JPH059783B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing a silver halide color photographic material, and more particularly to a method for processing a bath containing a soluble silver salt. [Prior Art] Generally speaking, in the processing of silver halide color photographic light-sensitive materials, the issues of environmental conservation and the saving of silver resources have become important in recent years, and methods to reduce pollution and methods to efficiently recover silver have strongly emerged. desired. For this reason, it has been proposed to provide a preliminary washing process between the bath containing soluble silver salts and the subsequent washing process as a method to recover the silver flowing into the washing water and simultaneously reduce polluting substances from the washing water. ing. However, the pre-washing bath has a serious drawback in that if the astringent liquid of the pre-washing water stays in the tank for a long period of time due to long-term storage or continuous processing of small quantities, sediments or suspended matter will be formed, which will have a negative effect on photographic performance. I found out. Furthermore, it has been found that this precipitate has the disadvantage of clogging the pipes of the automatic processor. [Object of the Invention] The object of the present invention is first to solve the above-mentioned drawbacks, and to remove precipitates from a bath containing a soluble silver salt into a subsequent bath without substantially undergoing a water washing step. An object of the present invention is to provide a method for processing a silver halide photographic material in which the generation of floating substances is suppressed. [Structure of the Invention] The object of the present invention is to develop a silver halide color photographic light-sensitive material and then to process it in a bath containing a soluble silver salt, without substantially going through other processing steps such as washing with water. , the following general formula [] to [X
] This is achieved by treatment with a bath containing at least one of the compounds represented by: Here, the bath of the present invention is supplied with a replenisher in an amount of 1 to 20 times the processing solution brought in by the photosensitive material from the pre-bath, and the processing solution in the bath is kept constant by means such as overflow. dripping General formula [] MmPmO ₃ m General formula [] Mn ₊₂ PnO _3o+1 General formula [] E ¹ −A ¹ −Z−A ² −E ² General formula [] General formula [] General formula [] R ₄ N [CH ₂ PO ₃ M ₂ ) ₂ General formula [] General formula [] General formula [] General formula [] General formula [X] [In the formula, M represents a hydrogen atom, an alkali metal atom, or an ammonium group, and A ¹ , A ² , A ³ , A ⁴ , A ⁵
and A ⁶ each represent a substituted or unsubstituted alkylene group, Z is an alkylene group, cyclohexane-
1,2-ylene group, o-phenylene group, -R-O
-R-, -R-O-R-O-R- or >N-A ⁷
(R represents an alkylene group, A ⁷ represents a hydrogen atom, a hydrocarbon group, a lower aliphatic carboxylic acid residue or a lower alcohol residue), E ¹ , E ² , E ³ ,
E ⁴ , E ⁵ and E ⁶ are each hydroxyl group, -COOM
or −PO ₃ M ₂ and R ¹ is −COOM or −
Represents PO(OM) ₂ , R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -(CH ₂ ) _p -COOM (p is 1 to 4
) or phenyl group, R ³ represents a hydrogen atom or -COOM, R ⁴ represents a lower alkyl group, aryl group, cyclohexyl group, aralkyl group or nitrogen-containing 6-membered ring group, R ⁶ and
R ⁷ each represents a hydrogen atom, a lower alkyl group, a carboxyl group, or -NJ ₂ (J represents a hydrogen atom, a hydroxyl group, a lower alkyl group, or a hydroxyethyl group), and R ₈ represents a hydrogen atom, a lower alkyl group, a hydroxyl group. group, _-PO3M2 or _{-NJ2 ,} X, Y and ^Z1 each represent a hydrogen atom, hydroxyl group, -COOM group or _PO3M2 , ^R9 and _R10 each represent a hydrogen atom, ^an alkali group, Represents a metal atom, an ammonium group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, or a cyclic alkyl group, and R ¹¹ is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. represents a monoalkylamino group, a dialkylamino group having 2 to 12 carbon atoms, an amino group, an aryloxy group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, or an amyloxy group, Q ¹ , Q ² and Q ³ each represents a hydroxyl group, an alkoxy group having 1 to 24 carbon atoms, an aralkyloxy group, an aryloxy group, -OM ¹ (M ¹ represents a cation), an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a dialkylamino group base,
Represents an arylamino group or an alkyloxy group, and R ¹² and R ¹³ each represent a hydrogen atom, a lower alkyl group, or an imine residue (lower alkyl group or -
R ¹⁴ , R ¹⁵ and R ¹⁶ are each a hydrogen atom, a hydroxyl group, an -O-alkyl group (optionally substituted with CH ₂ CH ₂ COONa), and R 14 , R 15 and R 16 are
~ _{4), represents PO3M2, -CH2PO3M , -NR2 ( R} represents an alkyl group ₎ or -N( _{CH2PO3M2 ) 2} .
