JPS6147958A - Treatment of silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the stability of washing water and stabilizer by exposing a silver halide color photosensitive material then subjecting continuously the material to developing, bleaching and fixing and adding acetoamide halide to the washing water or stabilizer in the stage of subjecting the photosensitive material to the washing or stabilizing process thereafter. CONSTITUTION:A latent image is taken by exposing a color negative film, color paper, etc. The film or paper is thereafter fed continuously to developing, bleaching and fixing process stages. The film or paper is then subjected to the washing or stabilizing process. The compd. of XCH2CONH2 (where X is halogen), for example, BrCH2CONH2 or the like is added to said process stage. The air oxidation of the thiosulfate in the washing water or stabilizer and the settlement of iron ions by iron bacteria are prevented by the addition of such compd. A chelate agent, etc. may be added together with said compd. The processing water for the washing process and stabilizing process is thus stabilized, the formation of the precipitate and suspended matter is suppressed and the processing water is considerably economized.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a processing method for silver halide color photographic light-sensitive materials, and in particular relates to a processing method that can significantly reduce the amount of water used in the washing process and the like. be.

(Prior art) Traditionally, the processing process for silver halide photographic materials includes a washing process and a stabilization process. Directions have been suggested to reduce the amount of water it. For example, S, R
,Goldwasser+@Water Flow R
ates in immersion - Wash
ing of Motion Picture File
m"SMPTE, 444, pag6J4cr-koj3,
(May.

1yzz) proposes a method of reducing the amount of water used for washing by arranging the washing tank in multiple stages and causing the water to flow countercurrently. This method has been adopted in various automatic processors 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 discovered that the residence time is long and new problems arise, such as the generation of various types of sediment and suspended matter.

Such problems also occur when the water washing step is replaced with a stabilization step, or when the stabilization step (C) follows the water washing step.

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

In order to solve these problems, many (precipitation prevention means) have been proposed. For example, L, EWest, "W"
ater Ouamety Cr1teria"Photo
, Sci, , and Eng, +volta 4. <(/
26) describes the addition of chelating agents and fixicides.

Also, JP-A Shoyo 7-4 JIA No. 2, same tr-ioz/lI
-Yo issue and Doyo 7-/j7 Ko Hirohiro issue describe the addition of various anti-piping agents such as thiazolylbenzimiguzole compounds and isothiazolone compounds, but they have poor solubility and Satisfactory results have not been obtained due to problems with the safety of the compound or insufficient precipitation prevention effects. Also, as a method for adding various chelating agents, see JP-A-77-1R! No. 4c, same j7-rr/
≠No. 3, same! 7-/, 32/II-, same j-r-/
No. 1 & 3/, etc., but all of the chelating agents are insufficiently effective or have an adverse effect on image storage stability, resulting in unsatisfactory results.

Furthermore, as a method of using a sulfite and a chelating agent in combination, Japanese Patent Application Laid-open Nos. 7-97JJO, 6F-41731, and JP-A-Sho! However, the effect is still insufficient.

Accordingly, 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 completely suppress the formation of precipitates and suspended matter in washing water or stabilizing liquid.

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

(Structure of the Invention) For the above-mentioned purpose, in a method of continuously developing a silver halide color photographic light-sensitive material that has been imagewise exposed, stabilization is provided over a bleach-fixing step or a washing step after a bleach-fixing step. It has been found that this can be effectively achieved by including at least one of the compounds represented by the following general formula (I) in the chemical conversion step.

General formula (IN

Precipitates and suspended solids generated in washing water or stabilizing liquid by using the compound represented by the above general formula (I),
In particular, iron ions and thiosulfate The compounds of the present invention are effective in water washing and water stabilizing solutions in which salts coexist.

As a result of analyzing the precipitation mechanism of washing water and stabilizing solution in which iron ions and thiosulfate coexist, the present inventors found that the air oxidation of thiosulfate using iron ions as a catalyst and the iron ions caused 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 for precipitate formation.

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 (1) specifically promotes the stabilization of the washing water stabilizer. This is what I discovered.

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

F-CH2C0N)i 2 ■−λ α-CH2CONH2 Br CH2CONH2 ■-Hiroshi l-CH2CONH2 Among the compounds of general formula (I), l-j is particularly preferred.

The compound represented by the general formula (I) is a known compound, can be easily synthesized, and is commercially available, so it can be easily obtained.

The amount of the compound of general formula (I) to be added is preferably from jXlo-5 to i per liter of washing water or stabilizer.

mol More preferably 1-l/X10-2X/(f
It is 2 mol.

