alkanolamine, an anti-staining agent such as an organic amine, other additives, and a cloth solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.

It is preferable to use a bleach accelerator in the bleach-fixing solution of the present invention, and for example, compounds described in Japanese Patent Application No. 160943/1983 can be used, and the following general formula [A-Imm
It is preferable to use the compounds shown in [A-IV] because the effects of the present invention can be achieved well.

General formula [A-I] Qr-1 In the formula, Ql represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed). where R1 represents a hydrogen source alkyl group.

However, Q' has the same meaning as Ql.

General formula [A-I] In the formula, R2 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amine group, an acyl group having 1 to 3 carbon atoms, an aryl group, or Represents an alkenyl group.

A represents or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X does not represent -S, -0 or -NR''. , R and R" have the same meaning as R2 and R3, respectively, X' has the same meaning as X, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, an ionic heterocyclic residue, an alkyl group, or an atom. , RII is a hydrogen atom, an alkyl group having 1 to 6 atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (including those in which a 5- to 6-membered unsaturated ring is fused to carbon)
or represents an amine group, n1 to nG and m1 to m5
each represents an integer from 1 to 6. B has 1 or more carbon atoms
6 represents an alkylene group, Y represents -N or -CH, R1 and R5 are R2 and 1 respectively, and 3
is synonymous with However, R1 and R5 are each -B-
87 can also be represented by J, ku, R2 and Ra, R and R'
, R4 and R5 may each be combined to form a ring.

Note that the compound represented by the formula also includes enolated products and salts thereof.

General formula [A-III 7] In the formula, R6 and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amine group, an acyl group having 1 to 3 carbon atoms, and an aryl group. group, alkenyl group or -B+ -3-Z+. Alternatively, R6 and R7 may be combined to form a ring. Yl is
N- or CI-(-, B1 represents an alkylene group having 1 to 6 carbon atoms, Zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or an integer of represent.

General formula [A -IV 3 (Q')z In the formula, Ar is a divalent aryl group or a combination of an aryl group and an oxygen atom and/or an alkylene group.
B2 and B3 each represent a lower alkylene group, R8, R9, Rho and [)1
1 each represents a hydroxy-substituted lower alkyl group,
X and y each represent O or 1. G' represents an anion, and 2 represents 0, 1 or 2.

Specific examples of bleach accelerators preferably used in the present invention are shown below.

Exemplary compound (A-1>　　　　　　(A-2)(A-3) <A-4) (A-5) (A-6) (A-7) H, N-CS N HN HCS-N H.

(A-9) The bleach accelerator addition m is about 0 per 12 bleach-fixing solutions of the present invention.
,01 to 100g, more preferably 0.05 to 50g, particularly preferably 0.0g.
5 to 15a.

Addition of the bleach accelerator accelerates bleaching, but under conditions where the color developing solution is mixed into the bleach-fixing solution, the occurrence of poor color recovery is further amplified. However, by setting the thickness of the photographic constituent layer to 25 μm or less as in the structure of the present invention, such an increase in color restoration defects can be effectively prevented.

In recent years, low replenishment has been carried out for the purpose of reducing pollution load and processing solution cost.

Generally, contamination and accumulation of color developer in bleach-fix solution worsens poor color recovery and density increase in unexposed areas (bleach-fix fog); The amount increases even more in the case of a concentrated low replenishment method aimed at reducing the frequency of dissolution and the flow of waste liquid.

The present invention is particularly effective for such low replenishment type processing, and the mixing rate of the color developer into the bleach-fix solution is 4.0% to 100%.
% range, and in particular 6.0% to 100% range, where the influence of color developer contamination accumulation increases, and 9.%.
It is more effective when it is in the range of 0 to 100%.

