JPS6135447A - 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 kinds of compds. represented by the formula in which each of R1-R4 is independently H or alkyl, preferably, one of them is 5-20C alkyl and the other 3 are H, and X is an acid, preferably, such as nitrous, nitric, or chloric acid. Accordingly, the stability of the rinsing water or the stabilizing soln. itself can be enhanced without impairing the stability of a dye image and said compd. is especially effective when the water or the soln. contains ferric ions and thiosulfate.

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 water t-e in washing steps and the like. be.

(Prior art) In the processing process of silver-genide photographic photosensitive materials, washing, drying, and stabilizing processes are required. Due to this problem, it has been suggested that the amount of water such as the amount of water used for rinsing should be reduced. For example, 8. R,
Qoldwass6r.

''Wat6rF'low Rates in
Immersion-Washing of
Motion picture film “SMP
TE, j 4', page, 24 (f ~2 evening 3, (
May/Tata i), the washing tank should be multi-tiered.
A method has been proposed in which the amount of water used for washing water is reduced to t' by causing the water to flow countercurrently. This method has been adopted in various automatic processors as an effective means for saving water.

However, washing water containing iron ions from the bleaching process and thiosulfate from the fixing process is extremely unstable, 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 various types of sediment and suspended matter 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 cause Q adhering to photosensitive materials, clogging, dirt, and potash in the filters of automatic processors, and various other troubles.

In order to solve these problems, many precipitation prevention means have been proposed. For example, L,EWest+”Wa
ter Quality Cr1teria'Photo
,Sci,,and Eng,,vo19AA (/
The addition of chelating agents and bactericidal agents is described in (Ret.).

In addition, %Kaisho Tafu F≠λ No., Tafu R-1091≠Even No. and Tafu/Tuff, No. 2≠ include various anti-puff agents such as thiazolylbenzimidazole compounds and isothiazolone compounds. However, satisfactory results have not been obtained due to poor solubility, problems with stability of the compound, or insufficient precipitation prevention effect. In addition, methods for adding various chelating agents are described in JP-A-97-11112, JP-A No. 17-TR/A3, TAFU/3COL ≠≦, JP-A-1989-11112, No. 63/, etc. However, none of the chelating agents have been sufficiently effective or have had an adverse effect on image storage stability, so no satisfactory results have been obtained.

Also, as a method of using sulfite and a chelating agent in combination, JP-A-1987-'? Although it is described in No. 7r30, No. +9-41731, and Tatar Gza No. 732, 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 provide a solution to 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 significantly reduced. The goal is to improve its stability.

(Structure of the Invention) The above 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 including at least one compound represented by the following general formula (I) in the process.

General formula (1) In the formula, R1, R2# Rs and R4 may be the same or different and represent a hydrogen atom or an alkyl group. Here, the alkyl group may be substituted with a halogen atom (eg, chlorine atom, bromine atom), etc., and may be polished. Especially R1-R4
It is preferable that three of them are hydrogen atoms and the remaining p is a C5-C2G alkyl group.

X represents an acid, especially nitrous acid, nitric acid, chloric acid, perchloric acid, carbonic acid, thiocarbonic acid, acetic acid, propionic acid, oxalic acid,
Benzene sulfonic acid, hydrochloric acid, and picric acid are preferred.

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 impaired, staining did not occur significantly, etc.). In particular, the compounds of the present invention are effective for stabilizing washing water fc in which iron ions and thiosulfate coexist.

The present inventors analyzed the precipitation mechanism of washing water and stabilizing solution in which iron ions and thiosulfates coexist, and found that
Air oxidation of thiosulfate using iron ions as catalyst and iron/ζ
Precipitate formation of iron ions by cutilia, decomposition of thiosulfate by sulfur bacteria, 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 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 washing water and stabilizing liquid. I found something to do.

Furthermore, the compound of the present invention is highly preferred in terms of stability, and furthermore, it has high water solubility, so it is particularly preferred for use in washing water or stabilizing liquid.

