JPS6135445A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance stability of rinsing water or a stabilizing soln. itself without impairing stability of a dye image by incorporating a specified compd. in a rinsing or stabilizing step after a bleaching step and a fixing step or a bleach- fixing step. CONSTITUTION:The rinsing or stabilizing step following the bleaching and fixing steps or the bleach-fixing step uses, preferably in an amt. of 1X10<-5>-1.0mol/l of rinsing water or stabilizing soln., at least one kind of compds. represented by the formula in which R1 is 1-6C alkyl, preferably, 3-6C alkyl, and R2 is 1-20, preferably, 10-18C alkyl, and X is halogen, preferably, Cl or Br. This compd. is effective for the rinsing water or stabilizing soln. contg. iron ions and thiosulfate and kills bacteria and mold contained in them to more enhance the stability of them.

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 particularly to a processing method that can significantly reduce the amount of water used in a water washing process and the like.

(Prior art) Traditionally, the processing process for silver halide photographic materials includes a washing process and a stabilization process. It has been suggested that the water ti should be reduced. For example, S, R,
, Goldwasser.

'Water Flow Rates in I
mmersion-Washing of Motion
n Picture FilmSMPTEju, pa
ge211g~2Ai3, (May.

/9! According to ;j), a method is proposed in which the amount of washing water is reduced by making the washing tank multistage and causing the water to flow countercurrently. This method has been adopted in various automatic processors as an effective means for saving water. However, the washing water is very unstable as it contains iron ions from the bleaching process and thiosulfates from the fixing process.
It has been found that if the amount of water used for washing is significantly reduced, the residence time of the washing water becomes longer, causing new problems such as the generation of various types of sediment and suspended matter.

This problem also occurs when the water washing step is replaced with a stabilization step, or in the stabilization step following the water washing step.

These sediments and floating substances adhere to photosensitive materials, clog or stain the filters of automatic processors, and cause various troubles.

In order to solve these problems, many precipitation prevention means have been proposed. For example, L, EWe s t +
"'Water Quality Cr1teria"
Phot, Sci, and Eng, vol. J
J(/rit) describes the addition of chelating agents and bactericides.

Also, Japanese Patent Publication No. 7-4!4A2, JTT-10JL
Guj issue and the same! 7-/! No. 72114A describes the addition of various anti-piping agents such as thiazolylbenzimidazole compounds and isothiazolone compounds, but there are cases where the solubility is poor, there are safety issues with the compounds, or there are problems with preventing precipitation. Satisfactory results have not been obtained because the effect is opaque. In addition, as a method of adding various chelating agents, Japanese Patent Application Publication No. 4T4C, No. 2, J-7-
jl/113, 17-/32/ZAA, II-
No. 143/, etc., but all chelating agents have insufficient effects or have an adverse effect on image storage stability, so that no satisfactory results have been obtained.

Further, as a method of using sulfite and a chelating agent in combination, JP-A-17-97130, JP-rff73f and J
However, the 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 prevent the washing water or stabilizing solution from impairing the stability of dye images even when the amount of washing water or stabilizing solution is significantly reduced or when the need for replenishment is greatly reduced. The goal is to improve the stability of

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

In the formula, R1 represents a C1 to C6 alkyl group, but C3
~C5 alkyl groups are preferred. In addition, the alkyl group is
It may be substituted with a halogen atom (chlorine atom, bromine atom, etc.), a hydroxyl group, or the like. Further, R1 may be all the same or different from each other.

R2HCl represents an alkyl group of C20. This alkyl group can be a halogen atom, a hydroxyl group (chlorine atom, bromine atom, etc.), a carboxyl group, a sulfonic group, a phosphonic acid group, an acyno group, etc. = It is okay if some parts of the head have been changed. Especially C1G"'-'C1
The alkyl group of 8 is preferred.

X represents a halogen atom, such as a fluorine atom, a chlorine atom,
They are bromine and iodine atoms. Particularly preferred are chlorine atom and bromine atom.

