JPS6175354A - Method for processing color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the stability of washing water or a stabilizing soln. and to reduce the amount of the liq. used by adding a specified benzotriazole deriv. to a washing stage or a stabilizing stage after a bleach-fixing stage or bleaching and fixing stages. CONSTITUTION:A compound represented by formula I (where R1 is alkyl, halo gen, nitro, sulfone, amino or carboxyl, each of R2 and R3 is lower alkyl, and n=0 or 1), e.g., a compound represented by formula II or III is prepd. When an imagewise exposed color photographic sensitive silver halide material is continuously developed, the compound is added to washing water or a stabilizing soln. by about 1X10<-5>-1mol/l in a washing stage or a stabilizing stage after a bleach-fixing stage or bleaching and fixing stages. The formation of a precipi tate and suspended matter in the liq. can be inhibited without deteriorating the stability of a dye image.

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. The direction of reducing water tt is suggested. For example, S, R
, Goldwasser.

'Water Flow Rates in Im
mersion-Washing of Motion
Picture Fi1m'SMPTE, gu, p3
ge2ur-2jJ, (May.

A method has been proposed in which the amount of water used for washing can be reduced by making the washing tank multi-stage and causing the water to flow counter-currently. This method has been adopted in various automatic slag machines as an effective means for saving water. However, due to mosquitoes, iron ions from the bleaching process and thiosulfate from the fixing process are brought in during processing, making the subsequent washing water extremely unstable. It has been discovered that a new problem occurs in that the water stays for a long time and various precipitates and floating substances are generated.Such problems can be solved by replacing the water washing process with a stabilization process or continuing with the water washing process. This also occurs during the stabilization process.

These precipitates and floating substances adhere to the photosensitive material and clog or stain the filter of the automatic processing machine, causing various troubles.

In order to solve these problems, many precipitation prevention means have been proposed. If you line up, L, EWest, "W"
ater Quality Cr1teria “Pho
t, Sci,, and Eng,, vol PAJ (
/ P6 describes the addition of chelating agents and bactericides.

In addition, JP-A No. 17-41≠λ, No. 5r-top Iuj, and No. 17-1172φ≠ describe the addition of various anti-puff agents such as thiazolylbenzimidazole compounds and isothiazolone compounds. However, the solubility is poor2)1
However, satisfactory results cannot be obtained due to problems with the safety of the compound or insufficient precipitation prevention effect. In addition, the method of adding each chelating agent is as described in JP-A No. 17-RJT A2 and J7-JR/1.
No. 43, J7/72/4C4, No. 5r-trt
Although it is described in J.I. No. 1, etc., the chelating agent of bzn is also insufficiently effective and has an adverse effect on storage stability, resulting in unsatisfactory results.

Furthermore, as a method of using sulfite and a chelating agent in combination, JP-A No. 17-97JJO and J. #7 Jr issue and the same! However, the effect is still insufficient.

(Object of the Invention) Therefore, the object of the present invention is to improve the stability of the washing water bath or 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 the stabilizing liquid in the washing water tank 7'j.

Another object of the present invention is to significantly reduce the amount of washing water or stabilizing solution used to clean the skin, or to significantly reduce the amount of replenishment, without impairing the stability of the color mixture. The purpose of washing water 1-fc is to improve the stability of the stabilizing liquid itself.

(Misappropriation of the Invention) The above object is to provide a method for continuously air-processing an imagewise exposed phosphorescent silver halide color photographic light-sensitive material, including a water washing process after a bleach-mud layer process or a bleach-fix process.
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 stabilization step.

General formula N) In the formula, R1 represents a substituted If on a benzene ring, and represents an alkyl group, a halogen atom (for example, a chlorine atom or a bromine atom), a nitro group, a sulfonic acid group, an amino group, or a carboxyl group. Note that the alkyl group may be substituted with a halogen atom (chlorine atom, bromine atom, etc.), hydroxyl group, etc. Especially as R1, C1 to C2
is preferably an alkyl group or a haloken atom.