m represents an integer from 3 to 6, n represents an integer from 2 to 20, l represents 0 or 1, and q represents 0, 1 or 2.
, and r represents an integer from 2 to 16. That is, the present invention provides a method for adding compounds that form stable chelate compounds with metal ions, especially iron ions and calcium ions, to a treatment bath following a bath containing a soluble silver salt for the purpose of desilvering, such as a fixing bath or a bleach-fixing bath. By adding a compound having a chelate-forming ability that forms a stable complex with magnesium ions, etc. to the bath, it is possible to prevent the occurrence of precipitates and suspended substances in the treatment bath, especially when the bath is left unattended after treatment. Even in such cases, it has an excellent effect in preventing the generation of precipitates and suspended matter. Furthermore, silver halide color photographic materials with excellent storage stability can be processed. Furthermore, the stability can be further increased by adding to the bath a compound that releases sulfite ions in an aqueous solution, such as sodium sulfite, ammonium hydrogen sulfite, and the like. The bath containing soluble silver salt of the present invention refers to a bath for the purpose of desilvering in the processing of silver halide color photographic light-sensitive materials, and is a bath containing soluble silver salt as a result of processing, and these baths include There are fixing baths, bleach-fixing baths, one-bath development-fixing baths, hardening fixing baths, one-bath development bleach-fixing baths, and the like. Further, the effects of the present invention are remarkable when the soluble silver salt contained in these baths is a silver thiosulfate complex salt. The compounds represented by the general formulas [] to [X] of the present invention are compounds that form stable chelate compounds with metal ions, and in particular, the compounds of the present invention form stable complex compounds with iron ions, calcium ions, and magnesium ions. It is effective in forming Representative specific examples of the compounds represented by the general formulas [] to [X] are as follows. (1) Na ₄ P ₄ O ₁₂ (2) Na ₃ P ₃ O ₉ (3) H ₄ P ₂ O ₇ (4)
H ₅ P ₃ O ₁₀ (5) Na ₆ P ₄ O ₁₃

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(15) (HOC ₂ H ₄ ) ₂ NCH ₂ COOH

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The compounds represented by these general formulas [] to [X] can be added in an amount ranging from 0.01 to 500 g per liter of the treatment bath according to the present invention. Good results can be obtained by adding preferably in the range of 0.1 to 50 g/l, more preferably in the range of 1 to 10 g/l. Compounds that also release sulfite ions that can be used in the present invention are those that release sulfite ions when added to an aqueous solution, and typical specific compounds are listed below. S-1 Na ₂ SO ₃ S-2 K ₂ SO ₃ S-3 (NH ₄ ) ₂ SO ₃ S-4 NaHSO ₃ S-5 KHSO ₃ S-6 (NH ₄ )HSO ₃ S-7 Na ₂ S ₂ O ₅ S-8 K ₂ S ₂ O ₅ S-9 (NH ₄ ) ₂ S ₂ O ₅ These sulfite ion-releasing compounds can be used in an amount of 0.05 to 250 g/l per liter of the treatment bath according to the present invention, preferably in a range of 0.1 to 20 g to obtain good results. In the bath according to the present invention, these sulfite ions or chelate-forming compounds may be present due to carryover of the sensitive material from the previous bath containing soluble silver salt.