Further, when the above-described low replenishment method is applied to the bleach-fix solution of the present invention, it is expected that iodine ions will accumulate in the bleach-fix solution of the present invention. Traditionally, the accumulation of iodine ions is
Although it is known that the desilvering rate decreases, in the bleach-fix solution of the present invention, not only does the desilvering property not substantially deteriorate even due to the accumulation of iodine ions, but surprisingly,
Increased density in unexposed areas (so-called fog) that tends to occur when the film is immersed in a bleach-fix solution without going through a washing process such as a water washing process after color development processing, and when the film thickness of the photographic constituent layer is reduced to 25 μm or less. It has become clear that this rarely occurs. ' At this time, it is preferable that the bleach-fix solution contains iodine ions in an amount of o, ooos mol/y or more, more preferably 0.001 mol/y or more.

There is no particular restriction on the processing time with the bleach-fix solution of the present invention, but it is preferably a short time in order to speed up the processing.
It is generally used for 9 minutes or less, preferably 6 minutes 30 seconds or less, more preferably 5 minutes 30 seconds or less.

The bleach-fix solution of the present invention is used at a temperature of 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower. It is also desirable to use it while suppressing evaporation.

The bleach-fix solution of the present invention may be used as a processing solution for bleaching and fixing the silver halide photographic light-sensitive material for photography according to the present invention immediately after color development, or may be used as a processing solution for washing, rinsing, stopping, etc. after color development. It may be used as a bleach-fixing solution after carrying out a pre-fixing treatment after color development, or as a bleach-fixing solution after carrying out a pre-fixing treatment after color development. Furthermore, after the treatment with the bleach-fixing solution of the present invention, washing with water and then stabilization may be performed, or the washing process may be omitted or the amount of washing water may be extremely reduced as described in JP-A-57-8543. Multistage countercurrent stabilization treatment technology and JP-A-58-1483
It can also be applied to a treatment technique using a water washing alternative treatment liquid as described in Publication No. 4. In addition to the steps of color development, bleach-fixing, and washing with water, various auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.

The photographic silver halide emulsion applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Couplers are used in the emulsion layer of color photographic materials.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Experiment 1) The following layers were provided on a triacetate film base, and the silver halide emulsion layer had a total silver content of 88/100Ci2.
100, and further coated so that the dry film thickness of all the photographic constituent layers was 30 μm, to obtain photosensitive material sample A for comparison.

Layer 1: A dispersion of black colloidal silver 0.80, which exhibits high absorbency to light in the wavelength range of 400 to 700 ni by reducing silver nitrate with hydroquinone as a reducing agent, is prepared in gelatin and coated with an antihalation layer. .

Layer 2: Middle layer made of gelatin.

Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (A
gI: 6 mol %), gelatin and 0,96Q cyan coupler (C'-1), 0.028 (l) 1-hydroxy-4-[4-(1-hydroxy-8-acetamide-
3゜6-disulfo-2-naphthylazo)phenoxy]-
N-[δ-(2,4-di-amylphenoxy)butyl]
-2-Naphthamide disodium (hereinafter referred to as colored cyan photoluminescent silver halide emulsion layer).

1! i4...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (Aol: 8 mol%), gelatin and 0.411J of cyan coupler (C-1>, 0.026g of colored cyan coupler (CG- A highly sensitive red-sensitive silver halide emulsion layer containing 0.15 (l) of TCP in which 1) was dissolved.

Layer 5...o, oag 21.5-G C-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1))
An intermediate layer containing dibutyl phthalate (hereinafter referred to as DBP) and gelatin.

Layer 6...low-sensitivity green-sensitive silver iodobromide emulsion (Ag I; 1
5 mol%), gelatin and the following magenta coupler (
M-1) 0.6g, O,066g of 1-(2,4,6
-trichlorophenyl)-4-(1-naphthylazo)-
0.3 g of T in which 3-(2-chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) was dissolved.
Low-sensitivity green-sensitive silver halide emulsion layer containing CP.

Layer 7: Highly sensitive green-sensitive silver iodobromide emulsion (A(II:1
1 mol%>, gelatin and the following magenta coupler (
M-1) 1.2 g of T in which 0.19 g, 0.04 Jl of colored magenta coupler (CM-1) was dissolved
A highly sensitive green-sensitive silver halide emulsion layer containing CP.