R2 represents a lower alkyl group, and the number of carbon atoms is /
Early evening is preferable. These alkyl groups may be substituted with a halogen atom, hydroxyl group, amino group, sulfonic acid group, carboxyl group, or the like.

Mayu, n FiOmat represents l.

By using the compound represented by the above general formula (I), washing with water can remove precipitates and suspended matter that occur in the stable solution.
It was possible to effectively suppress the photographic characteristics without adversely affecting the IC (for example, the stability of the dye artist was not impaired, there was no significant occurrence of stay/, etc.). In particular, the compounds of the present invention are effective in stabilizing solutions using washing water and water in which iron ions and thiosulfates coexist.

The present inventors analyzed the precipitator #4 in which iron ions and thiosulfate coexist in washing water and stabilizing solution, and found that air oxidation of thiosulfate using iron ions as a catalyst and iron bacteria caused Precipitate formation of iron ions, decomposition of thioate salts 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 safety of washing water and stabilizing solution can be further improved by sterilizing 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 (anti-pepper agents), and as a result, the compound of the general formula (I) specifically stabilized the washing water stabilizer. It's a good idea to encourage your friends.

Specific pH values of general formula (I) are shown below, but are not limited thereto.

■−μ ■−μ −r The compound represented by general formula (1) is a known compound,
Some of them are commercially available and can be easily obtained.

The addition t of the compound of general formula (I) is preferably 1×10 −5 to 7.0 mol (F) per liter of washing water or stabilizing solution, more preferably 1×10 −4 to 2×10 −2 mol.

In the 7 tons of washing water of the present invention, iron salt as a bleaching component and thiosulfate as a fixing component are inevitably brought into the stabilizing solution from the previous bath (bleach bath, fixing bath, bleach-fixing bath) due to continuous processing. It will be done. The content of these t is 1xio-6~/X as iron g, although there are differences depending on the method of stabilization for washing or t.
/+7 1moJ/A! .

Preferably /X/ o-5 to z x lo-2 mol/l
.

lXl0-4~jX10-1m as thiosulfate concentration
o l /l preferably lXl0 3~JX10-1m
It is ol/l.

Washing water of the present invention 7? , c) In the stabilizing solution, the general formula (IN
In addition to the nine compounds indicated by , there are other antibacterial and antifungal agents (
anti-piping agent) t- May be used in combination.

If you keep it, it can be used as an anti-pyretic agent. -101/≠! Thiazolylbenzimidazole compounds as shown in No.
Intiazolone compound shown in II μλ,
Or chlorophenol compounds such as trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds.

Thiocyanic acid and isothyanic acid compounds, thiamide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, chemical compounds such as sulfonium chloride, etc. grade ammonium salt, or
General-purpose anti-inflammatory agents such as antibiotics such as Niziline may be used in combination, and combinations with thiazolylbenzimidazole compounds and inthiazolone compounds are particularly 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, fine surfactants to prevent drying load and unevenness, specific fluorescent brighteners to improve whiteness, sulfites as preservatives, A bismuth salt or the like that promotes chelation with iron can be added as necessary.

Orori, E, WeSt, '''Water Qua
lity Cr1teria'Photo, Sci, an
d Eng,, volri, /l6A(/ta4j)
It is good to add the compounds described in et al.

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, phosphonocarboxylic acid, alkylphosphonic acid, and aminopolyphosphonic acid.

Among them, l-hydroxyethylidene-/,/-diphosphonic acid, nitrilo-N,N,N-1 rimethylenephosphonic acid and ethylenediami/-N.

Preferably used in combination with N,N',N'-tetramethylenephosphonic acid.Addition of these chelating agents (degree: washing water/l/X/0-5~7X/0-1 mol)
Preferably lx10-4 to lx10-2 mol
It is.

The washing treatment method used in the present invention is preferably a countercurrent washing method using a tank of λ~ for the purpose of reducing the amount of washing water. In this case, the amount of washing water t required is approximately jOul-10θOml per 1rrL2 of color photosensitive material.

