JPS6143750A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance stability by processing an imagewise exposed silver halide color photographic sensitive material in a bleach-fixing step or a rinsing step or the like following said step using a compd. represented by a specified formula. CONSTITUTION:The imagewise exposed silver halide color photographic sensitive material is continuously processed in a bleach-fixing step or the rinsing step or stabilizing step of said preceding step using at least one kind of compds. represented by the formula, X being halogen, preferably, in an amt. of 1X10<-5>- 1.0, especially, 1X10<-4>-2X10<-2>mol per liter of the rinsing water or stabilizing soln. As a preferable rinsing process, a counter-current water-rinsing system using 2-5 baths is applied in order to save a consumption of rinsing water.

Description

[Detailed description of the invention] (Field of industrial application) The present invention relates to a processing method for silver halide color photographic light-sensitive materials, and in particular to a processing method that can significantly reduce the amount of water used in the washing process and the like. .

(Prior art) Conventionally, the processing process for silver halide photographic materials includes a washing process and a stabilization process. Some suggestions have been made to reduce the amount of water used. For example, S, R,
Goldwasser.

”Water Flow 1ates in I
mmersion-Washing □r Motio
n Picture Fi1m″SMPTE, J Hiroshi,
page λur~ko! J.

(May, /j-j) proposes a method of reducing the amount of flushing water by making the flushing tank multistage and causing the water to flow countercurrently. This method has been adopted in various automatic machines as an effective means for saving water.

However, iron ions from the bleaching process and thiosulfates from the fixing process are very unstable in the washing water, and if the amount of washing water is significantly reduced, It has been found that a new problem arises in that the residence time becomes longer and each scale precipitates and floating substances are generated.

Such problems similarly occur when the water washing step is replaced with a stabilization step or in the stabilization step following the water washing step.

These precipitates and floating substances may adhere to photosensitive materials or clog or stain the filters of automatic developing systems, causing various troubles.

In order to solve these problems, many precipitation prevention means have been proposed. For example, L, E-West, “W
ater Quality Cr1teria″Pho
t, Sci, and Eng,, Volta A
6 (/l, j) describes the addition of chelating agents and bactericides.

In addition, JP-A-17-1rZtIJ, 5r-ioz/Hiroj, and J'7-/j7.2≠Hiro contain various piping preventives such as thiazolylbenzimidazole compounds and isothiazolone compounds. Although the addition of agents has been described, satisfactory results have not been obtained due to poor solubility, problems with the safety of the compound, or insufficient precipitation prevention effect. In addition, as methods for adding various chelating agents, Japanese Patent Application Publication No. 8 ((j7-fj 4A2, 37-!rlltJ, 37-/32/'At, 4II-/163/, etc.) However, all of the chelating agents are insufficiently effective or have an adverse effect on image storage stability, making it impossible to obtain satisfactory titration results.

Furthermore, as a method of using sulfite and a chelating agent in combination, JP-A No. 57-77530 and Jt. -4r7JI and the same jter? Although it is described in No. ♂732, its effect is still insufficient.

(Object of the Invention) Therefore, an object of the present invention is to improve the stability of the washing water or the stabilizing solution itself without impairing the stability of the dye image.

Another object of the present invention is to suppress the formation of precipitates and suspended substances in washing water or stabilizing liquid.

Another object of the present invention is to maintain the stability of the washing water or stabilizing solution without impairing the stability of the dye image even when the amount of washing water or stabilizing solution is significantly reduced or when the amount of replenishment is drastically reduced. The goal is to improve the stability of the liquid itself.

(Structure of the Invention) The above object is to provide a method for continuously developing a silver halogenide color photographic light-sensitive material that has been imagewise exposed. It has been found that this can be effectively achieved by including at least one compound represented by the following general formula (I) in the process.

General formula % Formula % In the formula, X represents a halogen atom. This may be the same or different. Specifically, they are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In particular, a bromine atom is preferred.

By using the compound represented by the above general formula (I), the precipitates and suspended matter generated in the washing water or stabilizing solution can be removed.
It was possible to effectively suppress the staining without adversely affecting photographic properties (for example, the stability of the dye image was not affected, staining did not occur significantly, etc.). In particular, the compounds of the present invention are effective for washing water or stabilizing solutions in which iron ions and thiosulfate coexist.