However, baths containing soluble silver salts contain small amounts of these compounds. Furthermore, if the bath containing the soluble silver salt is a bleach-fix solution in which sulfite and an oxidizing agent coexist, the sulfite can be contained in a smaller amount than in the fixer because it impairs photographic performance. For this reason, in the water washing bath following this bath, these compounds are diluted and further reduced, and therefore the effect of the present invention is not recognized. Also, as understood from the examples shown later,
When the compounds brought in from the bath containing soluble silver salts become more dilute than a certain level, the occurrence of precipitates and suspended matter becomes even more pronounced. It was unexpected that very favorable effects were obtained by adding these compounds to the bath according to the present invention, and no deterioration of photographic performance was observed. In addition to the above-mentioned compounds, a fungicide, a compound that improves image preservability, etc. may be added to the bath according to the present invention. For example, compounds conventionally known to be added to the stabilizer after washing with water, such as nitro alcohols, phenol derivatives, nitrogen-containing heterocyclic compounds, quaternary salts, and surfactants, may be used. The bath according to the present invention is suitable for concentrating and recovering soluble silver salts or pollution-loading substances contained in sensitive materials or attached to the surface and eluted during washing with water from a bath containing soluble silver salts. , consisting of one tank or two or more tanks. If there are two or more tanks, a so-called counterflow system may be used in which the processing liquid flows back from the rear bath to the front bath. A separate replenishment system may be provided for the water used for the processing liquid to be replenished to the bath according to the present invention, but if a washing bath is provided after the bath, the water in the washing bath or a part of its overflow may be used. The quality of the water should be that it can be used for rinsing. The amount of treatment liquid to be replenished to the bath according to the present invention can be arbitrarily selected, but is generally particularly preferably about 1/200 to 1/10 of the amount of water to be replenished to the washing bath, or
This is 1 to 20 times the amount of liquid carried by the photosensitive material from the bath containing soluble silver salts. In the present invention, a substantial water washing process is performed between the bath containing the soluble silver salt and the processing bath of the present invention without providing a treatment process using a relatively large amount of running water, which is conventionally known as a water washing process. A non-processing process is used. The chelating compounds or sulfite ion-releasing compounds of the present invention can be added directly to the bath of the present invention, such as by addition to replenishing water. [Effects of the Invention] Next, the effects of the present invention will be listed. (1) Preventing the formation of sediments and floating substances that occur when the product is left in a bath containing soluble silver salts. (2) When a washing bath is provided following the above-mentioned bath, the generation of precipitation that occurs when left in the washing bath is suppressed and the safety period until precipitation occurs is more than doubled. [Examples] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example Sakura color paper (in roll form) (Konishiroku Photo Industry KK) was printed with a photoprint, and then subjected to continuous replenishment processing (referred to as running processing) using an automatic processor (RP-1180 processor manufactured by Noritsu Koki Co., Ltd.). Processing step 1 Color development 33°C 3 minutes 30 seconds 2 Bleach-fixing 33°C 1 minute 30 seconds 3 Bath according to the invention 30-35°C 1 minute 4 Washing 30-35°C 3 minutes 5 Drying 75-80°C approximately 2 minutes Main The bath according to the invention has two tanks (one tank takes 30 seconds), and the latter tank is refilled with water, and the overflow flows into the previous tank, and the overflow from the previous tank is made to reduce the amount of liquid in the processing bath. I kept it constant. The washing tank is divided into three tanks (referred to as 1st, 2nd, and 3rd washing tanks in the order of the flow of the photosensitive material), and the washing water flows into the 3rd washing tank, and the overflow from the tank is sent to the 2nd washing tank. The overflow from the second washing tank is put into the first washing tank, and the overflow from the first washing tank is made to flow out of the treatment system. The composition of the treatment liquid is as follows. [Color development tank liquid] Benzyl alcohol 15ml Triethanolamine 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbon 30.0g Hydroxylamine sulfate 3g Polyphosphoric acid (TPPS) 2g Polystyrene sulfonic acid (molecular weight 10000) 1g 3 -Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to make 1 liter. [Color developer replenisher] Benzyl alcohol 20ml Triethanolamine 20ml Potassium sulfite 3.0g Potassium carbon 3.