By using the compound represented by the above general formula (1), the precipitates and suspended matter generated in the washing water or stabilizing solution can be removed.
This could be effectively suppressed without adversely affecting the photographic properties (for example, the stability of the dye image was not significantly affected, staining was not significantly generated, etc.). In particular, 7ICF water washers containing iron ions and thiosulfate coexist.
The compounds of the present invention are effective against i-stabilized solutions.

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, decomposition of thiosulfate by sulfur bacteria, turbidity due to bacterial colonies, and mold growth were found to be the central mechanisms of precipitate formation.

A- Therefore, it has been found that the stability of the washing water and stabilizing solution can be further improved by sterilizing bacteria and mold in the washing water and stabilizing solution. That is, as a result of examining the addition of various antibacterial agents and antifungal agents (anti-pepper agents), the present inventors found that the compound of the general formula (I) specifically promotes the stabilization of the washing water stabilizer. I have come to the conclusion that this is the case.

Further, the compound of the present invention is a more preferable compound in terms of safety, and has high water solubility, so it is a preferable compound to be used as washing water or a stabilizing liquid.

Specific sequences of general formula (1) are shown below, but are not limited to these.

Some of them are commercially available and can be easily obtained. For example, it is commercially available as Berculin 3rO (Chipakaigy Co., Ltd.).

The amount of the compound of general formula (I) to be added is preferably 1X10-5 to 1 per washing water or stabilizing solution/71.

mol L is preferably lXl0-4~. Z×10−
It is 2 mol.

In the washing water or stabilizing solution of the present invention, iron salt as a bleaching component and thiosulfate as a fixing component are inevitably extracted from the pre-bath (bleach bath, fixing bath, bleach-fixing bath) due to continuous processing. brought in. These contents may vary depending on washing or stabilization methods.
Although there are differences, the iron concentration is tX/o-6~/
X/ o-1 mol/l! % good tL<i, 1xlO-
5~jxlO-2 mol/l, thiosulfate concentration: lXl0-4~. tX/0" mail/l preferably lXl0-3~JX/0" mail/I
It is I.

In addition to the compound represented by the general formula (1), other antibacterial agents and antifungal agents (anti-pepper agents) may be used in combination with the washing water or stabilizing liquid of the present invention.

For example, as an anti-piping agent, JP-A-77-1Jt724A≠
Thiazolylbenzimidazole compounds as shown in No. and No. 1g'-10, lXl1j, isothiazolone compounds as shown in JP-A-57-rtμ-, or trichlorophenol. Female lolophenol compounds or bromophenol compounds.

Alternatively, organic tin or organic zinc compounds, thiocyanic acid or isothyanic acid compounds, acid amide compounds, diazine or triazine compounds, thiobase compounds, alkylguanidine compounds, or benzalkonium General-purpose anti-inflammatory agents such as grade ammonium salts such as chloride or antibiotics such as penicillin may be used in combination. 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 '2 with. Or, E. West, “Water
Quality Cr1teria'Photo, Sci
, and Eng,, vol. A6 (/ta47)
You may add the compound described in etc.

In addition, 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).
Examples of chelating agents include aminopolycarboxylic acid-based, phosphonocarboxylic acid-based, alkylphosphonic acid-based, and aminopolyphosphonic acid-based chelating agents.

Among them, % l-hydroxyethylidene-l,/-diphosphonic acid, nitrilo-N,N,N'-trimethylenephosphonic acid, and ethylenediamine-N.

It is preferable to use N,N',N'-tetramethylenephosphonic acid in combination. The concentration of these chelating agents is
l per tylxio-5~/X/(7-tmall Preferably, /'l!, 10 4~/x10-2mall
It is.

The washing 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 washing water required is approximately j0ml/000rnl per m2 of color photosensitive material.