The present inventors analyzed the precipitation mechanism of washing water and stabilizing solutions in which iron ions and thiosulfates coexist, and found that iron ions are produced by air oxidation of thiosulfate using iron ions as a catalyst and by iron bacteria. Precipitate formation and decomposition of thiosulfate by sulfur bacteria and turbidity due to bacterial colonies and mold growth were found to be the central mechanisms of precipitate formation.

Therefore, it has been found that the stability of the washing water and stabilizing solution can be further improved by sterilizing the bacteria and mold in the washing water and stabilizing solution. That is, the present inventors investigated the addition of various antibacterial agents and antifungal agents.
It has been found that the compound of the general formula (I) specifically promotes the stabilization of a washing water stabilizing solution.

Further, the compound compound of the present invention is particularly preferable for use in washing water or a stabilizing solution because of its high water solubility, and is also particularly preferable from the point of view of high safety.

Specific examples of general formula (I) are shown below, but the invention is not limited thereto.

1-' CH2B r NC-C-CH2CH2CN r H2C1 NC-C-Cl-l2CH2CN t The compound represented by the general formula (I) of the present invention is a known compound, and Hokuside HFjO2 (Hokuko Chemical R.
1J#), etc., and can be easily obtained.

The amount of the compound of general formula (I) to be added is preferably /xl0-5~/, more preferably /X10-'~2X10-2 mol per wash water or stable H/.

Iron salt as a bleaching component and thiosulfate as a fixing component are inevitably brought into the washing water or stabilizing solution of the present invention from the previous bath (bleach bath, fixing bath, bleach-fixing bath) due to continuous processing. Although these contents differ depending on the water washing or stabilization method, the iron concentration is / x / 0
=/X/Omol/l, preferably /X10
-4X10-2 mOt/l, as thiosulfate concentration/
X10-'～Yo×''-1 mol/l preferably /X/(
7-3~3X/-0-' mot/l.

In addition to the compound represented by the general formula ([), other antibacterial agents and antifungal agents (anti-piping agents) may be used in the washing water or stabilizing liquid of the present invention.

For example, Tokkai Sho is used as an anti-piping agent! 7-1, 7λ≠≠ and 5r-iort4! ! Thiazolylbenzimidazole compounds as shown in No.
Isothiazolone compounds as shown in No. 7-rjll, lolophenol compounds such as trichlorophenol, bromophenol compounds, organotin and organozinc compounds, thiocyanic acid and inothianic acid. or acid amide compounds, diazine or triazine compounds, thiourea compounds, alkylguanidine compounds, μ-class ammonium salts such as benzalkonium chloride, or penicillin. General-purpose anti-inflammatory agents such as antibiotics may also be used together. In particular, combination use with thiazolylbenzimidazole compounds and inthiazolone compounds is preferred.

In addition, various compounds may be added to the washing water of the present invention. For example, hardening agents such as magnesium salts and aluminum salts, surfactants to prevent drying load and unevenness, fluorescent brighteners to improve whiteness, sulfites as preservatives, and iron. A bismuth salt or the like may be added as necessary to promote chelation with.

Or, E. West, “Water Qu
alityCriteria″Pbot, Sci, an
d Eng.

Compounds described in Mol, &6 (/Aj), etc. may be added.

Further, in the washing water of the present invention, it is preferable to use various chelating agents in addition to the compound of general formula (I). Chelating agents used in combination include inorganic phosphoric acid type, organic carboxylic acid type,
Examples of chelating agents include aminopolycarboxylic acid-based, phosphonocarboxylic acid-based, alkylphosphonic acid-based, and aminopolyphosphonic acid-based chelating agents. Among them, l-hydroxyethylidene-/,/-diphosphonic acid, nitrilo-N, N
.

N-)rimethylenephosphonic acid and ethylenediamine N
, N, N', N'-tetramethylenephosphonic acid is preferred. Addition of these chelating agents? I? 1
The degree is washing water/per unit/X10-'~/X10-'m
ol is preferably 1xlO-4 to/xIO-2mat.