Also, the amount of water for washing varies depending on the number of washing tanks. For details, see S. R. Godwasaer, - Water Fl.
ow Rates in Immersion-W
Ashingof Motion Picture
Film” SMPTE, Alfi.

p2g624'Jt' ~kojJ%Miyf/P
j j ).

The pH of the washing water in the present invention is usually around 7, but it may become I) HJ to P due to the pH of the washing water brought in from the previous bath. Friend, the washing temperature is from evening to uo 0c.

Preferably it is 100C to Js0C. as needed,
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 solution used in the stabilization step, a processing solution that completely stabilizes the dye image is used. A typical example is p
Examples include T solution, which has a buffering capacity of H3 to B, and T solution, which contains all aldehyde (formalin if kept). If necessary, the stabilizing liquid may contain the various compounds* described above for use in the subsequent washing water.

For the purpose of reducing the amount of water in the stabilizing liquid, a multistage countercurrent system comprising a λ tank is preferable.

Even in this case, the required amount of stabilizing liquid is the color photosensitive material! /, about 5 per 2 (7, IN/ 000'/It).

In addition, the temperature of the stabilizing liquid is z, 1AoOc, preferably 1OO
It is C~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 includes color negative film 1. It can be applied to any processing of general color photosensitive materials such as color J-par, color positive film, color reversal film, etc., and silver halide color photosensitive materials, but it is particularly preferable for color paper and color negative film.

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

People, color development [Elephant - Bleach fixing, washing with water, drying B, color development - bleach constant layer, washing with water, stabilizing, drying, C, color development - washing with water - bleach fixing, washing with water, drying, color development (& - Guanbai) Constant blue - water washing - stable - drying E, color scum - bleaching - constant layer - washing - drying F, color phenomenon - washing with water - constant bleaching - constant layer - washing - drying Here, in B and D, "stable" pre-bath is “
"Water washing" does not work even if it is removed.

The color pigments used in the present invention (color pigments [
Contains elephant medicine. Preferred series are p-7 unilene diamine derivatives, and representative series are shown below, but the invention is not limited thereto.

D-/N,N-diethyl-p-phenylenediamine D-22-amino-terdiethylaminotoluene D-J Coramino-! -(N-ethyl-N-laurylamino)toluene D-4L ≠-[N-ethyl-N-fβ-hydroxyethyl)amino]aniline D-t λ-methyl-Hiro-[N-ethyl-N-(β-
hydroxyethyl) aminocoaniline D-AN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-φ-aminoaniline D-7N-(-2-amino-yo-diethylaminophenylethyl)methanesulfonamide D-4N, N-dimethyl-p-7 22 enediacine D-1 μm amino-3-methyl-N-ethyl-N-methoxyethylaniline D-io μm amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline])-// ≠-amino-3-methyl-N-ethyl-N
-β-Butoxyethylaniline or these p-phenylenediamine derivatives may be used in the form of salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The above compounds are described in US Pat.
．． 01! No., same λ,! ! Ko.

Ko4Ai No., Ko4Ai, j64. Core No. 1, same co, jri 2.
36≠ issue, same 3. trlr,? ! No. 0, same 3゜tri,
rλ! The number etc. are written. The amount of the aromatic-grade amine Fugen crude drug used is about 9 o, ig to about -20 per liter of Fugen solution.
jq, more preferably about 0. jl to approximately iog.

The color solution used in the present invention may contain hydroxylamines, which are known in the art.

Hydroxylamines are more commonly used in the form of water-soluble acid salts, which can be used in the free amine form in the coloring solution.

Common classes of salts include sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and others. Hydroxylamines may be substituted or unsubstituted,
It is acceptable even if the nitrogen atom of hydroxylamine is substituted with an alkyl group.

, the color wind source solution used in the present invention preferably has a pH of
2 to 1, preferably 2 to 2, and o, and the color effect liquid may contain a compound of the wind source liquid component already published in the pond.

For example, as alkaline agents and pH buffering agents, caustic soda, caustic potash, soda carbonate, potassium charcoal, tribasic sodium phosphate, tribasic potassium phosphate, potassium metaborate, borax, etc. are used singly or in combination.