Also, the amount of water for flushing varies depending on the number of flushing tanks, so please see S, R@Godwasser, @WaterFl for details.
ow Rates in Immersion-W
ashingof Motion Picture F
i1m'8MPTE.

A 4', page, 2 It f ~ 2 r J
, May (/ri11).

The pH of the washing water in the present invention is usually around 7, but may reach pH 3 or higher due to the pre-bath retention. In addition, the water washing temperature is preferably j-μ00C1 and 1O0.
C~3j0C. 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 providing the water washing step.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. As a representative example,
Examples include a liquid having a buffering capacity of pH 3 to O, a liquid containing aldehyde (for example, formalin), and the like.

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

From the purpose of reducing the water outlet of the stabilizer, 2~! A multi-stage countercurrent system is preferred.

Even in this case, the required amount of stabilizing liquid is approximately j OmB to /000rnl per m2 of color photosensitive material.

In addition, the liquid temperature of the stabilizing liquid ζs, ao 'c, preferably lθ
It is 0C to 3!0C. If necessary, a heater, weave controller, circulation pump, filter, floating pig, squeegee, etc. may be installed in the stable tank.

The processing method of the present invention can be applied to any processing of general silver halogenide color photosensitive materials such as color negative film, color converter, color positive film, color reversal film, etc., but it is particularly applicable to color converter ξ- and color negative films. It is preferable that

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

A. Color development - bleach-fixing - washing and drying B. Color development - bleach-fixing - washing and stabilizing - drying C. Color development - washing, bleaching, fixing, washing, drying, color development - bleaching, constant washing, stabilizing, drying E, color development - bleaching, constant washing, washing, drying F, color development - washing - washing, constant bleaching, 1 Washing with water and drying Here, "washing with water" is a "stable" pre-bath in %B%D
may be removed.

The colored liquid used in the present invention contains colored chestnuts. Preferred examples are p-phenyl 3-diamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-/N,N-diethyl-p-) unilene diamine D-22-diamine, diethyl minotoluene])-3,2-diamine,! t-(N-Ethyl-N-Lauryl Ryomino)Toluene D-gu Gu [N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-j, 2-methyl-4Z-[N-ethyl-N −(β−
hydroxyethyl) aminocoaniline D-AN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-guaminoaniline D-7N-(,2-diethylaminophenylethyl)methanesulfonamide D-4N, N-dimethyl-p-phenylenesia/≠
- Mine D-ta t-amino-3-methyl-N-ethyl-N-methoxyethylaniline 1)-IOll, -amino-3-methyl-N-ethyl-
N-β-ethoxyethylaniline])-//11. -amino-3-methyl-h-ethyl-
These p-phenylenediamine derivatives can be used in the form of salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The above compound is disclosed in US Pat.
, No. 013, same co, ! 32.

, 2hiro 1 issue, same co, jJJ, , 27/ issue, same co,
2, 31.11, 3.7J [, Riso issue, 3゜6
It is described in issues such as yr, r, and 2z. The aromatic-grade compound is used in a developer solution of approximately O0/g.
~about, zog, pvc good-zshi < rts about o, sg to about iog.

The color image solution used in the present invention may contain hydroxylamine, as is well known.

Although hydroxylamines can be used in the form of free amines in the color solution, 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. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The color developer used in the present invention preferably has a pH of ~1, preferably ~//, and the color developer may contain other known developer component compounds. can be included.

For example, as the alkaline agent and pH buffering agent, caustic soda, caustic potash, soda carbonate, potassium carbonate, tertiary sodium phosphate, tertiary potassium phosphate, potassium metaborate, boric acid, 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 that sodium hydrogen phosphate or potassium, potassium or sodium phosphate λ hydrate, sodium bicarbonate or potassium, boron, etc. Various salts are used, such as acids, alkali nitrates, and alkali sulfates.