The washing treatment method used in the present invention is preferably a countercurrent washing method using a Col J tank for the purpose of reducing the amount of washing water. In this case, the amount of water required for washing is approximately 7,000 m1 per m2 of color photosensitive material. Also, the amount of flushing water varies depending on the number of flushing tanks, so please refer to S, R,
Godwasser.

”Water Flow Rates in
Immersion-Washing of Mo
tion I'1cuturc Film”SMPT
E, 6' I, pagc 2 It I ~λj3, M
3γ can be output based on ay (/ri11).

The pH of the washing water in the present invention is usually around 7, but
The pH may drop to 3 or above due to carryover from the previous bath. In addition, the water washing temperature is j-110°C1 preferably /
(70C to Jj'C. If necessary, a heater, temperature controller, circulation pump, filter, floating pig, squeegee, etc. may be provided in the washing tank.

The stabilization treatment step used in the present invention may be performed after the water washing step, or the stabilization treatment step may be performed immediately without the water washing step.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. A typical example is p
Examples include liquids having a slowing ability of I-I 3 to B, liquids containing aldehydes (for example, formalin), and the like.

The stabilizing liquid may contain the various compounds described above for use in the washing water, if necessary.

For the purpose of reducing the amount of water in the stabilizing liquid, a multistage countercurrent type consisting of tanks λ to j is preferable. Even in this case, the required amount of stabilizing liquid is approximately j0ml/m" of color photosensitive material.
~ / 000 ~ becomes Otsu.

In addition, the temperature of the stabilizing liquid is j-≠00C1, preferably Bao
'(I'~3j0C) If necessary, a heater, temperature controller, circulation pump, filter, floating pig, squeegee, etc. may be provided in the stabilizing tank.

The processing method of the present invention can be applied to any of general silver halide color light-sensitive materials such as color negative film, color paper, color positive film, and color reversal film, but color paper and color negative film are particularly preferred.

Typical processing steps in the present invention are shown below, but are not limited thereto.

People, color development - bleach fixing - washing - drying B, color development - 17 white fixing h゛1 - washing - stabilization - drying C, color development -
Washing - Bleach fixing - Washing - Drying, Color development - Bleach fixed - Washing - Stabilizing - Drying Wash with water and dry. Here, in B and D, the "stable" pre-bath "
"Water washing" may be removed.

The color developer used in the present invention contains a color developing agent. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-/N,N-diethyl-p-phenylenecyamine D-22-amino-yo-diethylamine toluene D-32-amino-yo-(N-ethyl-N-lacrylamino)toluene D-see ≠-[N- Ethyl-N-(β-hydroxyethyl)aminecoaniline I)-j Comethyl-Hiro-[N-ethyl-N-(β
-Hydrooxyethylamino]aniline D-A N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-≠-aminoanili/D-7N-(λ-amino-diethylaminophenylethyl)methane Sulfonamide D-,rN,N-dimethyl-p-phenylenediamine D-ta Hiro-amino-3-methyl-N-ethyl-N-methoxyethylaniline p-10 Hiro-amino-3-methyl-N-ethyl- N-β
-ethoxyethylaniline])-// Hiro-amino-3-methyl-N-ethyl-
N-β-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The above compound is a US patent! ,/ri3
, 0Ij No., same λ, 11.

λ≠7, same, Z, J#t, λ7/-, same, jriλ
, 36≠ issue, same J, lt&, 250 issue, same 3゜6ri r
, sdj issue, etc. The use of the aromatic-grade amine developing agent is about θ, 79
to about 20.9, more preferably about o, r9 to about 109 degrees of rotation.

As is well known, the color developer used in the present invention may contain hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. Hydroxylamines may be substituted or unsubstituted, and a desired atom of hydroxylamines may be substituted with an argyl group.

The force 2-developers used in the present invention preferably have p J
(ri~/2, more preferably 7~ii, o), and the color developer may contain other known developer component compounds.

For example, alkali agents, caustic soda as pH buffering agents,
Caustic potassium, sodium carbonate, potassium carbonate, sodium chloride, tertiary potassium phosphate, potassium metaborate, borax, etc. are used alone or in combination.

In addition, for the purpose of providing buffering capacity, for formulation convenience, or to increase ionic strength, it may be added to Various salts are used, such as alkali nitrate, alkali tC acid, and the like.