In addition, sodium or potassium hydrogen phosphate, potassium or sodium phosphate, and sodium bicarbonate may be added for the purpose of providing 9% buffering capacity, for convenience in formulation, or to increase ionic strength. Or potash, boric acid, alkali nitrate 1
Various salts are used, such as alkali halosulfate.

In addition, various chelating agents can be added to the color sludge to prevent precipitation of calcium and magnesium. Examples include polyphosphates, aminopolycarboxylic acids, phosphonocarmenic acids, aminopolyphosphonic acids, /-human xyalkylidene, /-diphosphonic acids, and the like.

If necessary, any phenomenon accelerator can be added to the color wind source liquid. For example, cationic dyes such as various pyrimidyl compounds, other carbonyl compounds, and phenosafranine compounds represented by U.S. Patent No. 96≠t, BuO reference, Special Publication Shodal No. 2103, and U.S. Patent No. 3゜171.247. , neutral salts such as thallium nitrate and potassium nitrate, Special Publication Akihiro≠-230≠, US Patent λ,! No. 133.720, same.

r3i, r3x, the same, Tata 0. Ri No. 70, same co!
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 77,/j7, and thioether compounds described in U.S. Pat. No. 3,20/, λφλ, may also be used.

However, 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 solution if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used.

Organic antifoggants such as benzotriazole, 6-nidropenzimidazole, etc. - Nitroinindazole! -) 1 tilbenztriazole,! - Nitropenzotriazole,! -Nitrogen-containing heterocyclic compounds such as chlorobenzotriazole, corchiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and l-phenyl-y-mercaptotetra 7''-A/, 2-mercaptobenzimidazole , mercapto-substituted heterocyclic compounds such as λ-mercaptobenzothiazole, and mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred are nitrogen-containing heterocyclic compounds. The inhibitor may be eluted from the color photosensitive material during processing and 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 iron complexes, aminopolycarmine refined iron complexes are preferred, and their addition @too
, o l~i , omol/l preferably u O, Oj
−0, j Omol/l. The fixing agent in the t1 fixer or bleach-fixer includes thiosulfate. Particularly preferred is ammonium thiosulfate, and the addition rate is 0.6 l-Omol/l, preferably 0.1-2
．． It is 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, US Patent No. 370414/, Special Publication Showax
-trod issue, gy-xtzrt issue, Tokukai Sho! 3-3
No. 2731, No. 13-JA-33, and No. 13-37
The thiourea compounds shown in the specification of No. 0/4, or JP-A-Shoj J-/λμ-Hiro No. J3-7!63
/ issue, same! 3-yo7131, 13-327344i
j.

No. 13-4173λ, same! ≠−j Kota 3≠ and U.S. Pat. A
No. 10-/ll-0/Kota No., same! J-211A2
No. 13-/@/Guj No. 13-10IL23
No. 2, j4'-jj727, and Re5earch
The heterocyclic compound described in Disclosure/7/22, etc., or JP-A-13-241?
No. 27, No. J-2-201rJJ, No. 13-3714
/I No. 13-41430, No. 1j-2107, μ
No., and the same! j-2tjO6 No. 6 Mei Mi book, etc., or JP-A Shomu, r-ru HiromuO
Compounds such as the quaternary amines described in the specifications of JP-A-Kokai Akihirota and the thiocarbamoyls described in the specifications of JP-A-Kokai Akihirota Co., Ltd. may also be used.

Implemented FPU/Color negative film HR- manufactured by Fuji Photo Film Co., Ltd.
After a low exposure of 100 (double exposure), use Fujicolor Negative Processor FF-400 (Fuji Photo Film Co., Ltd.)
(manufactured in Japan) by using the following treatment process continuously.

Process time Temperature stabilization process ≠
01 JrQC±3 degrees Tank capacity refill amount (bottom), 3°C-7l φj 'C/ r l J O 'C/ r l jri'c rl - 'c H3ko O 'C/ j l J ? In addition, the water washing process is a two-stage countercurrent water washing from water washing (■) to water washing (2).

It takes about 2 microns per shot.