In addition, various chelating agents can be used in the color phenomenon solution to prevent precipitation of calcium and magnesium. For example, polyphosphates, aminopolycarboxylic acids,
Phosphonocarboxylic acids, aminopolyphosphonic acids, l-
Examples include hydroxyl-kylidene/,/-diphosphonic acids.

If necessary, any development accelerator can be added to the color developing solution. For example, various pyrimidiram compounds and other cationic compounds, such as phenosafranin, are typified by U.S. Pat. Cationic dyes, neutral salts such as thallium nitrate and potassium nitrate, US Pat.

, t3i, t3x, same co, riso, ri7o, same J
, 177.127, non-ionic compounds such as polyethylene glycol and its derivatives, and polythioethers, as described in US Patent No. 3. ．． The thioether compounds described in No. 201.2μ2 may also be used.

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

In the present invention, an optional antifoggant can be added to the color developer as necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium chloride, potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include benzotriazole, 6-nidrobenzimidazole, and! - ditroisoindazole! -Methylbenzotriazole, j-nitrobenzotriazole,! -Nitrogen-containing heterocyclic compounds such as chloropenttriazole, cochinazolylbenzimidazole, cochiazolylmethylbenzimidazole, hydroxyazaindolizine, and l-phenyl-
! -Mercapto-substituted heteros such as mercaptotetrazole, comelcabutobenzimidazole, and mercaptobenzothiazole! compounds, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid.゛Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developing solution.

The bleaching solution or bleach-fixing solution used in the present invention contains an iron complex as a bleaching solution. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amounts added are o, o
i~i, omol/l preferably o, o r, o
, s Omol/l. Further, thiosulfate is included as a fixing agent in the fixing solution or bleach-fixing solution. Particularly preferred is ammonium thiosulfate salt, and the amount added is 0, /-, t, Omol/l, preferably Fio, z-x, Omol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound may be added. Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

In addition, bromine ions,
In addition to iodine ion, U.S. Patent No. 37013411 Special Publication AS
-grot number, tter number 26316, JP-A-Shoj3-3
No. 2731, tJ-34, 233, and 13-
370/l, the thiourea-based compound shown in the specification, or JP-A-33-/J-Hiroshi≠24! No., same j3-
Ta JA No. 31, tJ-37131, tJ3-32
No. 73, No. 33-6j732, U.S. Patent No. 33-6j73, U.S. Pat. tμμ, 10-/4AO/Kota, j3-2g4
L26, same! 3-/≠/No. 123, 13-10u,
No. 232, j≠-31727, and Re5earc
h Disclosure / 7/, No. 22 Specification il
: Heterocyclic compounds described in, etc., or JP-A-3-2
4!9.27, same j, 2-ko or 32, same 33-3
No. 7uIr, No. 13-93-1.30, j3-λr
otj No. 11-21,104, etc., or JP-A-Sho <zr-rμ
Compounds such as quaternary amines described in the specification of ≠UO or thiocarbamoyls described in the specification of JP-A No. 23μ may also be used.

Example 1 Color negative film HR manufactured by Fuji Photo Film ((T))
After imagewise exposure of -100 (217 shots), the following processing steps are carried out using Fuji Color Negative Processor 1'p-zoo (Fuji Photo Film (copper)).
Degree color development process 3//II 31 'C±
0.3°C bleaching process at2oz
3t 'C±3 °C Fixing process 3/Ijt1
31'C±3°C water washing ■ /1301
33 °C ± 3 °C water washing ■ -
'00 33 °C±36C stable process ≠01
7♂00±3°C Tank capacity Replenishment amount (11 meters) Co/l ≠j itH2゜/lri JriH-rl, 2゜1373 3.The water washing process is two steps from water washing ■ to water washing ■ Countercurrent water washing was used.

In addition, the amount of processing liquid brought in from the front tank of the 6 tanks is approximately 2 times per 24A shot.