In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium. For example, polyphosphate, aminopolycarbon r1!1
phosphonocarboxylic acids, aminopolyphosphonic acids,
If necessary, any development accelerator can be added to the color developer containing l-hydroxyalkylidene/,/-diphosphonic acid, etc. For example, US patent λ, 6≠Jf
, tO Hong No. 303, U.S. Patent 3゜/
7/, various birimidium compounds represented by No. 2ll7 and other calaonic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 4c≠-230, U.S. Patent 2 ，
133.220, 2+331.132, RITO, 770, 2.177, nonionic compounds such as polyethylene glycols, derivatives thereof, and polythioethers described in US Pat. 20/, 1ll
You may use the thioether compound described in No.-2.

In addition, sodium sulfite, potassium sulfite, potassium bioxide, or sodium bisulfite, which are commonly used as preservatives, can be added.

In the present invention, an arbitrary anti-capri agent can be added to the color developer if necessary. As the antifoggant, an alkali metal such as potassium bromide, sodium bromide, and potassium iodide, a logenide, and an organic antifoggant can be used. Examples of organic anti-foaming agents include benzotriazole, 6-nidropenzimidazole, etc. - ditroisoindazole, j-methylbenzotriazole, j-nitropenzotriazole,! -Nitrogen-containing heterocyclic compounds such as chlorobenzotriazole, λ-thiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, hydroxyazaindolizine and/or -phenyl-y-mercaptotetrazole, comelkabutobenz Mercapto-substituted heterocyclic compounds such as imidazole, comelcabutopenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heterocyclic compounds.

These anti-capri agents may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

The whitening solution or bleach-fixing solution used in the present invention contains an iron complex as a whitening solution. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and their additive role is 0.0/
~/, 0m0L/l preferably 0.0! -0. ! (
7 mot/l. Also.

The fixing agent in the fixer or bleach-fix solution includes thiosulfate. Particularly preferred is ammonium thiosulfate, and the amount added is 0. /-j, Omot/l, preferably 0, j-,2, 0 mol/1. It is common to add sulfite as a preservative, but other
Ascorbic acid, a carbonyl bisulfite adduct, or a carbonyl compound may be added. Furthermore, a 7% buffering agent, a fluorescent whitening agent, a chelating agent, a fungicide, etc. may be added as necessary.

In addition, bromine ions,
In addition to iodine ions, U.S. Patent J7 (7At41,
ct-riot issue, same≠2-atrr6 issue, JP-A-Sho! 3
-3 cores 3! No. j3-3t133, and No. 33-
370/l, thiourea-based compounds as shown in No. 11:, or JP-A-1989-1983/ShirotAyu Section No. 1, No. 11:
3-ta j63/issue, same! r3-67tJI No. 3-
No. 32736, No. j3-61732, No. j'l-jλ
j3≠ and thiol-based compounds as shown in US Pat.
-jrit≠≠, 30-/4tO/λri, j3-
λg≠16, 33-/Hiroshi 1623, 63-10
≠No. 13λ, No. j≠-36727, and Re5ear
Heterocyclic compounds described in ch Disclosure /7/2F, etc., or JP-A-3-2-2013
No. 7, same! No. 2-20132, j3-37≠it issue,
The thioether compounds described in the specifications of J3-P1 Otsu No. 30, JJ-, 210&≠, and jj-λtrot, or the quaternary amines described in the specification of JP-A SHO AT-T≠≠μθ Compounds such as thiocarbamoyls described in the specification of JP-A-Kokai Akihiro Tersan 23≠2, etc. may also be used.゛Example/.

Fuji Photo Film Sin's color negative film HR-/Q
After imagewise exposure of O (x≠ images), the images were continuously processed using the following processing steps using a Fujicolor negative processor FP-Zoo (Fuji Photo Film (ceramic)).

oPJl Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Town Hall
Town - ~ ~ Town
~'l'l'lrri Cli f1
huge ``l'''' ζ foundation
5h turtle h)
5 5\ ) \lv
′+o vine taste ()! (%%
(Note that the water washing process was a two-stage countercurrent water washing from water washing (2) to water washing (2).