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

Tank fluid Replenisher Sodium nitrilotriacetate Sodium sulfite ≠, Og Sodium charcoal 30. Ofi J Co, 0g potassium bromide
i, ag o, 7g hydroxylamide/sulfate co, da, p J, j, 9
Hiro-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate μ, jg j, O
fi Add water /l ll
pHlo,oo 10. oz <Bleach solution> Tank solution Replenishment amount Ammonium bromide /60. Og 17tji
Ammonia water (=t%) =! , Op /j Ethylenediamine-sodium iron tetraacetate /J0.09 /1AJ9 Glacial acetic acid l≠, θd lμ, 0 Add distilled water /l /73pH6,O
j, 7 Fixer> Tank liquid Replenishment amount Sodium tetrapolyphosphate Co, Ofi 2. -g Sodium sulfite u, 09 11.4Ai Thiosulfate a/
Monium (70%) /7! , 0vtllriJ, 0ra1 Sodium Bisulfite Section, Otsug
z, add ip water /l
llpHp, ≦ iA Stabilizing liquid> Tank liquid Replenishing machine 7 1, 0rnl I
, Owrl Dry Well (Fuji Photo ≠, Om!
Hiroshi, orrtt film (Made)) Add water /l /1 Under the above conditions, color negative film i / day! AO book processing, 6
A friend who has been processing for 0 days. and.

Table 1 shows the number of days until floating matter and sediment appear in the washing tank ■ and the washing tank ■. The results are also shown in Table 1.

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

If the present invention is applied (ttit, 7.r), the stability of the washing water will be significantly improved in both washing (1) and washing (2).9.

The actual row was exposed to a color filter made by Fuji Photo Film (floor) in one way.
/ 000 (manufactured by Kutsuyoshi Photographic Film (Foundation))
Time Flat 1.3 C C C C Distance Tank Capacity Replenishment l (m/m”) 'Ctrl 1tt 361 O /71 2j0 The water washing process is a three-stage countercurrent water washing from washing ■ to washing ■. Sentence.

Also, the amount of processing liquid brought into the various front tanks is approximately tOd per 1rrL2 of color bonnet.

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

Color slag liquid> Tank liquid Replenishment liquid water roovit
r00ytl Nitrilotriacetic acid/jNa λ, O1
λ, Oy benzyl alcohol /lAm1
/I punishment resin ethylene glycol lOgo 1
0tpil sodium sulfite λ, og
Co, rgHydroxylamine sulfate J, Ofl
J, jji potassium bromide /, 09
-Ra+ ToIJ Lamb 3ofi 3zlN-Ethyl-N-(β-methanesulfonamidoethyl)-J-Methyl 1 μm Amino niline sulfate jJ[r,oy r,oy Add water 1000rxl 1000
pH10, it io, ≦! Bleach-fix solution> Tank solution Replenisher water ≠00tR1≠0
0ml ammonium thiosulfate <70 yen + full liquid) tro1rLt3o
orut sodium sulfite 1rjq
Jtf) Iron (In) ammonium ethylenediaminetetraacetate zzg tiog Ethylenediaminetetraacetic acid/12Na 1g 109 Add water 1000rnl 1000m
100O4, 70O, YoO A friend who processed Color Epermit on IQ7FL2 under the above conditions for 60 days. And washing tank■,■
Table 2 shows the number of days until floating matter and sediment appear in (1) and (2). In the same manner, various compounds were added to the washing water (tank fluid and replenisher fluid) and the results are also shown in Table 1.

Note that the mark Q in the table has the same meaning as implementation die i/.

If the present invention is used, TA/j-/r), washing water ■.

Not only does the stability of ■ and ■ improve significantly, but it can also be used in combination with other anti-piping agents and chelating agents (A/A~/
r) Even when washing with water (d), which has poor stability, no sediment or suspended matter was generated during the 40-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) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R_1 is a substituent on the benzene ring and represents an alkyl group, a halogen atom, a nitro group, a sulfonic acid group, an amino group, or a carboxyl group. R_2 and R_3 represent a lower alkyl group, and n
represents 0 or 1. )