Iron salt as a bleaching component and thiosulfate as a fixing component are inevitably brought into the water washing and water stabilizing solution of the present invention from the previous bath (bleach bath, fixing bath, bleach-fixing bath) through continuous processing. . These contents differ depending on the water washing or stabilization method, but depending on the iron concentration, /X10 −/×1
0 mol/11° Preferably, /×10 −j
xlo mol/no, as thiosulfate 0 degrees/X1
0 -jXlo-'mol/l preferably H/x1
0 −JXlo mol/l.

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

For example, JP-A No. 77-/672 Hiromu and J-1r-10j/Hiro! are used as anti-piping agents. Una, thiazolylbenzimidazole compounds as shown in the No. 1, inthiazolone compounds as shown in JP-A No. 7-r1 Hiroλ, or lolophenol compounds as represented by trichlorophenol. or bromophenol compounds, or organotin or organozinc compounds, or thiocyanic acid or thianic acid compounds, or acid amide compounds, or diazine or triazine compounds, or thiourea compounds. It is better to use a general-purpose anti-pipe agent such as alkylguanidine compounds, μ-class ammonium salts such as benzalkonium chloride, and antibiotics such as penicillin. In particular, combination use with thiazolylbenzimidazole compounds and isothiazolone compounds is preferred.

In addition, various compounds may be added to the VC water in 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, and fluorescent brighteners to improve whiteness.
Sulfite as a preservative, bismuth salt to promote chelation with iron, etc. can be added as necessary. Or ttl L, E, West t, @Wat
Cr Oua 1 i ty Criteria'Ph
ot, Sci@and Eng,, vol. 16 &
(Compounds described in /96 etc. may be added.

Further, in the washing water of the present invention, it is preferable to use various cleaning agents in addition to the compound of general formula (I). Examples of the chelating agent used in combination include inorganic phosphoric acid-based, organic carzenic acid-based, aminopolycarboxylic acid-based, phosphonocarboxylic acid-based, alkylphosphonic acid-based, and aminopolyphosphonic acid-based chelating agents. Among them, l-hydroxyethylidene/,/-diphosphonic acid, nitrilo-
A combination of N 1 hetrimethylenephosphonic acid and ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid is preferred. The concentration of these rate agents added is jXlo ~/×lOmo per liter of washing water.
l preferably fl/X10 −/X10”-2mn
It is 1.

The washing method used in the present invention has the purpose of reducing the amount of water used for washing. A countercurrent flushing system in the tank is preferred. In this case, the amount of water required for washing is approximately 1/m of color photosensitive material! Ogo~1000rrtl.

In addition, the flushing water and meter differ depending on the number of flushing tanks, so
Details, S.R. Godwasser, “WaterF
low Rates in Immersion-
Washingof Moti□n Picture
Fi1m' SMPTE +111-1l11-1p
a! −, 2jJ, May(/Fjj).

The pH of the washing water in the present invention is usually around 7, but it may reach p)IJ~-2 due to the pH of the washing water brought in from the previous bath. Also, the water washing temperature tar-tAo'c.

Preferably [10'C to jj'c. as needed,
A heater, temperature controller, circulation pump, filter, floating pig, squeegee, etc. may be provided in the washing tank.

The stabilization process used in the present invention may be performed after the water washing process, or may be performed immediately without removing the gold film from the water washing process.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. Typical example is t'z
, a solution having a buffering capacity of pH 3 to O, and a solution containing an aldehyde (for example, formalin).

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 stabilizer, 2~! A multistage countercurrent system consisting of tanks is preferred. In this case as well, the required stable i amount is approximately rernl- per m2 of color photosensitive material.
It becomes 1000ml.

Also, warm up the stabilizer liquid! ~≠o 'C, preferably tri
o°C to 3!0C. 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 the general silver halide color photosensitive materials such as color negative film, color paper, color positive film, color reversal film, etc., 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.

A, Color development - Bleach fixing - Water condition - Drying B. Color development - Bleach fixing - Washing - Stable - Drying C. Color development - Washing - Bleach fixing - Washing - Drying. 1 drying E, color development - constant bleaching 1 washing 1 drying F, color development - washing with water 1 bleaching 1 washing 1 drying Good too.

The color developer used in the present invention contains a color developing agent. A preferred example is tffp-7, a 22-diamine conductor, and representative examples are shown below, but the invention is not limited thereto.