In addition, the amount of processing liquid brought in from the front tank of the six tanks was approximately UD per 1.2-diameter image.The prescriptions of each tank liquid and each replenisher are shown below.

<Color developer> Tank liquid Replenisher Sodium nitrilotriacetate i, op i, /1 Sodium sulfite ≠, 09 ≠, μg Sodium carbonate 3θ, Of! Jλ, QI Potassium bromide Hahirop O,71/Hydroxylamine sulfate Ko, Hiro1 2,47/4'-
(N-Ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate ≠, jg r, OP Add water /1 /1pH10,oo
10. or bleaching solution> Tank solution replenishment amount ammonium bromide/60. Ofl/7G,?
Ammonia water C21%) 21,01/ /
r fl ethylenediamine-sodium iron tetraacetate/30. θI/μ31 glacial acetic acid,
l, 0tnl /4 (, add 0rnl water
it 1tpH&,or,
7 <Fixer> Tank liquid Replenishment amount Sodium tetrapolyphosphate λ, op ko, q Sodium sulfite Hiroshi, QI ≠, g Ammonium thiosulfate (70%) /7! , 0rul/P
j, 0rul Sodium Bisulfite Hiroshi, g+
j, H) Add water /l
/1-pH6,G g,g Stable liquid> Tank liquid Replenishment amount Holly I, (hut r
, add 0ml dry well (Fuji Photo Film (manufactured by TJ) a, ord, oat water,
Under the above conditions, the 2-negative film was left untreated for 1 day and then treated for 60 days. Table 1 shows the number of days until floating matter and sediment appeared in the washing tank (2) and the washing tank (2). Similarly, Table 1 also shows the results when various compounds were added to the washing water (tank liquid and replenisher liquid).

Note that the O mark in the table indicates that no floating matter or precipitate was generated even after 60 days of treatment.

According to the present invention (Ifa 6.7, r), the stability of the washing water was significantly improved both in water and during washing.

Example.

After image-wise exposure of Fuji photographic film (Ill color paper)
It was continuously processed using the following processing steps using TOOO (Fuji LA Film 1tIJl'l).

Snow ゛One ＼ The washing process was a three-stage countercurrent washing from washing ■ to washing ■.

In addition, the amount of processing liquid brought in from the six tanks rented in advance was about to - per meter of color paper.

The prescriptions for each tank fluid and each replenisher are shown below.

Color developer> Ri/replenisher Replenisher water too much 100m
1 nitric acid vinegar I
, op benzyl alcohol / Hiro rtrl
/lsl diethylene glycol / Oml
/ Ozl Sodium Sulfite λ, Op
2. Ill Hydroxylamine Sulfate J, 077
J, ill potassium bromide haop
+ Sodium carbonate JOI Jj
lN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl Kazuhiro-aminoaniline-sulfate j, 01/r, 09 Add water (I000*t 1000tntp1.1
10. jj 10.4 Bleach-fix solution> Tank solution Replenisher water 4 LOO scraps 1
4AOO*1 Ammonium thiosulfate (70% soluble) / 10ml 300ml Sodium sulfite
/19 3477 Ethylenediaminetetraacetate iron (III) ammonium jj, 9 /10
9 Ethylenediaminetetraacetic acidφ CoNa! ji 10/
i Add water / 000RI / 0
00RIpi-I 4.7O
A,! 0 70m2 of color paper for 7 days under the above conditions
The samples were treated for 10 days. And washing tank■
Table 4 shows the number of days until floating matter and sediment appear in , ■ and ■. Table 2 also shows the results when various compounds were added to the washing water (tank liquid and replenisher liquid) in the same manner.

Note that the O mark in the table has the same meaning as Example/.

According to the present invention, () to /! -/I), washing water 0), ■,
Not only does the stability of
/r), even in water washing with extremely poor stability, AO
No sediment or floating matter was generated during the day-to-day treatment period.

Claims (1)

[Scope of Claims] In a method of continuously developing a silver halide color photographic light-sensitive material that has been imagewise exposed, the following general steps may be used in the bleach-fixing step or the washing step or stabilization step after the bleach-fixing step. A method for processing a silver halide color photographic light-sensitive material, which comprises at least one compound represented by formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a halogen atom.)