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

<Color developer> Tank liquid Replenisher Sodium nitrilotriacetate 1. Oll /, 19 Sodium sulfite 4.0g μ, 4! g Sodium carbonate 30. Ofi 32,09 Potassium Bromide
1. Reference g O, 7g hydroxylamine sulfate Ko Mamoru J Ko, B Hiro-(N-ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate a, zg z, og Add water /lll1l-+23 - H <Bleach solution> Tank solution Replenishment amount Ammonium bromide 140.09 /7A9 Aqueous ammonia (t%) 21. Og /j ethylenediamine-tetraacetic acid sodium iron salt /30. Oll /≠3g glacial acetic acid /11.0rtJ Add 111.0ml water ll /73pHl
,,θ J,7 <Fixer> Tank liquid Replenishment amount Sodium tetrapolyphosphate -0092#i Sodium sulfite a, og μ, μg Ammonium thiosulfate (70%) /71.0ml/93.0ml Sodium bisulfite 44.49 j, add 1g water /71 11pH414,
J-2 Goo (stabilizing liquid) Tank liquid Replenishment amount E/lz Marine r, Oml r, 0r
nl drywell u, 0ral It,
0 m1 (manufactured by Fuji Photo Film 1 Co., Ltd.)) After adding water, the color negative film fI day aO main processing (~, 1
The treatment was carried out for 0 days. Table 1 shows the number of days in which floating matter and precipitates were generated in the washing tank (■) and the washing tank (■). Similarly, Table 7 also shows the results when various K compounds were added to the washing water (in the tank solution and replenisher solution).

-2- According to the present invention, (A A * 7m'), water washing ■
The stability of the rinsing water was significantly improved both in .

Example Fuji photographic film (copper color paper) After exposure, Fuji Color Bark Processor FMPP-/
000 (manufactured by Fuji Photo Film Co., Ltd.) and was continuously processed in the following processing steps.

−,27− D time temperature
Wash twice ■ 4401 33 °
C±3 °C Tank capacity refill amount (tnl/m2) rH1ti 3j71 AO 171. 2J0 Note that the water washing process was a three-stage countercurrent water washing from water washing (■) to water washing (2).

The amount of processing liquid brought in from the various front tanks was approximately AOmB per 7.2 sheets of color paper.

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

<Color phenomenon 1 liquid> Tank liquid Replenishment liquid water r 00ml
za00rnl Nitrilotori Vinegar W1・j Na −
2,092,0g benzyl alcohol lJm
e /♂-diethylene glycol / 0
ryl: / 0m13 Sodium sulfite
Co, Og 2.5g Hydroxylamine sulfate
3.09 3.3g potassium bromide i,
og - Sodium carbonate 30g
3! flN-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-l-aminoaniline sulfate s, og r, ogpH
10,/! 10. tJ <Bleach-fix solution> Tank solution Replenisher water l10Orne
u00ml ammonium thiosulfate (70% solution) /jOml 3θOn
l Sodium sulfite l♂g 3t9 Ethylenediaminetetraacetic acid iron (ml) Ammonium szg 110g Ethylenediaminetetraacetic acid CoNa jfi 10f
i Add water 10100O/θ00m1
pHA, yo A, t.

Under the above conditions, color paper was processed for 10y12 days, and processed for 12 days. Table 2 shows the number of days until floating matter and sediment appeared in the washing tanks (2), (2), and (2). In the same way, wash water (in tank liquid and replenisher liquid)
Table 2 also shows the results when all of the various compounds were added.

-3l- According to the present invention (bian is, iB, washing water ■).

The stability of ■ and ■ is not only significantly improved, but also suitable for use in combination with other anti-piping agents and chelating agents (A/A-
/I), even in water washing with extremely poor stability, to
No sediment or floating matter was generated during the 1-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) (R_1)_3P^■-R_2X^■ (In the formula, R_1 represents an alkyl group of C_1 to C_6, and R_2 represents an alkyl group of C_1 to C_2_0. X represents a halogen atom.)