1)-/N,N-diethyl-p-phinidinecyabane D-2,Z-amino-y-diethylaminetoluene D-32-amino-j-(N-ethylhelaurylamino]toluene D -Hirohiro-[H-ethyl-N-(β-hydroxyethyl]amino]aniline D-J'-monomethyl-Hiro-[N-ethyl-to-(β
-hydroxyethyl)amino'aniline D-AN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-Hiroshi-aminoaniline D-7N-(J-amino-yo-diethylaminophenylethyl)methanesulfonamide ])-4N,N-dimethyl-p-phenylenediacine D-2 Hiro-amino-3-methyl-N-ethyl-N-methoxyethylani+77 D-io Hiro-amino-3-methyl-N-ethyl- he-β-ethoxyethylaniline])-// Hiro-amino-3-methyl-N-ethyl-
N-β-Butoxyethylaniline These 1)-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The above-mentioned compound is disclosed in US Patent λ, l J, No. 0/j, U.S. Patent λ, j! λ.

λμ1, same λ, ztt, core 1, same λ, j octopus, 3
No. 44C, J, Ar1.910, No. 3°t,
It is written in the Yoλyo issue, etc. The amount of the aromatic-grade amine developing agent used is about 0.0. /p~aboutcoop
, more preferably 0 degrees from about o, zI to about io, 51.

As is well known, the color solution used in the present invention may contain hydroxylamine at-.

Although hydrogynylamines 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. The hydrodonylamines may be substituted or unsubstituted (the nitrogen atom of the hydrodonylamines may be substituted with an alkyl group).

The color developer used in the present invention preferably has a pH of 1 pH 2.
~ lλ, more preferably 2 ~ / / , 0, and the color developer may contain other known developer component compounds.

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, borax, etc. are used singly 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 , alkali nitrate 1
Various salts are used, such as alkali halosulfate.

In addition, various intermediate rate agents can be used in the color developer to prevent precipitation of calcium and magnesium. For example, there are polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, l-hydrophosphonic acids, diphosphonic acids, diphosphonic acids, and diphosphonic acids.

Any development accelerator can be added to the color developer if necessary. For example, various pyrimidylam compounds represented by U.S. Patent Neutral salts such as thallium nitrate and potassium nitrate, Special Publication Show μμm JO4c, US Patent λ,! ! ! , Tata O, the same.

13/, No. 132, λ, yro, No. 270, λ,
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 77/27,
US patent! , 20/, thioether compounds described in Lambda Ko No. 2 may 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 arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, alkali total halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, and! -Nitroisoindazole, j-methylbenzo I liazole,! -Nitrobenzotriazole,! -chlorobenzotria/-
Nitrogen-containing heterocyclic compounds such as L, 2-f azolyrubenzimiguzole, 2-thiazolylmethyl-benzimidazole, hydrodiazaindolizine, and l-phenyl-j-mercaptotetrazole, λ-mercaptobenzimidazole, 2 Mercapto-substituted heterocyclic compounds such as -mercabutobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. 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 developer.

The bleaching solution or bleach-fixing solution used in the present invention contains an iron complex as a bleaching solution. Among iron complexes, aminopolycarboxylic acid iron complexes are preferred, and their addition tt40,
0 /-/', Omol/l tL<pl O, Oj
= 0, j 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 its addition amount is t40, /-j, 0rnol/j, preferably t4o, s-λ, 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. 370/, J61, Japanese Patent Publication No. 4
ct-rsot, Interchanger 26616, JP-A-J
-3,27JJ, J'3-J4λ3'3, and JJ-370It, or JP-A-63-/21AIA21t,
same! J-4143/No. 13-471rJI No. 6
3-3u7JG No. 63- & J-732 No. 3-3u7JG No. 63- & J-732 No. 3-3u7JG
521314 and U.S. Pat. No. 3,113,131, etc., or JP-A-Kokai Akoter syt Hiromu, JP-A-Ko-/Ko-0/Kota-No., JP-A-KOKAI!
No. 3-21rlA2, No. j3-/41423, No. 232 to 3-101, No. j4cm3j7λ7, and Re5earch Disclosure / 7/
2? Heterocyclic compounds of No. La books, etc., or JP-A-F@! 3-2≠227, same j2-20rJJ,
Same j3-371A/I, same JrJ-4j630, same! ! --jO & Hirogo, and the same! ! -2t! The thioether compounds described in Specification No. 06, etc., or JP-A Akihiro
Compounds such as the quaternary amines described in -r≠Hirohiro Q specification or the thiocarbamoyls described in JP-A-2-IA234 may also be used.