Layer 8...0.2 (l yellow colloidal silver, 0.2 g antifouling agent (HQ-1) dissolved, 11 g DBP
and a yellow filter layer containing gelatin.

Layer 9: DIP of 0.93 (] in which a low-sensitivity blue-sensitive silver iodobromide emulsion (Aol: 6 mol %) of 0.9511, gelatin and a yellow coupler (Y-1) of 1,849 was dissolved. A low-speed blue-sensitive silver halide emulsion layer containing.

Layer 10: 1.2 g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (Ag 1 mol%), gelatin and 0,46 (
0,23Q in which J's yellow coupler (Y-1) was dissolved
A highly sensitive blue-sensitive silver halide emulsion layer containing DBP.

Layer 11: Second protective layer made of gelatin.

Layer 12: first protective rIi layer containing gelatin.

Yellow coupler (Y-1) Magenta coupler (M-1) CI! Cyan coupler (C-1) This sample was cut into pieces, subjected to model exposure according to a conventional method, and processed using a piece processing device according to the following steps (hereinafter referred to as hand processing). Ta.

Processing process Processing temperature ('C) Number of tanks Processing time 1 Color development 37.8 1 tank 3 minutes 15 seconds 2 Bleach fixing 37.8 1 tank 6 minutes 30 seconds 3 Washing 30-34 2 tanks 4 minutes 20 seconds 4 Am Constant 30-34 1 tank 2 minutes 10 seconds 5 drying The following dry color developing solution, bleach-fixing solution and stabilizing solution were used.

[Color developer] 1.

i 7 IchiL''triami'pentanoic acidi Add water to make 1i, add sodium hydroxide!i
20%'fAFi I) 810.06 NiHI adjustment.

[Bleach-fix solution] 1 Ferric organic acid shown in Table 1 [Stabilizer 1 Table 1 Table 1 (continued) A part of the bleach-fix solution after the above treatment was mixed with an aperture ratio of 10 Ci'/
j! (The opening conditions correspond to a general automatic development layer, and 1
This means that the bleach-fix solution of No. 2 has an air contact area of 10 cm'. ) at 38° C. for one week, and the above treatment was performed again using the bleach-fix solution after storage. The amount of residual silver (In(1/
d12) was measured by fluorescent X-ray method. Furthermore, after measuring the cyan dye concentration using a Sakura photoelectric densitometer PDA-65 (Konishi Roku Photo Industry ■!11), using this value, the same sample was heated to V temperature using a 3% red blood salt solution according to a conventional method. The color recovery rate was calculated by setting the cyan dye density after treatment for 3 minutes to 100.

On the other hand, 1. The other part of the bleach-fix solution after the above treatment was heated to 0°C.
The samples were stored for one week and the occurrence of precipitation was observed.

The results are summarized in Table 2.

Table 2 ◎ No precipitation occurred O Slight precipitation observed ∆ Thin precipitation deposited on the bottom × Slightly large precipitation ×× Significant precipitation occurred Table 2 shows the film thickness of photographic constituent layers other than those of the present invention. A photosensitive material having
These are the results of processing with a bleach-fix solution containing various bleaches mixed with a color developing solution, but in experiments 1-1 to 1-5 in which NTAFe complexes other than the present invention were used as bleaching agents, no residue remained under any conditions. Results that satisfy the silver content and color restoration rate cannot be obtained. On the other hand, in experiments 1-6 to 1-10 in which a DTPAFe complex salt other than the present invention was used as a bleaching agent in a high pH range, for example, in experiment 1-6, when the bleach-fix solution before storage was used, the amount of residual silver was Although the results are satisfactory in terms of both the color recovery rate and the color recovery rate, the amount of residual silver and the color recovery rate both deteriorate significantly in the bleach-fix solution after storage. In addition, in experiments in the low 1) H range, even when the bleach-fix solution before storage was used, the desilvering performance was good, but the recoloring rate deteriorated significantly, and when the bleach-fix solution was used after storage, In this case, the desilvering property deteriorates significantly. i.e. DTPA
It can be seen that when an Fe complex salt is used as a bleaching agent, a tired bleach-fix solution is not satisfactory. On the other hand, when using the bleaching agent of the present invention, Exemplary No.
) The color restoration rate is good in the H range, but the desilvering property is insufficient; in the low pH range, although the desilvering property is satisfactory, the color restoration rate deteriorates, and when the bleach-fix solution is stored at low temperatures, Significant precipitation occurs. Overall, in the processing of photosensitive materials with conventional photographic constituent layer thicknesses, it is not possible to satisfy all of the desilvering properties, color recovery rate, and low-temperature precipitation properties, especially when using a bleach-fix solution after storage. do not have.