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g Polystyrene sulfonic acid (molecular weight 10000) 1.0g 3-methyl-4- Amino-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 7.0g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.5g Potassium hydroxide 3.0g Add water to bring the total volume to 1 liter. [Bleach-fix tank solution] Ferrous ammonium ethylenediaminetetraacetate dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.10 with potassium carbonate or glacial acetic acid Add water Add to make the total volume 1 liter. [Bleach-fix replenisher A] Ethylenediaminetetraacetate ferrous ammonium dihydrate 260g Potassium carbonate 42g Add water to make a total volume of 1L. The pH of this solution is 6.70±0.1. [Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to make a total volume of 1L. The pH of this solution is 4.60±0.1. Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution, and water (in the pre-wash tank, which is the bath according to the present invention), and add the above color developer replenisher every 3 minutes while processing the color paper. A running test was conducted while replenishing the bleach-fixing replenishers A and B and the above water through a quantitative cup. The amount of replenishment was 324 ml to the color development tank per 1 m ² of color paper, 25 ml each of bleach-fix replenisher A and B to the bleach-fix tank, and 200 ml of water to the pre-wash tank. . Washing water was replenished at 10 liters per 1 m ² of color paper by continuously adjusting the flow rate using a flow meter according to the amount of processing. Experiment 1 (Reference example) When convergence was reached after the above continuous treatment (Note 1), the liquids from the first and second pre-washing tanks were taken, and the compounds shown in Table 1 were added to them, respectively. The solution was stored at room temperature as a 1-liter solution in a 1-liter beaker, and the formation of precipitates and suspended matter was observed over time. The results are shown in Table 2. (Note 1) Amount of bleach-fix solution refilled to the bleach-fix bath (replenishment amount A+
Convergence was reached when the total amount of replenishment amount B+the amount of color developing solution attached to the photosensitive material became twice the tank capacity.

[Table] Invention compound numbers

[Table] From Table 2 above, the general formulas [] to [X
The compounds represented by ] are effective against the generation of precipitates and suspended matter, and when used in combination with compounds that release sulfite ions, a more favorable effect is exhibited. On the other hand, citric acid, which is a chelating agent used for comparison, and hydroxylamine sulfate and hydroxyurea, which are generally known as antioxidants like sulfites, are not effective. As described above, the compound of the present invention is very preferable because it prevents the generation of precipitates and suspended substances, and it is also very preferable to combine a compound that releases sulfite ions with a compound represented by the general formulas [] to [X]. No floating matter occurs even after 50 days. In addition, the silver concentration in the second pre-wash tank was about 1/5 of that in the first tank, and precipitation occurred quickly in the case where nothing was added. However, it can be seen that the method of the present invention is extremely effective in suppressing the generation of precipitates and suspended matter, regardless of the fact that the soluble silver concentration is diluted and precipitates and suspended matter are likely to occur. Experiment 2 (example of the present invention) Add 3 g/l of sodium sulfite and 3 g/l of the chelating agent exemplified compound (61) of the present invention to the water replenished to the pre-wash tank, and run in the same manner as in Experiment 1 until convergence is reached. I processed it. After reaching the convergence state, a small amount of running treatment (Note 2) was performed, and when the pre-wash tank reached convergence (Note 3), it was left as it was and the pre-wash tank and the wash tank were observed. The results are shown in Table 3. Similarly, a small amount of running (Note 2) was carried out using the experiment 1 in which plain water was used as the pre-wash replenisher, and when convergence was reached, the water was left to stand and the pre-wash tank and wash tank were observed. The results are shown in Table 3. (Note 2) The photosensitive material was processed in an amount such that the daily replenishment amount of pre-washing replenisher was 1/5 of the capacity of the pre-washing tank.