Example l Color negative film HR-10 manufactured by Fuji Photo Film ■
After 0 (ZIA photographing'Jf imagewise exposure), the film was continuously processed in the following processing steps using a 7-dicolor negative processor B'p-too (manufactured by Fuji Photo Film ■).

Electric) C-) UQ (p Yutsuki Mai Ward + o + Moq Uta Takashi Kaname Ku Ku □□□In addition, the washing process was a step countercurrent washing from washing ■ to washing ■.

In addition, the amount of processing liquid brought in from the front tank of each tank was about 2 trtl per -μ image taken.

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

Ku color present @! Liquid〉 Tank liquid Replenisher Sodium nitrilotriacetate i, op Ha/Sodium sulfite μ, op tA, Hiroy Sodium carbonate 30.09 32. Ofi Potassium bromide Halg O, 79 hydroxylamine sulfate Ko, Li λ, tI Hiro-(N
-ethyl-to-β-hydroxyethylamino]-λ- methylaniline sulfate 11J9 J,Qi Add water /l /73pHio,oo
io, or bleaching solution> tank solution replenishment amount ammonium bromide it, o, og lyt
g Ammonia water (λt%) 2j, og
is ethylenediamine-tetraacetic acid sodium iron salt /30.09 /Hiro J, 51 glacial acetic acid /Hiro, Oml /IA, Oa
t Add water /l /1p)l
6. Oj, 7 Fixer > Tank liquid Replenishment amount Sodium tetrapolyphosphate 2.0g 2.2g Sodium sulfite Hiro, Og Hiro, Hiro I Ammonium thiosulfate (70%) /7J-0Oml /
3.0rIL1 Sodium bisulfite μ, tg
z, ig Add water /l
/1p) l iA ijku Stabilizing liquid> Tank liquid Replenishment amount Formalin r, 0rnl r, 0
Butrywell (manufactured by Fuji Photo Film ■) tA, oml Hiroshi, O
The color negative film was processed for 1 day and then for 2 days under the above conditions with the addition of water and the above conditions. The number of days until floating matter and sediment appear in the washing tank (■) and the washing tank (■) is shown in Table 1. Similarly, Table 1 also shows the results when various compounds were added to the washing water (tank liquid and replenisher liquid).

Note that the mark B in the table indicates that no floating matter or precipitate was generated even after the treatment for days.

According to the present invention (44.7, l, ri), the stability of the washing water was significantly improved in both washing (①) and washing (③).

Example 2 After imagewise exposure of color paper manufactured by Fuji Photo Film
The film was continuously processed using the following processing steps using 0 (Fuji Photo Film ■1R).

啄υ Noodles ″ uuuu 勺 町 町 勺 町 勺 - honor, humiliation, resemblance
Note that the water washing step was a three-stage countercurrent water washing from water washing (①) to water washing (③).

Furthermore, the amount of processing liquid brought in from the various front tanks was about toy per color paper/WL2.

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

Color developer> Tank liquid Replenisher water royal
100rd2) IJ H triacetic acid-JNa 2.
017 2,09 Benzyl alcohol 1 /r Godiethylene glycol iom
t 10 Sodium sulfite 109
2. xi Hydrondylamine sulfate! ,09
J, j9 potassium bromide 1.09
+ Sodium carbonate JOII 3j
17N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-aminoaniline sulfate 10jif, Oj9 Add water 1000111 10001!
IIp)1 10. /j
10. &! <Bleach-fix solution> Tank solution Replenisher water ll-001jtl
u00111 Ammonium thiosulfate <70% m solution) /! Oml JOOOr
n1 dish fC acid sodium ff9 36
17 Ethylenediaminetetraacetic acid iron (■) ammonium Yozzi /1077
Add ethylenediaminetetraacetic acid/JNa rpiog water to 1000tul 1000r
dpH4, 70t, JO Color paper f1 day, 10m2 processed under the above conditions,
The treatment was carried out for to days. The number of days until floating matter and sediment appear in the washing tanks ■, ■, and ■ is shown in the table. Table 1 also shows the results when various compounds were added to the washing water (tank liquid and replenisher liquid) in the same manner.

Mizumoto IJIIVc! h < 1th ~ it), the stability of the washing water ■, ■, ■ is significantly improved (,
(71
Even in water washing (6/6~it), which had extremely poor stability, no precipitates or suspended matter were generated during the treatment period of 2 days.

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)