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

1-/・NH! 1 (nlc12H25NHC-NH2・HCll-coNH (nC12H25NHC-NH2・CH3C0OH-J NH (n'lc 14H2gNHC-NH2・HNO3■-
HiroNH (n)C14H2gNHC-NH2・H2co3NH (n)C10H21NHC-NH2・1-IC1O4I H2NCNH2・H2CO3 The compound represented by the general formula (I) is a known compound, and some are commercially available, so it can be easily obtained. can be obtained. For example, it is commercially available as Hokuside to (Hokuko Kagaku ■) Hikodo.

The amount of the compound of general formula (I) to be added is preferably 1 x 10-5 to 1 in washing water or in a stabilizing bath.

mot, preferably /xIO'~2XlO-2mo
It is l.

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/(7-/x10
mot/l.

Preferably, /×10'~! ×10”moL
/L.

As thiosulfate concentration I×10'~zxio''
mol/L preferably /X10-3 to 3X10-1m
o L/L.

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-37-/J7. Z≠q and the same jl'-10! As shown in issue /11j,
Thiazolylbenzimidazole compounds, inthiazolone compounds as shown in JP-A-37-13≠λ, lolophenol compounds as typified by trichlorophenol, or bromophenol compounds, Or organotin or organozinc compounds, or thiocyanic acid or isothyanic acid compounds,
Alternatively, acid amide compounds, diazine or triazine compounds, thiourea compounds, or ammonium salts such as benzalkonium chloride, or antibiotics such as nidiline. You may also use a general-purpose anti-spill agent such as. In particular, combination use with thiazolylbenzimidazole compounds and isothiazolone 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 io-rum salts, surfactants to prevent drying load and unevenness, fluorescent brighteners to improve whiteness, and sulfite as a preservative. Salt, bismuth salt for promoting chelation with iron, etc. can be added as necessary. Or L, E, West,
”Water 0ual i IyCri16ria
'Phol, Sci, and Eng,,votri,
You may add the compound described in A6 (/ri6ri etc.).

It is preferable to use various chelating agents in addition to the compound of general formula (I) in the washing water of the present invention. The chelating agent used in combination is inorganic phosphoric acid.

Chelating agents such as organic carboxylic acids, aminopolycarboxylic acids, phosphonocarboxylic acids, alkylphosphonic acids, and aminopolyphosphonic acids can be mentioned. Hikokamo, l-hydroxyethylidene-/,/-diphosphonic acid, nitrilo-N, N.

A combination of N-)IJ methylenephosphonic acid and ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid is preferred. The addition concentration of these chelating agents [L
Adjust the amount of water for washing/X10-/X/0-1mot
Preferably, it is 1 x 10 to 1 x 10-2 mol.

The washing treatment method used in the present invention is preferably a countercurrent washing method using tanks 2 to j' for the purpose of reducing the amount of washing water. In this case, the amount of water required for washing is the color photosensitive material i m 2
It will be about jOml~ioooomi per serving.

In addition, the amount of water used for washing differs depending on the number of washing tanks, so please refer to S, R, Godwass6r, "WaterFl" for details.
ow Rates in Tmmersion-W
Ashing of Motion piclur
e l;'i1m'SMPTE, A 4', pag
eJFJ' ~2! J, May (Li 31).

The pH of the washing water in the present invention is usually around 7, but it may reach pHJ or higher due to carryover from the previous bath. Also, what is the washing temperature? -≠0OC1 preferably 1O0
It is 0-3J0C. 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 the water washing step.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes a five-color patch image is used. A typical example is P.
Examples include a liquid having a buffering capacity of HJ to B, a liquid containing an aldehyde (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 system consisting of tanks λ to j is preferable.

Even in this case, the necessary stabilizer Iiii' is about J-0ral to /000rr per 1 m2 of color photosensitive material.
It becomes tl.

Also, what is the temperature of the stabilizing liquid? -≠00C1 preferably 100
C~3j0C. If necessary, a heater, a tank I controller, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the stabilizing tank.

73- The processing method of the present invention can be applied to any of general silver halide color photosensitive materials such as color negative film, color paper, color positive film, color reversal film, etc., but it is particularly applicable to color H7ξ- and color negative films. is preferred.

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

A, color development - bleach fixing, washing, drying B, color development - bleaching, fixing, washing, stabilization, drying C, color development - washing, bleaching, fixing, washing, drying, color development - bleaching, fixing, washing, stabilization. 1 drying E, color development - constant bleaching 1 washing 1 drying F, color development - washing 1 bleaching 1 washing 1 drying Here, in B and D, ``Water washing'' which is a ``stable'' pre-bath is removed. It's okay.