(Experiment 2) Using comparative sample A used in Experiment 1 above, bleach-fix solution N
An experiment similar to Experiment 1 was conducted using Samples 3-1 to 3-9. However, after adding 50g/ffi of each of the additives listed in Table 3 to the bleach-fix solution,
was adjusted by adding acetic acid.

The bleach-fixing time was 6 minutes.

The results are shown in Table 3, and the data on residual silver m and color recovery rate are as follows: Table 3 (Continued) As is clear from Comparison Table 3, all of the above experiments were carried out using the bleach-fix solution after storage over time. It can be seen that, in particular, by adding the additive of the present invention, the occurrence of precipitation is improved, but the deterioration of the color recovery rate is particularly significant.

(Experiment 3) In the comparative photosensitive material II A used in Experiment 1 above, the dry film yf 30 μm of the photographic constituent layer was changed to a film thickness of 27 μm, 25 μm 122 μm 1 by changing only the gelatin coating m.
Light-sensitive material samples NO, B, C, D, E, and F were obtained in exactly the same manner except that the thicknesses were 20 μm and 18 μm.

The above photosensitive material samples NO, B, C, D, E and F were treated in the same manner as in Experiment 1 and evaluated in the same manner.

However, the bleach-fix solution No. used was shown in Table 4 below, and 75 a/fl of triethanolamine was added to each. Further, data on the amount of residual silver and the rate of color recovery are shown only for those using bleach-fix solutions after storage over time.

The results are summarized in Table 4.

Table 4 Table 4 (Continued) From the results in Table 4, when the bleach-fix solution of the present invention is used, both the desilvering property and the color recovery rate can be satisfied by reducing the film thickness of the photosensitive material to 25 μm or less. be able to.

In addition, bleach-fix solution No. 3-1 to 3-9. Bleach-fix solution No. 4-1 to 4-9. 5-1 to 5-9 to which 75 Mff1 of triethanolamine was added in the same manner instead of
Similar experiments were repeated for No. 6-1 to No. 6-9, and all showed good low-temperature precipitation properties, as well as desilvering and recoloring properties.
, 3-1 to 3-9 were the best, and then deteriorated in the order listed above, but almost the same results were obtained.

(Experiment 4) Photosensitive material sample No. prepared in Experiment 3 above.

F was treated under the same conditions as in Experiment 2, and the same evaluation was performed. However, the bleach-fixing solutions used were those shown in Table 5, and the additives shown in Table 4 were added at 509/2.

Evaluation was performed in the same manner as in Experiment 2, and the results are shown in Table 5.

Table 5 Table 5 (Continued) The results of all of the above experiments shown in Table 5 show that similar effects can be obtained even if the types of additives of the present invention are changed.

Looking more closely, example No. 1 is a bleaching agent.

It can be seen that Knee 1, I-2 and I-3 are excellent, and I-1 is particularly preferred.

Combining the results of Experiments 1 to 4 above, we found that using the processing method of the present invention, that is, using the ferric complex salt of the present invention as a bleaching agent for photographic light-sensitive materials having a photographic constituent layer thickness of 25 μm or less. l) H containing the additive of the invention is 3.
Only in the method of processing with a bleach-fix solution of 0 to 6.8,
It can be seen that regardless of whether or not a bleach-fix solution was stored, good desilvering properties and restoring properties were exhibited, and the occurrence of precipitation during low-temperature storage was prevented.