Continuous processing in which a small amount of sensitive material is processed is called small-volume running. (Note 3) The total amount of the pre-wash replenisher solution that enters the pre-wash bath and the bleach-fix solution that adheres to the photosensitive material is 2 times the tank capacity.
When it doubles, it is considered to have reached convergence.

[Table] As is clear from Table 3 above, the generation of floating matter and precipitates in baths following baths containing soluble silver salts occurred in 7 days in the second bath and 18 days in the first bath. On the other hand, this invention did not occur even after 50 days, indicating that it is extremely superior. Also, the washing tank is generally left empty for long-term storage, but if you leave the water in the first washing tank, where precipitation is likely to occur, without discarding the water, the comparison shows that precipitation has formed on the second day. In contrast, the present invention occurred on the fifth day. This indicates that it also has the effect of preventing sedimentation in the washing tank. In addition, there is a concern about the influence on the photographic performance of the photosensitive material, especially the image storage stability, but there was no problem as it was almost the same as the comparison without additives.

Claims (1)

[Scope of Claims] 1. In a method for developing a silver halide color photographic light-sensitive material, the silver halide color photographic light-sensitive material is color-developed and processed in a bath containing silver thiosulfate, followed by other processing steps. silver thiosulfate in a treatment bath consisting of two or more tanks containing at least one of the compounds represented by the following general formulas [], [], [], [], [], and []. A replenisher in an amount of 1 to 20 times the amount of processing solution brought into the processing bath by the photosensitive material from the bath containing acetic acid is supplied to the final tank of the processing bath, and the processing solution in this tank is transferred to the previous tank. 1. A method for processing a silver halide color photographic material, which comprises processing by backflowing the material. General formula [] E ¹ −A ¹ −Z−A ^{2 −E} 2General formula [] General formula [] R ⁴ N (CH ₂ PO ₃ M ₂ ) ₂ General formula [] General formula [] General formula [] [In the formula, M is a hydrogen atom, an alkali metal atom or an ammonium group, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and
A ⁶ is each substituted or unsubstituted alkylene group, Z
is an alkylene group substituted with a hydroxy group or N-A ₇ (A ₇ represents a lower aliphatic phosphonic acid group),
E ¹ , E ² , E ³ , E ⁴ , E ⁵ and E ⁶ are each a hydroxyl group, -COOM or -PO ₃ M ₂ , X, Y and Z ¹
is a hydrogen atom, a hydroxyl group, -COOM or -
PO ₃ M ₂ , R ⁴ is a carboxyl group-substituted cyclohexyl group, R ⁶ and R ⁷ are a hydrogen atom, a lower alkyl group (the group may be substituted with a carboxyl group), a carboxyl group or -NJ ₂ (J is hydrogen atom,
hydroxyl group, lower alkyl group, hydroxyethyl group), R ⁸ is a hydrogen atom, -COOM or -PO ₃ M ₂ , R ⁹ is a substituted alkyl group having 1 to 12 carbon atoms, a substituted alkenyl group or an acyl group, R ₁₀ is a hydrogen atom, an alkali metal atom, ammonium, or a substituted alkyl group having 1 to 12 carbon atoms, R ₁₁ is an aralkyloxy group, an arylamino group, or an acyloxy group, Q ¹ and Q ² are each -OM ¹ (M ¹ is a cation ) or acyloxy group, Q ³ is −OM ¹ ,
Acyloxy group or aralkyloxy group and q represent 0, 1 or 2. ] 2 The amount of the compound represented by the general formula [], [], [], [], [] and [] is 0.1 to 50 g/
Claim 1, characterized in that
A method for processing a silver halide color photographic light-sensitive material as described in .