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

-7≠- D-/N, N-diethyl-p-phenylenediamine D-22-amino-! -diethylaminetoluene D-32-amino-j-(N-ethyl-N-laurylamino)toluene D-4! ≠-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-! --Methyruder-[N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-I N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-guaminoaniline]) -7N -(,2-amino-!-diethylaminophenylethyl)methanesulfonamide 1) -1N,N-dimethyl-p-phenylenediamine D-ta ≠-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-iop -amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline 1)-ii Reference-amino-3-methyl-N=ethyl-
N-β-Butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, p-)luenesulfo ZW& salt. The above compound is disclosed in US Pat. No., same λ,! ! λ.

J4'/issue, same co! tt, No. 271, same λ,! octopus,
3AII No. 3. tri, rij'θ, same 3゜6rir, tko! It is stated in the number etc. The use of the aromatic-grade amine developing herbal medicine is approximately o, iy to approx.
20f, more preferably about θ,! The concentration is from t to about ioy.

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. 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 is preferably 1) H
The color developer may contain compounds of other known developer components.

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 alone or in combination.

In addition, for the purpose of providing buffering capacity, for convenience of formulation, or for increasing sulfur loading, it is also possible to add sodium or potassium hydrogen phosphate, potassium or sodium hydrogen phosphate, sodium bicarbonate or potassium, or boron. Various salts are used, such as acids, alkali nitrates, alkali sulfates, etc.

In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium. Examples include polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, l-hydroxyalkylidene-7,/-diphosphonic acids, and the like.

Any development accelerator may be added to the color developer, if necessary. For example, various birimidium compounds represented by U.S. Pat. cationic dyes such as, neutral salts such as thallium nitrate and potassium nitrate, JP Akihiro μ-ta No. 304/-, U.S. Pat. j33,270, same λ63/, l'! No. 2, same co, Ri! Using nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, etc. described in θ, 7θ, 2.177.127, and thioether compounds described in U.S. Patent No. 3,20/2≠2. Good too.

-/t- Also, sodium sulfite, potassium sulfite, potassium bisulfite, or sodium bisulfite, which are commonly used as preservatives, can be added.

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

Examples of organic antifoggants include benzotriazole, 6-nidrobenzimidazole, j-nitroisointasole, j-methylbenztriazole, and! - Nitrobenzotriazole,! -Nitrogen-containing heterocyclic compounds such as chlorobenzotriazole, 2-thiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and l-phenyl-
! Mercapto-substituted heterocyclic compounds such as -mercaptotetrazole, co-melcabutobenzimidazole, 2-mercaptobenzothiazole, and also 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 the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.0/
-/, Omot/L preferably 0, Oj-0,!
Omot/l. The fixing agent in the fixing solution or bleach-fixing solution contains thiosulfate.Ammonium thiosulfate is preferably used, and the amount added is 0.0%.
/～! , Omot/l, preferably ijO, j-2,0m
It is oL/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. 37063611 Special Publication Sho pt.
-rso6, same hiroter 26! t6, JP-A-33-3
No. 273jt, No. 13-34233, and jt3-
Thiourea compounds as shown in the specification of No. 3701t, or JP-A No. 24A, No. 3701-2
2jtJi issue, 1.3-j713/issue, 13-32
No. 734, No. 33-61732, No. 734, No. 33-61732, Same! ≠−! Thiol-based compounds as shown in U.S. Pat. No. 3, U.S. Pat. 0-/≠0/2 issue, same! ! -21
No. 442, No. jJ-/4'/4.2J, No. j3-/
θ≠232, same! ≠-3j727 and Re56a
rch 1) Heterocyclic compounds described in ISCLOSUR6/7/2 specification etc., or JP-A-1983-
Y'1927, Y'12-20132, Y'33-37
vit issue, j3-21630 issue, tz-2sot
11-2tj01゜ specification, etc., or JP-A-Sho pr-r4t≠≠
Quaternary amines described in the specification of No. O or JP-A Akihiroter≠
Compounds such as thiocarbamoyls of 23 Ko No. 2 Specification 2 l- may also be used.

Example 1 Color negative film HR-70 manufactured by Fuji Photo Film ■
After imagewise exposure of 0 (24! shots), Fuji Color Negative Processor );'p-j00 (Fuji Photo Film ■
The following treatment steps were performed continuously using the following treatment steps.

QQ O00 I'v1 Town Town)
) Washed with water.

Further, the amount of processing liquid brought in from each type of front tank was about 2 - per 2 shots/shot.

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

<Color developer> Tank liquid Replenisher Sodium nitrilotriacetate i, oy i, /y Sodium bisulfite g, oy ≠, ay Sodium carbonate 30. Of 32. Of potassium bromide 1. daf 007f hydroxylamine sulfate co, 4tg λ, 62μ-
(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate, jf,! t
, add water to 11 11p H
10,0010,0! <Bleach solution> Tank solution Replenishment amount Ammonium bromide / 60,01 / 76 f Aqueous ammonia (2!%) 2! , Of /yoethylenediamine-tetraacetic acid sodium iron salt 130. Of /≠3glacial acetic acid
/ P, (hnl / 4A, 0
Add ml water /1 /1pHt,
, or r, t <Fixer> Tank liquid Replenishment amount Sodium tetrapolyphosphate λ, Of 2.29 Sodium sulfite ≠, Of ≠, ≠ 1 Ammonium thiosulfate (70 ti) /71 d/ri 3. d of
Sodium bisulfite ≠, tf! t, /f Add water /1 /1pH4,4z,
a - Co j - <Stabilizing liquid> Tank liquid Refill needle Formalin If, 0vtl!
I, 0ml dry well (Fuji ≠, Oml
≠, 0wt1゜film■) Add water and process the color negative film under the above conditions for 4I-0 for 7 days.
The treatment was carried out on day 1. Table 1 shows the number of days until floating matter and sediment appeared in the washing tank (2) and the washing tank (2). At the same time, 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 the treatment for t0 days.

According to the present invention, the stability of the washing water was significantly improved in both the (AA, 7.t)% washing (2) and the washing (2).

Example 2 After image-wise exposure of a color filter manufactured by Fuji Photo Film ■, a color filter manufactured by Fuji Photo Film ξ-Processor FMPP-10 was used.
00 (manufactured by Fuji Photo Film ■) and was continuously processed in the following processing steps.

-2♂- Similar to the above, the washing process was a three-stage countercurrent washing from washing (■) to washing (■).

Also, the amount of processing liquid brought in from each type of front tank was about 1000 ml of color paper/m.

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

<Color developer> Tank liquid Replenisher water room l
00ml nitrilotriacetic acid/Na 2. Of
2. Of benzyl alcohol n side 1r
rrtl diethylene glycol /(hnl
10ml sodium sulfite 2. Of
2.3? Hydroxylamine sulfate 3. Of
3.19 Potassium bromide i, or
-Sodium carbonate 30f 3Jf
N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl≠-aminoaniline sulfate z, or r, o The circles in the table have the same meaning as in Example 1.

Add water to 10100O1000mlp
H10,/r 10. Is! r <Bleach-fix solution> Tank solution Replenisher water aootni a
ooty ammonium thiosulfate (70% solution)/! θgo JOOvtl Sodium sulfite / If Jjr Ethylenediaminetetraacetic acid ml) Ammonium, tsy 1ioy
Add ethylenediaminetetraacetic acid/2Na sy toy water to 1000rn11000rnl
pH &, 70 6.10 Color paper was treated with 10-2 for one day under the above conditions,
The treatment was carried out for to days. Table 2 shows the number of days until floating matter and sediment appeared in the washing tanks (2), (2), and (2). Table 2 also shows the results when various compounds were added to the washing water (tank liquid and replenisher liquid) in the same manner.

3 l- According to the invention (A/j-/I), washing water ■.

The stability of ■ and ■ is not a fool, but it can be used in combination with other anti-piping agents and chelating agents (A/A-/I
), and even in water washing (3), which had extremely poor stability, no precipitates or suspended matter were generated during the treatment period for days.

Patent applicant: Fuji Photo Film Co., Ltd. -3≠-

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) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3 and R_4 may be the same or different and represent a hydrogen atom or an alkyl group. X represents an acid.)