Example 2 Bleach-fix solution No. 3-6.4-6 used in Example 1.
The photosensitive materials NO, F used in Example 1 were treated in the same manner as in Experiment 2 of Example 1 using Samples No. 5-6 and 6-6.

However, here, poly(ethyleneimine) 5CMI/ffi and the bleach accelerator shown in Table 6 were added to the bleach-fix solution. The bleach-fixing time was 3 minutes and 15 seconds. The results are shown in Table 6, and the data on the amount of residual silver and the rate of color restoration are shown only for those using the bleach-fix solution after storage over time, as in Experiment 2 of Example 1.

Table 6 Table 6 (Continued) From Table 6, bleaching is accelerated by the addition of a bleaching accelerator, but It! which is outside the present invention! With J thickness, the occurrence of defective color restoration becomes more significant. On the other hand, it can be seen that when the film thickness is kept within the range of the invention, the defective color recovery is effectively improved.

Example 3 Using the photosensitive material No. F used in Example 1, the bleach-fix solution No. 1-7.3-7.4 used in Example 1 was used.
-7. Using 5-7 and 6-7, Fruit 11 of Example 1
! The second sample was treated in the same manner. However, here, the bleach-fix solution contains 50 g/ffi of monoethanolamine. The matrix of K in the bleach-fix solution was changed as shown in Table 7. The results are shown in Table 7. Data on residual silver W and color recovery rate are shown only for those using the bleach-fix solution after storage over time, as in Experiment 2 of Example 1.

Table 7 As is clear from Table 7, in the comparative bleach-fix solution, KI
By adding , the magentastin becomes smaller, but the desilvering ability is greatly reduced. However, in the bleach-fix solution of the present invention, the addition of Kl suppressed the magentastin to a low level, while the decrease in desilvering ability was small and good results were obtained.

Example 4 Using the photosensitive material No. F prepared in Example 1, the bleach-fix solution No. 3-5.4-5 used in Example 1 was used.
．． 5-5 and 6-5 were used and treated in the same manner as in Experiment 3 of Example 1. However, here, 509/
Poly(propylene imine) Il was added to each of the bleach fixing solutions to change the level of bleaching agent in the bleach-fix solution as shown in Table 8. The results are shown in Table 8. Data on the amount of residual silver and the rate of color recovery are shown only for those using the bleach-fix solution after storage over time, as in Experiment 2 of Example 1.

Table 8 Table 8 (Continued) As is clear from Table 8 of the present invention, all of the above experiments show that the bleach-fixing solution of the present invention has a bleaching agent content of 0.02 mol/l to 1.30 mol/l. 12, preferably 0.10 to 1.20 mol/ff1
1 More preferably, when the content is in the range of 0.20 to 0.8 mol/liter, desilvering and restoring ability is high even when stored over time, and low temperature occurrence during low temperature storage is low.

Claims (1)

[Scope of Claims] After imagewise exposing a silver halide color photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least a color developing solution and bleach-fixing ability are removed. In the method for processing a silver halide color photographic light-sensitive material, the silver iodide content of the silver halide contained in the silver halide emulsion layer is 0.5.
mol% or more, and the total dry film thickness of all the photographic constituent layers on the side having the silver halide emulsion layer on the support is 25 μm.
or less, and furthermore, the p of the processing liquid having bleach-fixing ability is
H is in the range of 3.0 to 6.8, and the following general formula [I]
A silver halide color photograph characterized by containing at least one selected from a ferric complex salt having a compound represented by as a ligand, a poly(alkylene imine), and a compound represented by the following general formula [II] How to process photosensitive materials. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a hydrogen atom or a lower alkyl group, and n_1, n_2 and n_3 each represent an integer from 0 to 3. However, the total of n_1, n_2 and n_3 is an integer from 2 to 4, and the total number of carbon atoms in ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼ is 2 or more. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_2 is a hydroxyalkyl group with 2 to 6 carbon atoms, R_3 and R_4 are hydrogen atoms, respectively
6 alkyl group, hydroxyalkyl group having 2 to 6 carbon atoms, benzyl group, or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where n in the above formula is an integer from 1 to 6, and X and Z are:
Each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ]