JP3491233B2 - Silver halide photographic processing composition and processing method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improvement in a photographic processing solution for processing an exposed silver halide photographic light-sensitive material. More specifically, for sequestering harmful metal ions or for use as a bleaching agent,
A silver halide photographic processing composition containing a novel chelating agent for photographic use and a processing method.

[0002]

BACKGROUND OF THE INVENTION Generally, in order to process an exposed silver halide photographic light-sensitive material to obtain an image, it is necessary to perform processing with various processing solutions including a developing solution and a fixing solution. More processing steps are required, especially for obtaining color images. Since the treatment liquid used for these treatments contains a large number of components, if the water used for its preparation contains metal ions such as calcium, magnesium and iron, it reacts with them to cause precipitation. And generate sludge. Then, there are drawbacks such as clogging of a filter attached to the automatic developing processor or adhesion to the surface of the photographic light-sensitive material being processed to cause contamination. or,
Even if pure water is used to prevent this when preparing the processing solution, metal ions may be eluted from the photographic light-sensitive material during processing, or metal ions may be brought in from the previous processing step. It was extremely difficult to completely prevent the generation of sludge. Furthermore, some of the various components contained in the treatment liquid lose their effectiveness because their oxidation and decomposition are promoted by the action of metal ions, so when treated with this treatment liquid,
There are drawbacks such as generation of fog and deterioration of photosensitivity.

In order to prevent these undesirable effects of metal ions on the processing solution, it has been proposed and put into practice to add a so-called chelating agent for sequestering metal ions to the photographic processing composition. For example, British Patent 520,
Polyphosphates such as sodium hexametaphosphate proposed by US Pat. No. 5,933, alkylidene diphosphonic acids proposed by US Pat. No. 321,445, US Pat. No. 3,201,24
Examples thereof include aminopolymethylenephosphonic acid proposed in No. 6 and aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid. However, even when these chelating agents are blended, there are various drawbacks in practical use and they are not satisfactory. That is, since polyphosphate has a small sequestering power for metal ions and is particularly weak against heavy metal ions, it cannot be put to practical use.

Alkylidene diphosphonic acid has a problem that when calcium ions and sodium ions coexist at a certain concentration or more, solid precipitates are generated and the automatic development processor is hindered. Ordinary aminopolycarboxylic acids represented by ethylenediaminetetraacetic acid and aminopolymethylenephosphonic acids represented by aminotrimethylenephosphonic acid have excellent sequestering power, but a color developer containing hydroxylamine. However, there is a disadvantage that hydroxylamine is decomposed in the coexistence of metal ions and fog occurs when processed with this developing solution, and in a black and white developing solution, oxidation of the developing agent is promoted to deteriorate storage stability and It has the drawback of causing significant fog on the speed film.

As described above, all of the conventionally proposed chelating agents have some drawbacks, and in reality, they are not sufficiently effective when used in a photographic processing composition. Further, due to recent social and environmental requirements such as low pollution and economic requirements such as cost reduction, the replenishment amount of the photographic processing solution tends to be reduced more and more. The accumulation amount of metal ions also tends to increase.

The raw materials used for photographic materials are also
For the purpose of cost reduction, lower grade and cheaper ones tend to be used, and the amount of metal ions accumulated in a photographic processing solution is increasing.

For this reason, in recent years, there is a situation in which conventional techniques cannot control the situation. by the way,
In the processing of silver halide color photographic light-sensitive materials, the above-mentioned chelating agents, aminopolycarboxylic acids, are widely used in large amounts in bleaching solutions and bleach-fixing solutions as bleaching agents for removing image silver in the form of the metal complex salts. Has been. Examples of the metal complex salt of aminopolycarboxylic acid include ethylenediaminetetraacetic acid ferric iron complex salt, 1,3-propylenediaminetetraacetic acid ferric iron complex salt, diethylenetriaminepentaacetic acid ferric iron salt and the like.

Among these bleaching agents, ferric complex of 1,3-propylenediaminetetraacetic acid has a very high oxidative power, so that it can be rapidly processed especially for high-sensitivity silver halide color photographic light-sensitive materials. It is used in the bleaching solution for the purpose. However, ferric 1,3-propylenediaminetetraacetic acid complex salt oxidizes the color developing agent brought in from the pre-bath of the processing step due to its high oxidizing power, and forms unreacted coupler and dye in the light-sensitive material. However, it has the drawback of causing so-called bleaching fog.

Further, the ferric ethylenediaminetetraacetic acid complex salt is inferior in oxidizing power to the ferric complex salt of 1,3-propylenediaminetetraacetic acid, but in order to simplify the treatment process and accelerate the treatment, a bleaching process is performed. It is often used as a bleaching agent in the bleach-fixing step in which the fixing step and the fixing step are performed in one bath. In the bleach-fix bath, a bleaching agent that is an oxidizing agent and a fixing agent (thiosulfate ion) that is a reducing agent coexist, so there is a phenomenon that the bleaching agent decomposes into thiosulfate ion to decompose into sulfur. Then, sulfite ions are usually added to the bleach-fix solution as a preservative to prevent sulfuration of thiosulfate ions. However, when the ferric ethylenediaminetetraacetic acid complex salt is used in the bleach-fixing bath, the ferric ethylenediaminetetraacetic acid complex salt is very fast in the oxidation rate from divalent iron to trivalent iron, and therefore, in the bleach-fixing bath. There is a drawback that the iron trivalent state is always maintained and the preservative sulfite ion is continuously decomposed, and as a result, the sulfuration of thiosulfate ion is accelerated and the storage stability of the liquid is lowered.

As a method for solving this problem, Japanese Patent Laid-Open No.
-149358, 59-151154, 59-166977 and the like disclose techniques using a ferric iron complex salt of diethylenetriaminepentaacetic acid.

These techniques are certainly superior in storage stability to the bleach-fixing solution using a ferric ethylenediaminetetraacetic acid complex salt. However, when the color paper treatment is carried out using the ferric diethylenetriaminepentaacetic acid complex salt, there is a problem that stains are recognized on the edge portion and a failure called edge penetration is likely to occur.

Further, in recent years, from the standpoint of protecting the global environment, it has been desired to use materials having good biodegradability. However, the above-mentioned ferric ethylenediaminetetraacetic acid complex salt and diethylenetriaminepentaacetic acid ferric iron complex salt are extremely biodegradable. It is known to be poor in sex and is not preferable. Recently in Germany,
Since the EDTA concentration in drinking water is high, it will be 5
There is a voluntary regulation to reduce the amount of EDTA used to half the current amount.

As means for solving this problem, German Patent Nos. DE 3,939,755 and DE 3,939,756 describe nitrilomonopropionic acid diacetic acid (NMPDA), nitrilodipropionic acid monoacetic acid (NDPMA), The technique of using general nitrilotriacetic acid (NTA) as a benign degradation chelate has already been disclosed. However, the NMPDA
And NDPMA are in the easy-degradability test “Modified MITI method” that is approved by the Ministry of International Trade and Industry as a biodegradability evaluation method (if it is certified as good degradation by this method, it means rapid degradation in the natural world). It has been confirmed that it hardly decomposes, and is not a fundamental solution to this problem.

It has also been confirmed that the use of the ferric complex salts of NMPDA and NDPMA as a bleaching agent causes the bleaching fog described above. For one NTA, MITI
Although it has good biodegradability by the method, it is not suitable for practical use because the ferric iron complex salt has insufficient oxidizing power.

Therefore, it has a bleaching solution having a rapid desilvering property without causing bleaching fog and a rapid desilvering property, has an excellent storage stability of the liquid, and is free from edge stains.
Further, the appearance of a bleach-fix solution having excellent biodegradability is strongly desired.

[0016]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a bleaching ability for a silver halide photographic light-sensitive material which has a rapid desilvering property, has no edge stain and has excellent liquid storage stability. It is an object of the present invention to provide a processing composition for a silver halide photographic light-sensitive material and a processing method.

A second object is to provide a processing composition and a processing method for a silver halide photographic light-sensitive material capable of obtaining a stable processing solution without precipitation or sludge generation due to the presence of metal ions.

A third object is to provide a processing composition for silver halide photographic light-sensitive materials, which can be stably processed for a long period of time when it is processed by an automatic development processor and does not cause clogging of an attached filter. And to provide a processing method.

A fourth object is to provide a processing composition and a processing method for silver halide photographic light-sensitive materials which are excellent in biodegradability and suitable for protecting the global environment. Other purposes will be apparent from the following specification.

[0020]

The above objects of the present invention are achieved by the following photographic processing composition and processing method.

1. A silver halide photographic processing composition containing at least one compound represented by the following general formula [I]:

[0022]

[Chemical 1]

In the formula, n'is an integer of 1 to 3, A _{1 to} A ₄ ,
B _{1 to} B ₅ represent H, OH, C _n H _{2n + 1} , or (CH ₂ ) _m X, and n and m each represent an integer of 1 to 3 and 0 to 3, and X
Is (are M represents H, a cation or an alkali metal _{atom,.) -COOM, - NH 2} , represents an -OH. However, not all of B _{1 to} B ₅ represent H.

2. 2. The silver halide photographic processing composition described above, which is a bleaching solution or a bleach-fixing solution containing a ferric complex salt of a compound represented by the general formula [I]. Photographic processing agent composition 3. 3. The silver halide photographic processing composition as described in 1 above, wherein the silver halide photographic processing composition is a developer containing the compound represented by the general formula [I]. 4. The silver halide photographic processing composition as described in 1 above, wherein the silver halide photographic processing composition is a fixing solution containing a compound represented by the general formula [I]. 5. The silver halide photographic processing composition as described in 1 above, wherein the silver halide photographic processing composition is a stabilizing solution containing the compound represented by the general formula [I]. In the method for processing a silver halide photographic light-sensitive material, which comprises image-wise exposing a silver halide photographic light-sensitive material, color development, and then bleaching or bleach-fixing, the bleaching solution or the bleach-fixing solution is represented by the general formula [I]. The second of the compounds shown
6. Processing method of silver halide photograph containing iron complex salt At least one of the compounds represented by the following general formula [II]
Silver halide photographic processing agent composition characterized by containing

[0025]

[Chemical 2]

In the formula, B _{1 to} B ₄ and X _{1 to} X ₄ are H,
C _n H _{2n + 1} or (CH ₂ ) lY, where n and l are 1
Represents an integer of ~3,0~3, Y is -COOM (M represents H, a cation or an alkali metal _{atom,.), - NH 2,} -O
Represents H. However, all of B _{1 to} B ₄ do not represent H, all of X _{1 to} X ₂ do not represent H, and _two of X _{1 to} X ₄ do not simultaneously represent OH. m
_{1 to} m ₄ represent an integer of 1 to 3, A ₁ and A ₂ are -COOM ₁ and -C.
OOM ₂ (M represents H, cation, alkali metal atom),
Represents --NH ₂ , OH, Z ₁ and Z ₂ are --COOM (M ₁ and M ₂ are H,
Represents a cation, an alkali metal atom), an alkyl group having 1 to 3 carbon atoms, or OH.

8. 8. The silver halide according to the above 7, wherein the silver halide photographic processing composition is a bleaching solution or a bleach-fixing solution containing a ferric complex salt of the compound represented by the general formula [II]. Photographic processing composition.

9. The silver halide photographic processing composition
Is a development containing a compound represented by the above general formula [II].
7. A silver halide copy as described in 7 above, which is a liquid
True treatment composition 10. The silver halide photographic processing composition is
A fixing solution containing a compound represented by the general formula [II]
7. The silver halide photographic processing agent as described in 7 above,
Composition 11. The silver halide photographic processing composition is
It is a stabilizing solution containing the compound represented by the general formula [II].
7. The silver halide photographic processing agent as described in 7 above,
Composition 12. After imagewise exposure of a silver halide photographic light-sensitive material, color development
Halogen for imaging and then bleaching or bleach-fixing
In the processing method for silver halide photography, the bleaching solution or bleaching solution
Ferric complex salt of the compound represented by the above general formula [II]
For processing silver halide photographs containing silver 13. Compounds represented by the following general formula [III] or [IV]
It is characterized by containing at least one selected from the
A characteristic silver halide photographic processing composition. General formula [III] (R₁) (R₂) N-X₁-(Z-X₂)_n-N (R
₃) (R_Four) Where R₁~ R₃Is -L₁-Y₁Represents (L₁Is
A substituted or unsubstituted alkylene group having 1 to 3 carbon atoms
Then Y₁Is -OH, -NH₂Or -COOM (M is hydrogen ion,
Alkali metal ions or other cations)
). R_FourIs H, -CH₃, Or C₂H_FiveRepresents n is 0
Represents an integer of 4. Z is an alkylene group, -O-, -NH-,
−N (L₂−Y₂) − Or −CH (L₃−Y₃)-Represents (L₂, L₃
Is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms
Represent, Y₂, Y₃Is a hydrogen atom, -OH, -NH ₂Or −COO
M₁, -COOM₂(M₁, M₂Is hydrogen ion, alkali metal
On or other cations)). X₁, X₂Is charcoal
A substituted or unsubstituted alkylene group having a prime number of 1 to 6,
Is -CH (L_Four−Y_Four)-Represents (L_FourIs a substituted or unsubstituted
Represents an alkylene group having 1 to 4 carbon atoms, Y_FourIs a hydrogen atom,
-OH, -NH₂Or −COOM₁, -COOM₂(M₁, M₂Is hydrogen
Ion, alkali metal ion or other cation)
Represents). However, when n = 0, X₁Is a unit having 2 to 6 carbon atoms
It represents a substituted or unsubstituted alkylene group. General formula [IV] (R₁) HN-X₁-(Z-X₂)_n-NH (R₂) Where R₁, R₂, X₁, X₂, Z, n are general formulas
It is synonymous with each of [III]. However, when n = 0
X₁Is a substituted or unsubstituted alkylene having 3 to 6 carbon atoms.
Represents a group.

14. A bleaching solution and a bleach-fixing solution, wherein the silver halide photographic processing agent composition contains a ferric complex salt of at least one compound selected from the compounds represented by the general formulas [III] and [IV]. 14. The silver halide photographic processing agent composition as described in 13 above, wherein

15. 13. The silver halide photographic processing composition is a developing solution containing at least one compound selected from the compounds represented by the general formulas [III] and [IV]. The silver halide photographic processing composition as described above.

16. 13. The silver halide photographic processing composition is a fixing solution containing at least one compound selected from the compounds represented by the general formulas [III] and [IV]. The silver halide photographic processing composition as described above.

17. 13. The silver halide photographic processing composition is a stabilizing solution containing at least one compound selected from the compounds represented by the general formulas [III] and [IV]. The silver halide photographic processing composition as described above.

18. After imagewise exposure of a silver halide photographic light-sensitive material, color development is carried out, and then bleaching or bleach-fixing is carried out with a second compound of at least one compound selected from the compounds represented by the above general formulas [III] and [IV]. A method for processing a silver halide photograph, characterized by containing an iron complex salt.

19. The following general formulas [V], [VI] and [VI
A silver halide photographic processing composition comprising at least one compound selected from the compounds represented by the formula [I]. General formula [V] (R ₁ ) (R ₂ ) N- (C = X ₁ ) -W- (C =
_{X 2) -N (R 3)} ( in R ₄₎ formula, R ₁ to R ₄ is or each hydrogen atom - (CH _{2) m3} -C
H [(CH _{2) m2} -Z2] - (CH ₂₎ represents a _m1 --Z1. Z ₁ and Z ₂ are hydrogen atoms, —COOM (M represents hydrogen ion, alkali metal ion or other cation), —OH or —NH ₂ ,
m _{1 to} m ₃ represent an integer of 0 to 2. However, not all of R _{1 to} R ₄ are hydrogen atoms. W is a substituted or unsubstituted alkylene group having 1 to 5 carbon _{atoms, - (D 1 O) m4} -D 2 or _{-O- (D 3) m5 -O- (} D 1 ~D 3 is 1 to 3 carbon atoms Represents the methylene chain of). Further, m _4, m ₅ represents an integer of 1 to 3. X ₁ and X ₂ represent an oxygen atom or a sulfur atom. Formula _{[VI] (R 1) (} R 2) N- (C = X 1) - in (R ₃₎ formula, R ₁ to R ₃ and X ₁ are the same meanings as defined above, respectively general formula [V] . However, not all of R _{1 to} R ₃ are hydrogen atoms. General formula [VII] (R ₁ ) N-[(C = X ₁ ) -R ₂ ]-[(C =
X ₂ ) -R ₃ ] In the formula, R _{1 to} R ₃ and X ₁ and X ₂ are each represented by the general formula [V].
Is synonymous with each. However, not all of R _{1 to} R ₃ are hydrogen atoms.

20. The silver halide photographic processing composition is a second composition containing at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII].
20. The silver halide photographic processing composition as described in 19 above, which is a bleaching solution or a bleach-fixing solution containing an iron complex salt.

21. The silver halide photographic processing composition is a developing solution containing at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII]. 20. The silver halide photographic processing agent composition described in 19 above.

22. The silver halide photographic processing composition is a fixing solution containing at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII]. 20. The silver halide photographic processing agent composition described in 19 above.

23. The silver halide photographic processing composition is a stabilizing solution containing at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII]. 20. The silver halide photographic processing agent composition described in 19 above.

24. After imagewise exposure of a silver halide photograph, color development is performed, and then bleaching or bleach-fixing is performed by using at least one compound selected from the compounds represented by the above general formulas [V], [VI] and [VII]. A method for processing a silver halide photograph, characterized by containing a ferric complex salt.

The present invention will be described in detail below. Specific preferred examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0041]

[Chemical 3]

[0042]

[Chemical 4]

[0043]

[Chemical 5]

Of these, particularly preferred compounds are
(I-1), (I-3), (I-6), (I-8), (I-14) and (I-20). As an example of synthesizing the compound represented by the general formula [I], one example of the synthetic method for the exemplified compound (I-1) is shown below.

Synthesis Example of Exemplified Compound (I-1) 133.1 g (1 mol) of L-aspartic acid was suspended in 100 ml of water, and 128 g of sodium hydroxide was stirred while cooling with ice.
Add (3.2 mol) of 30% aqueous solution. Acrylic acid 8
6.5 g (1.2 mol) was added dropwise with stirring at room temperature, and the mixture was refluxed overnight. When adjusted to pH 2.2 with 6N hydrochloric acid under ice cooling, white crystals slowly precipitate. For purification, it is dissolved in an aqueous solution of sodium hydroxide, 6N hydrochloric acid is added to adjust the pH to 2.2, and precipitation is performed. This is filtered, washed with water, ethanol and ether, and dried at 90 ° C for 1 day. Yield 96.6g (Yield 47.1
%) Elemental analysis value: C, 40.980%; H, 5.4
04%; N, 6.827% Calculated value (C ₇ H ₁₁ NO ₆ ): C, 41.026%; H, 5.353
%; N, 6.800% Other exemplary compounds represented by the general formula [I] can be synthesized by the same generally known method.

Specific preferred examples of the compound represented by the above general formula [II] are shown below, but the invention is not limited thereto.

[0047]

[Chemical 6]

[0048]

[Chemical 7]

Of these, particularly preferred compounds are (II
-1), (II-2), (II-3), (II-4), (II-11), (II
-12) and (II-17). As an example of synthesizing the compound represented by the general formula [II], an example of the synthetic method for the exemplified compound (II-12) is shown below.

Synthesis Example of Exemplified Compound (II-1) 75 g (1 mol) of glycine was added to 100 ml of water, and a 30% aqueous solution of 128 g (3.2 mol) of sodium hydroxide was added with stirring under ice cooling. Methacrylic acid 206.4g (2.4mo
l) is added dropwise at room temperature with stirring and then refluxed overnight.
When adjusted to pH 2 with 6N hydrochloric acid under ice cooling, white crystals slowly precipitate. For purification, it is dissolved in an aqueous solution of sodium hydroxide, and 6N hydrochloric acid is added to adjust the pH to pH 2 for precipitation. This is filtered, washed with water, ethanol, ether, 90 ℃
And dry for 1 day.

Yield 160.5 g (yield 65.0%) The structure was confirmed by proton NMR, FD-MS and IR. Other exemplary compounds represented by the general formula [II] can be synthesized by the same generally known method.

Preferred specific examples of the compound represented by the general formula [III] or [IV] are shown below, but the invention is not limited thereto.

[0053]

[Chemical 8]

[0054]

[Chemical 9]

[0055]

[Chemical 10]

[0056]

[Chemical 11]

[0057]

[Chemical 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

[0060]

[Chemical 15]

Of these, particularly preferred compounds are (III-
1), (III-6), (III-7), (III-17), (III-18),
(IV-1), (IV-7), (IV-16) and (IV-18), and the most preferred compound is (III-1).

The compound represented by the above general formula [III] or [IV] is described in "Chelate Chemistry" No. 5 by Keihei Ueno.
Volume, the method described in Chapter 1 (Nankodo) and other generally known methods can be used for synthesis.

As a specific example of the synthesis of 1.3-propanediamine-N, N, N'-3acetic acid, which is a typical compound (III-1), the 42nd Annual Meeting of the Complex Chemistry Discussion Group (1992), p. 67. The detailed description is given in.

Hereinafter, the above general formulas [V], [VI], [VII]
Preferred specific examples of the compound represented by are shown below, but the invention is not limited thereto.

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

[0072]

[Chemical formula 23]

[0073]

[Chemical formula 24]

Of these, a particularly preferred compound is (V-
1), (V-2), (VI-1) and (VI-14) and [VII-2]
Is. As an example of synthesizing the compounds represented by the above general formulas [V] to [VII], an example of the synthetic method for the exemplified compound (V-1) is shown below.

Synthesis Example of Exemplified Compound (V-1) 266.2 g (2 mol) of iminodiacetic acid and 280 sodium hydroxide
g (7 mol) was dissolved in 1500 ml of water under ice cooling and
141 g (1 mol) of malonyl chloride are slowly added dropwise while stirring at (° C). After stirring for 2 hours, add 6N hydrochloric acid
The pH was adjusted to 2 and 1 liter of ethanol was added. By recrystallizing the obtained crystal using water / ethanol, 251 g of white crystal target product V-1 (yield 75
%) Was obtained. The structure was confirmed by proton NMR, FD-MS, and IR.

Other compounds represented by the above general formulas [V] to [VII] can also be synthesized by the same generally known method. First, the case where the processing solution of the present invention is a processing solution having a bleaching ability, that is, a bleaching solution or a bleach-fixing solution will be described.

In the present invention, the bleaching solution or the bleach-fixing solution contains a second compound represented by the general formula [I] to [VII].
It is particularly preferable to use it in the form of an iron complex salt. The amount of these compounds added to the processing solution having a bleaching capacity is 1 liter per liter.
The content is preferably in the range of 0.05 to 2.0 mol, and more preferably in the range of 0.1 to 1.0 mol.

In the bleaching solution or the bleach-fixing solution of the present invention, as the bleaching agent, in addition to the iron complex salts of the compounds represented by the above formulas [I] to [VII], ferric iron complex salts of the following compounds can be used. . [A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycinic acid [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A'- 5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriamine pentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxyethylethylenediamine Acetic acid [A′-10] ethylenediaminepropionic acid [A′-11] ethylenediaminediacetic acid [A′-12] hydroxyethyliminodiacetic acid [A′-13] nitrilotriacetic acid [A′-14] nitrilotripropionic acid [A '-15] Triethylenetetramine hexaacetic acid [A'-16] ethylenedia Mintetrapropionic acid The amount of the ferric iron complex salt of organic acid added is preferably 0.05 to 2.0 mol, and more preferably 0.10 to 1.5 mol / l, per liter of the bleaching solution or the bleach-fixing solution.

The bleaching solution and the bleach-fixing solution are described in JP-A 64-295.
Imidazole and its derivative described in Japanese Patent No. 258, or compounds represented by the general formulas [I] to [IX] described in the same publication and at least one of these exemplified compounds are effective for the rapidity of treatment. Can play.

In addition to the above accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and JP-A-6-123
The exemplified compounds described on pages 22 to 25 of JP-A 3-17445, the compounds described in JP-A-53-95630, JP-A-53-28426 and the like can also be used in the same manner.

The temperature of the bleaching solution and the bleach-fixing solution is 20 ° C to 50 ° C.
It is preferably used at 25 ° C to 45 ° C. The pH of the bleaching solution is preferably 6.0 or less, more preferably
It should be 1.0 or more and 5.5 or less. The pH of the bleach-fix solution is
It is preferably 5.0 to 9.0, and more preferably 6.0 to 8.5.
The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing bath during processing of the silver halide light-sensitive material, and is the so-called replenishing solution
It can be clearly distinguished from H.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

The preferred replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less, preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml, per 1 m ^{2 of the} silver halide color photographic light-sensitive material. The higher the degree, the more remarkable the effect of the present invention becomes.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air or oxygen may be blown in the processing bath and the storage tank of the processing replenisher, if desired, or suitable oxidation may be carried out. Agents, such as hydrogen peroxide,
Bromate, persulfate and the like may be added as appropriate.

As the bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is preferably at least 0.1 mol / l or more, more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when processing a color negative film. The content of thiosulfate is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when processing a color negative film.

The bleach-fixing solution or the fixing solution according to the present invention may contain, in addition to these fixing agents, one or more pH buffer agents comprising various salts. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. In addition, compounds known to be added to ordinary bleach-fixing solutions such as alkylamines and polyethylene oxides can be appropriately added.

Incidentally, silver may be recovered from the bleach-fixing solution according to the present invention by a known method. For the bleach-fixing solution, Japanese Patent Laid-Open No. 64-2
It is preferable to add a compound represented by the following general formula [FA] described on page 56 of the specification of No. 95258 and its exemplified compounds, and not only the effects of the present invention can be better exhibited but also a small amount of a light-sensitive material can be used for a long time. Another effect is that the amount of sludge generated in the processing liquid having fixing ability during the entire processing is extremely small.

General formula [FA]

[0089]

[Chemical 25]

The compound represented by the general formula [FA] in the above specification is described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718.
Can be synthesized by a general method as described in the specification. These compounds represented by the above general formula [FA] may be used alone or in combination of two or more kinds.

Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 to 200 g per liter of the treatment liquid. The processing time with the bleaching solution and the bleach-fixing solution is arbitrary, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 minutes.
It ranges from seconds to 1 minute 20 seconds. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably 10 seconds to 2 minutes.
It is in the range of 20 seconds.

When the ratio of ammonium ion to the total cations in the processing solution for silver halide color photographic light-sensitive material of the present invention is 50 mol% or less, not only the effect of the object of the present invention is better. However, it is one of the preferred embodiments of the present invention because it has little odor. It is particularly preferably 30 mol% or less, particularly preferably 10 mol% or less.

The bleaching solution and the bleach-fixing solution according to the present invention include
It may contain a compound represented by the general formula [II] described in Japanese Patent Application No. 4-64897 and hydroxyacetic acid. Next, the case where the processing solution of the present invention is other than the bleaching solution or the bleach-fixing solution will be described. When the processing solution of the present invention is a processing solution other than a bleaching solution or a bleach-fixing solution, 0.1 to 50 g, preferably 0.5 to 10 g, of the compound of the above formulas [I] to [VII] is added per 1 liter of these processing solutions. This gives good results. When compounding, two or more compounds represented by the above general formula may be used, or may be used in combination with another chelating agent. When preparing the treatment liquid, it may be added to the treatment liquid together with other components, or may be added together with the other components in a powder form into the kit or in the concentrated liquid kit. Good.

The photographic processing composition of the present invention can be applied to any processing solution for processing a silver halide photographic light-sensitive material. For example, general black-and-white developing solution, squirrel infectious developing solution, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, stop solution, hardening solution, stabilizing solution, fog solution and toning solution can be mentioned. However, the present invention is not limited to these. Further, the photographic processing composition of the present invention is used for the processing of all silver halide photographic light-sensitive materials such as color films, color photographic papers, black and white films for general use, X-ray films, lith films for printing and micro films. can do.

After the bleach-fixing treatment employed in the present invention, it is preferable to employ a stabilizing treatment with a stabilizing solution. For the purpose of the present invention, it is particularly preferable that the stabilizing solution contains a chelating agent having a chelate stability constant of 8 or more for iron ions. Here, the chelate stability constant is the value of “StabilityCons” by LG Sillen, AEMarttell.
tants of Metal-ion Complexes "The Chemical Societ
y, London (1964), S. Chaberek, AE Martell, “Organic
Sequestering Agents "means constants generally known by Wiley (1959).

The chelate stability constant for iron ions is 8
As the chelating agent as described above, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
Examples thereof include polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent as described above include, but are not limited to, the following compounds in addition to the compounds represented by the general formulas [I] to [VII] of the present invention. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid,
2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, Examples include sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1- Diphosphonic acid is most preferably used.

The amount of the above chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20, per liter of the stabilizing solution.
Good results are obtained in the range of g. Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilizer. These are supplied by various inorganic and organic ammonium salts, and specifically, for example, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, Ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate,
Ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, Ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate,
Ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidinedithiocarbamate. , Ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-
Trinitrophenol ammonium and the like. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably 0.001 mol to 1.0 mol, and more preferably 0.002 to 0.8 mol, per liter of the stabilizing solution.

Further, the stabilizing solution preferably contains sulfite. The sulfite may be any organic substance or inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt. Examples of preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. To be The above sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ^-3 mol / liter, more preferably 5 × 10 ^-3 mol / liter to 10 ^-1 mol / liter. Such an amount is added, and it is particularly effective in preventing stains. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

Other generally known compounds that can be added to the stabilizing solution are polyvinylpyrrolidone (PVPK-1).
5, K-30, K-90), organic acid salts (eg citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjuster (eg phosphate, borate, hydrochloric acid, sulfuric acid, etc.), antifungal agent (eg phenol derivative, catechol derivative, imidazole derivative, triazole derivative, siabendazole) Derivatives, organohalogen compounds, and other paper-antifungal agents known as slime control agents in the pulp industry) or optical brighteners, surfactants, preservatives, Bi, Mg, Zn,
There are metal salts such as Ni, Al, Sn, Ti and Zr. One or two or more of these compounds can be arbitrarily selected and used within a range that does not impair the effects of the present invention.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed. The presence of a soluble iron salt in the stabilizing solution is preferable for achieving the effects of the present invention. At least 5 × 10 soluble iron salts in the stabilizing solution
It is preferably used at a concentration of ^-3 mol / l,
It is more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / liter, and further preferably in the range of 12 × 10 ^{−3 to} 100 × 10 ⁻³ mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenishing solution, or they can be dissolved in the stabilizing solution (tank solution) from the photosensitive material to form the stabilizing solution (tank solution). It may be added, or may be added to the stabilizing solution (tank solution) by adhering it to the photosensitive material to be processed from the prebath and bringing it in.

Further, in the present invention, a stabilizing solution containing calcium ion and magnesium ion of 5 ppm or less which has been treated with an ion exchange resin may be used. You may use the method.

In the present invention, the pH of the stabilizing solution is 5.5 to 10.
A range of 0 is preferred. PH that can be contained in the stabilizing solution
The modifier may be any of the commonly known alkaline or acid agents.

The treatment temperature for the stabilization treatment is 15 ° C to 70 ° C.
C is preferable, and more preferably in the range of 20 to 55 ° C. The treatment time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds.

The replenishing amount of the stabilizing solution is preferably 0.1 to 50 times, particularly 0.5 to 30 times the carrying amount of the pre-bath (bleach-fixing solution) per unit area of the light-sensitive material from the viewpoint of rapid processing property and storability of dye image. preferable.

The stabilizing tank is preferably composed of a plurality of tanks, preferably not less than 2 tanks and not more than 6 tanks, particularly preferably 2 to 3 tanks, and further preferably 2 tanks. It is preferable to use a system in which the solution is supplied to the post-bath and overflows from the pre-bath.

As the color developing agent used in the color developing treatment step, there are aminophenol compounds and p-phenine diamine compounds, but in the present invention and the present invention, p-phenine having a water-soluble group is used. Diamine compounds are preferred. Such a water-soluble group has at least one amino group or a Benzen nucleus on the p-phenylenediamine compound, and specific water-soluble groups include-
_{(CH 2) n -CH 2 OH} , - (CH 2) m -NHSO 2 - (CH 2) n -CH 3, - (CH 2) m
_{-O- (CH 2) n -CH 3} , - (CH 2 CH 2 O) n -C m H 2m + 1 (m and n each represents an integer of 0 or more.), - COOH group, -SO ₃ H groups and the like are mentioned as preferable ones.

Specific examples of the color developing agent preferably used in the invention are shown below.

[0109]

[Chemical formula 26]

[0110]

[Chemical 27]

Of the above-illustrated color developing agents, preferred for use in the present invention are (A-1), (A-2), and (A-
3), (A-4), (A-6), (A-7) and (A-
15) and particularly (A-1) or (A
-3).

The above color developing agent is usually used in the form of a salt such as a hydrochloride, a sulfate or a p-toluenesulfonate. The amount of color developing agent added is preferably 0.5 × 10 ^-2 mol or more, more preferably 1.0 × 10 ^{-2 to} 1.0 × 10 ^-1 mol, and most preferably 1.5 per liter of the color developing solution. It is in the range of × 10 ^{-2 to} 7.0 × 10 ^-2 mol.

The color developing solution used in the color developing processing step is an alkaline agent usually used in developing solutions such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or the like. Borax and the like can be included. Further, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, or development regulators such as citrazinic acid, and preservatives such as hydroxylamine and hydroxylamine derivatives (such as diethylhydroxyl). Amines, disulfoethylhydroxylamine, dicarboxyethylhydroxylamine, etc.), hydrazine derivatives (eg hydrazinodiacetic acid), sulfites, etc. Furthermore,
Various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, and the like can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9-13. In the color developing solution, if necessary, as an antioxidant, for example, tetronic acid, tetronimide,
2-anilinoethanol, dihydroxyacetone, secondary aromatic alcohol, hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be combined.

In the color developing solution, various chelating agents can be used together as a sequestering agent. In addition to the compounds represented by the general formulas [I] to [VII] of the present invention, other chelating agents such as aminodicarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid Such as organic phosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, etc. aminopolyphosphonic acid, citric acid, gluconic acid, etc. oxycarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etc. phosphono Examples thereof include carboxylic acid, polyphosphoric acid such as tripolyphosphoric acid, and hexametaphosphoric acid.

The preferable replenishment amount of the color developing solution in the continuous processing is as to the light-sensitive material 1 for the color negative film.
It is preferably 1500 ml or less per m ² , more preferably 250 ml to 9
It is 00 ml, more preferably 300 ml to 700 ml. 20-300 ml, preferably 30-1 for color paper processing
It is 60 ml.

[0117]

EXAMPLES Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 Preparation of silver halide color photographic light-sensitive material (color paper) A support was prepared by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer. Each layer having the constitution shown below was applied to prepare a multilayer silver halide color photographic light-sensitive material. The coating liquid was prepared as follows. First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 100 g, (ST-2) 6.67 g, additive (H
Q-1) 0.67 g was dissolved in 6.67 g of high boiling organic solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was ultrasonicated in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1). A yellow coupler dispersion was prepared by emulsifying and dispersing using a homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 9.5 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (SU-3)
Was added to adjust the surface tension.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Chemical 28]

[0123]

[Chemical 29]

[0124]

[Chemical 30]

[0125]

[Chemical 31]

[Preparation Method of Blue-Sensitive Silver Halide Emulsion] 40
In 1000 ml of 2% gelatin aqueous solution kept at ℃, the following (A
30) while controlling the liquids) and (B liquid) to pAg = 6.5 and pH = 3.0
Simultaneously added over a period of minutes, and then the following (solution C) and (solution D)
Was simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (Solution D) ) Silver nitrate 300 g After adding water to 600 ml, desalting was performed using a 5% aqueous solution of Demol N and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.85 μm. A monodisperse cubic emulsion EMP-1 having a variation coefficient of particle size distribution of 7% and a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-A). Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer (STAB-1) 5.8 × 10 ^-4 mol / mol AgX Sensitizing dye (BS-1) 4.1 × 10 ^-4 mol / mol AgX Increase Sensitizing dye (BS-2) 1.2 × 10 ⁻⁴ mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
A monodisperse cubic emulsion EMP-2 of was obtained.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-B). Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX Stabilizer (STAB-1) 5.8 × 10 ⁻⁴ mol / mol AgX Sensitizing dye (BS-1) 4.1 × 10 ⁻⁴ mol / mol AgX [ Method for preparing red-sensitive silver halide emulsion] (solution A) and (B
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
To obtain a monodisperse cubic emulsion EMP-3.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-C) was obtained. Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 5.8 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4.1 × 10 ⁻⁴ mol / mol AgX

[0131]

[Chemical 32]

This sample was exposed by a conventional method and then processed using the following processing steps and processing solutions. Treatment process Treatment temperature Treatment time Replenishment amount (1) Color development 35.0 ± 0.3 ℃ 45 seconds 162ml / m ² (2) Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 60ml / m ² (3) Stabilization (3-tank cascade) 30〜 34 ℃ 90 seconds 248ml / m ² (4) Dry 60-80 ℃ 30 seconds Color developer Triethanolamine 10g Ethylene glycol 6g N, N-diethylhydroxylamine 3.6g 2,2'-hydroxyimino-bis-ethanesulfone Acid disodium salt 5.0 g Potassium bromide 20 mg Potassium chloride 3 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 5.0 × 10 ^-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) ) -Aniline sulfate) 5.5 g Potassium carbonate 25.0 g Potassium hydrogen carbonate 5 g Add water to make the total volume 1 liter, and adjust to pH 10.10 with potassium hydroxide or sulfuric acid. Color development replenisher triethanolamine 14.0 g ethylene glycol 8.0 g N, N-diethylhydroxylamine 5 g 2,2'-hydroxyimino-bis-ethanesulfonic acid disodium salt 7.5 g potassium bromide 8.0 mg potassium chloride 0.3 g diethylenetriamine penta Acetic acid 7.5 g Potassium sulfite 7.0 × 10 ^-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 8 g Potassium carbonate 30 g Potassium hydrogen carbonate 1 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.40 with potassium hydroxide or sulfuric acid.

Bleach-fixing solution Water 600 ml Organic acid Ferric complex salt (described in Tables 3 and 4) 0.15 mol Thiosulfate 0.55 mol Sulfite 0.20 mol 1,3-Propanediaminetetraacetic acid 2 g Ammonia water, potassium hydroxide, acetic acid To pH 7.
Set to 0 and finish the total volume to 1 liter.

However, as shown in Table 3 and Table, the ammonium salt and potassium salt of the above additives were appropriately used in order to adjust the ratio (mol%) of ammonium thione in the bleach-fix solution.

Bleach-fixing replenisher The above-mentioned concentration of each additive in the bleach-fixing solution was set to 1.6 and pH was adjusted to 5.8.
Was used. Stabilizing replenisher ortho-phenyl phenol 0.1g Uvitex MST (manufactured by Ciba _{Geigy) 1.0g ZnSO 4 · 7H 2 O} 0.1g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60 % Solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid, and adjust to 1 liter with water.

A running treatment was carried out using the color paper and the treatment liquid thus prepared. In the running process, the automatic developing machine was filled with the above-mentioned color developing tank solution, and also with the bleach-fixing tank solution and the stabilizing tank solution, and the above-mentioned color developing replenishing solution and bleach-fixing were performed every 3 minutes while processing the color paper sample. The replenisher solution and the stable replenisher solution were replenished through a metering pump.

The running treatment was carried out continuously until the amount of the bleach-fixing tank solution replenished in the bleach-fixing tank solution became three times the volume of the bleach-fixing tank solution. Note that 1R means that the bleach-fixing replenisher for the capacity of the bleach-fixing tank is replenished.

After the treatment, the exposure-exposed area was divided into two, and the amount of the remaining fluorescent X-ray silver was measured. Furthermore, the state of stains on the edge of the treated color paper at the end of the running test was observed. Further, a visual evaluation of the state of the bleach-fixing tank liquid (production of sulfide) at the end of running was carried out. The results are shown in Tables 3 and 4.

The meanings of the symbols in the columns of the occurrence status of sulfurization in Tables 3 and 4 are as follows. ◎ No sulfides are observed. ○ Very slight floating substances are observed on the liquid surface. △ Slight sulfides are observed. × Clearly sulfides are observed. × × A large amount of sulfides is observed. In addition, the meaning of the symbols in the edge stain column is as follows: ◎ No edge stain is observed at all ○ Very slight edge stain is observed Δ Slight edge stain is recognized × Clearly a problem Edge stains are recognized. XX Marked edge stains are recognized.

[0140]

[Table 3]

[0141]

[Table 4]

In Tables 3 and 4 and the table below, ED
TA / Fe is ethylenediaminetetraacetic acid ferric complex salt, PDTA / Fe
Is 1,3-propylenediaminetetraacetic acid ferric complex, DTPA / Fe
Is diethylenetriamine pentaacetic acid ferric iron complex salt, NTA.Fe is nitrilotriacetic acid ferric iron complex salt, (I-1) .Fe is ferric iron complex salt of exemplified compound (I-1), (I-3) .Fe is The ferric iron complex salt of Exemplified Compound (I-3) and (I-6) .Fe represent the ferric iron complex salt of Exemplified Compound (I-6). Others are the same.

From Tables 3 and 4 above, when the ferric organic acid complex salt of the present invention is used, the amount of residual silver is small, the edge contamination is good, and the bleach-fixing solution has good storage stability. I understand. Further, when the ratio of ammonium ions to all cations in the bleach-fixing solution is 50 mol% or less, the above effect is better, when it is 30 mol% or less, it becomes particularly good, and 10 mol% or less is the best. I know there is.

Example 2 In the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. A silver iodobromide color photographic light-sensitive material was prepared as follows.

Silver iodobromide color photographic light-sensitive material triacetyl cellulose film A support (60 μm) was subjected to undercoating on one side (surface), and then sandwiched between the support and the surface opposite to the undercoated surface. Each layer having the composition shown below was sequentially formed on the side surface (back surface) from the support side. Back side 1st layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back side 2nd layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg On the surface of a cellulose film support, layers having the compositions shown below were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material (a-1). 1st layer: Antihalation layer (HC) Black colloidal silver 0.13 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g 〃 (Oil- 2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm) 0.35 g 〃 (Average particle size 0.4 μm) 0.3 g Sensitizing dye (S-1) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) 〃 ( S-3) 0.3 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) 0.48 g 〃 (C-2) 0.20 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006g 〃 (D-2) 0.01g High boiling point solvent (Oil-1) 0.55g Gelatin 1.0g 4th layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 µm 0.92g sensitizing dye (S-1) 1.7 × 10 -4 ( mol / 1 mol of silver) 〃 (S-2) 1.6 × 10 -4 ( mol / 1 mol of silver) 〃 (S-3) 0.2 × 10 - ⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.22g Colored cyan coupler (CC-1) 0.03g DIR compound (D-2) 0.02g High boiling solvent (Oil-1) 0.30g Gelatin 1.0g 5 layers; intermediate layer (IL-2) gelatin 0.8 g 6th layer; low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (average grain size 0.4 μm) 0.58 g 〃 (average grain size 0.3 μm) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.22 g 〃 (MB) 0.40 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; High sensitivity green sensitive emulsion layer ( GH) Silver bromide emulsion (average grain size 0.7 μm) 0.88 g Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) 〃 (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) ) 〃 (S-8) 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.48 g 〃 (MB) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D) -3) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.12g Additive (HS-1) 0.07g 〃 (HS-2) 0.07g 〃 (SC-1) 0.12g High boiling point solvent (Oil-2) 0.15g Gelatin 0.9g 9th layer; low-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.3 µm) 0.25g 〃 (Average particle size 0.4 μm) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.71 g 〃 (Y-2) 0.30 g DIR compound ( D- ) 0.003 g 〃 (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.2 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm) ) 0.5 g Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g 〃 (Y-2) 0.20g High boiling point solvent (Oil-2) 0.05g Gelatin 0.9g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08μm) 0.3g 〃 (UV -2) 0.10g Additive (HS-1) 0.2g 〃 (HS-2) 0.1g High boiling point solvent (Oil-1) 0.07g 〃 (Oil-3) 0.07g Gelatin 0.85g 12th layer; 2nd protection Layer (PRO-2) Compound A 0.04g Compound B 0.004g Polymethylmethacrylate (average particle size 3 μm) 0.02g Methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) 0.13 g of copolymer (average particle size 3 μm) The above color photographic light-sensitive material further comprises the compound Su-
1, Su-2, viscosity modifiers, hardening agents H-1, H-2, stabilizers ST-1, antifoggants AF-1, AF-2 (those having a weight average molecular weight of 10,000 and 110,000), Dye AI
-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

[0146]

[Chemical 33]

[0147]

[Chemical 34]

[0148]

[Chemical 35]

[0149]

[Chemical 36]

[0150]

[Chemical 37]

[0151]

[Chemical 38]

[0152]

[Chemical Formula 39]

[0153]

[Chemical 40]

[0154]

[Chemical 41]

[Preparation of Emulsion] The silver iodobromide emulsion used in the 10th layer was prepared by the following method. A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

The solution <G-1> was heated at a temperature of 70 ° C., a pAg of 7.8 and a pH of
The seed emulsion corresponding to 0.34 mol was added while maintaining the ratio at 7.0 while stirring well. (Formation of internal high iodine phase-core phase) After that, <H-1>
And <S-1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) for 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining the pH at 10.1 and the pH at 6.0.
-2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a variation coefficient of grain size distribution of 12.4% and a silver iodide content of 9.0 mol%. <G-1> 100.0 g of ossein gelatin 10% by weight solution of compound-1 in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% aqueous acetic acid solution 650.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g bromide Potassium 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% aqueous ammonia solution Equivalent Finish with water 1030.5ml <H-2> Ocein gelatin 300.0g Potassium bromide 770.0g Iodide Potassium 33.2 g Finish with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent Finish with water 3776.8 ml The structural formula of compound-1 is shown below.

[0160]

[Chemical 42]

In the same manner, the average grain size of the seed crystal, the temperature,
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing the pAg, pH, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a variation coefficient of particle size distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. , 1-phenyl-5-mercaptotetrazole was added.

However, the silver iodobromide color photographic light-sensitive material sample was prepared so that the average silver iodide content was 8 mol%. The light-sensitive material sample thus prepared was subjected to wedge exposure according to a conventional method and then subjected to running processing according to the following processing steps. However, the running process was continuously carried out until the amount twice the capacity of the bleach-fix tank was replenished (2R).

Treatment process Treatment time Treatment temperature Replenishment amount (per 135 size 24EX) (1) Color development (1 tank) 3 minutes 15 seconds 38 ℃ 20ml (2) Bleach (〃) 45 seconds 38 ℃ 5ml (3) Fixed (〃) 1 minute 30 seconds 38 ℃ 33ml (4) Stabilization (3 tank cascade) 1 minute 38 ℃ 40ml (5) Dry (40-80 ℃) 1 minute Color developer Potassium carbonate 30.0g Sodium hydrogen carbonate 2.0g Potassium sulfite 3.0g Sodium bromide 1.2g Potassium iodide 1.2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter, and adjust to pH 10.00 with potassium hydroxide or 20% sulfuric acid. Color development replenisher Potassium carbonate 35.0 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.5 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline Sulfate Salt 6.0 g Potassium hydroxide 2.0 g Diethylenetriaminepentaacetic acid 3.0 g Water is added to make 1 liter, and the pH is adjusted to 10.15 using potassium hydroxide or 20% sulfuric acid. Bleaching tank solution Ferric salt of organic acid (Table 5 and Table 6) 0.33 mol Ethylenediaminetetraacetic acid 10 g Bromide salt 1.2 mol Glacial acetic acid 40 ml Adjust pH to 4.5 with ammonia water and acetic acid, and add water to make 1 liter.

However, as shown in Tables 5 and 6, in order to adjust the ratio (mol%) of ammonium ions in the bleach-fix solution, the ammonium salt and potassium salt of the above additives were appropriately used.

Bleach Replenishing Solution The concentration of each additive in the above bleaching solution was 1.2 times, and the pH was 3.5.
Used as. Fixer (tank solution and replenisher) Ammonium thiosulfate (70% solution) 350 ml Anhydrous sodium bisulfite 10 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Stabilizing solution (tank solution and replenisher) Hexamethylenetetramine 5 g Diethylene glycol 10 g

[0167]

[Chemical 43]

Adjust to pH 8.0 with KOH and add water to 1
Finish to liters. The same running treatment as in Example 1 was performed to measure the magenta transmission density (green light density) of the unexposed area of the film sample, and at the same time, the residual silver amount in the exposed area was measured by the fluorescent X-ray method.

The above results are summarized in Tables 5 and 6.

[0170]

[Table 5]

[0171]

[Table 6]

From Tables 5 and 6 above, it can be seen that when the ferric iron complex salt of the organic acid of the present invention is used, the amount of residual silver is small and the magenta transmission density in the unexposed area is small. Furthermore, when the ratio of ammonium ions to the total cations in the bleaching solution is 50 mol% or less, the above effect is better, and when it is 30 mol% or less, it is particularly good, and 10 mol% or less is the best. I know there is. Example 3 A color developing solution having the following composition was prepared as a photographic processing solution.

Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-Hydroxylethyl) aniline sulfate 4.7 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 10.00 with potassium hydroxide or 20% sulfuric acid.

Sample (A) was prepared from the above developing solution, and sample (B) was prepared by adding the exemplified compound (I-1) at a rate of 2 g / l. 2 g / l of the same exemplified compound (I-3)
The added sample (C), (I-6) added with 2 g of (D), (I-8) added with 2 g of (E), (I
-14) (2g) added (F), (I-20) 2g added (G), sodium hexametaphosphate (HMP)
Abbreviated) 2 g / l was added to sample (H), 1-hydroxyethylidene-1,1-diphosphonic acid (abbreviated as HEDP)
3.3 g / l of a 60% solution of (1) was added to the sample (I), and 2 g / l of ethylenediaminetetraacetic acid (EDTA) was added to the sample (J) and nitrilotrimethylenephosphonic acid (abbreviated as NTP). Seven kinds of samples were prepared by adding 2 g / l as a sample (K). P for each sample depending on the substance added
Since H has changed, the pH was adjusted to 10.0 using potassium hydroxide or dilute sulfuric acid, and the following experiments were conducted. The results of each experiment are shown together at the end.

Experiment 1 Developer samples (A)-(K) above
Then, ferric ion of 1,5 ppm and copper ion of 0.7 ppm were added, and the mixture was allowed to stand at 35 ° C. for 8 days, and then hydroxylamine was quantitatively analyzed to determine the reduction rate.

Experiment 2 The same light-sensitive material as that used in Example 2 was subjected to white stepwise exposure using a sensitometer and then left for 7 days in Experiment 1 to obtain developer samples (A) to (K). Each of these was used to perform color development processing according to the following steps.

Treatment process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 45 seconds 38 ℃ Settlement 1 minute 30 seconds 38 ℃ Stabilization 50 seconds 38 ℃ Dry 1 minute 40-70 ℃ For the above process The composition of the treated liquid is as follows. Bleaching solution 1.3-Propylenediaminetetraacetic acid diiron ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Add water to make 1 liter and adjust to pH 4.4 with aqueous ammonia or glacial acetic acid. .

Fixer and Stabilizer Same as used in Example 2. After completion of the color development process, the fog density of the blue reflection density in the unexposed area was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

Experiment 3 Calcium ion was added to each of the developer samples (A) to (K).
Add 200ppm and 3000ppm sodium ion, and add 8 at room temperature.
After standing for a day, the occurrence of precipitation was observed.

The results of Experiments 1 to 3 above are summarized in Table 7.

[0181]

[Table 7]

(Note) In Experiment 3, ◯ indicates that no precipitation occurred, and the larger the number x, the more precipitation occurred.

As shown by the results in the above table, the developer samples (B) to (G) according to the present invention show less decomposition of hydroxylamine, less fog and no precipitation due to the presence of metal ions.

On the other hand, in the comparative sample (I), although there was some effect on the inhibition of the decomposition of hydroxylamine and the occurrence of fog, there was no effect on the occurrence of precipitation due to the presence of metal ions, and it could not be used.

Further, the comparative sample (J) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but promotes the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Samples (A), (H) and (K) are not suitable for practical use because they decompose hydroxylamine to generate fog and also have a weak ability to prevent precipitation due to the presence of metal ions. Example 4 A first developing solution (black and white developing solution) for a reversal film having the following composition was prepared as a photographic processing composition.

[0186]   Potassium sulfite (50% solution) 45.0 ml   Sodium bromide 2.0g   Sodium thiocyanate 1.1g   3.0 mg potassium iodide   Diethylene glycol 20.0 ml   1-phenyl-3-pyrazolidone 0.58 g   Hydroquinone 6.3g   28.2g potassium carbonate   Potassium hydroxide 2.8g Make up to 1 liter with water.

Sample (L) was prepared by adding the above developing solution to sample (L) and adding ethylenediaminetetraacetic acid (abbreviated as EDTA) at a rate of 2 g / l. Similarly, the exemplified compound (I-
1) was added at a rate of 2 g / l as a sample (N), and ethylenediaminetetramethylenephosphonic acid (abbreviated as EDTP) was added at 2 g /
The sample to which 1 was added was used as the sample (O), and a total of 4 types of samples were prepared. Each sample uses potassium hydroxide or 20% sulfuric acid,
The pH was adjusted to 9.90.

To each of the above samples, 2.5 ppm of ferric ion and 200 ppm of calcium ion were added and stored at 37 ° C. for 8 days, and then quantitative analysis was performed to measure the reduction rate of phenidone and the occurrence of precipitation. I observed the situation.

The results obtained are shown in Table 8.

[0190]

[Table 8]

(Note) In the table, ○ indicates that no precipitation occurred at all,
The larger the number x, the more precipitation is generated. As shown by the above results, the comparative sample (M) effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of the developing agent phenidone.

On the other hand, the comparative samples (L) and (O) have little or no effect on the decomposition of phenidone, and have little effect on the prevention of precipitation. On the contrary, it can be seen that the sample (N) containing the chelating agent used in the present invention effectively prevents the occurrence of precipitation and also suppresses the decomposition of phenidone well. Example 5 As a photographic processing composition, a fixing solution and a bleach-fixing solution having the following compositions were prepared, and the effects of the exemplified compounds on the occurrence of precipitation due to metal ions were tested for both solutions.

[0193]   Fixer Ammonium thiosulfate 200g 20g ammonium sulfite 5g potassium metabisulfite Make up to 1 liter with water.

Bleach-fixing solution Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ammonium sulfite (40% solution) 20 ml Ammonium thiosulfate (70% solution) 180 ml Ammonia water (28% solution) 30 ml Make up to 1 liter with water. The fixing solution and the bleach-fixing solution are used as they are for comparison, and some of the exemplified compounds (I-1), (I-3), (I-6) and (I-
8), (I-14) and (I-20) were added at a rate of 5 g / l to prepare 8 kinds of samples. Ammonium water or acetic acid is used for these solutions, and pH 6 for fixing solution.
8. Adjust the bleach-fix solution to pH 7.1, and add calcium ion (added as CaCl2) to each solution.
00 ppm was added.

When this was left to stand, the comparative one, to which nothing was added, caused remarkable precipitation in both the fixer and the bleach-fixer, but the exemplified compounds (I-1), (I-3) and (I
No precipitation occurred in the cases of (-6), (I-8), (I-14) and (I-20). Example 6 As a photographic processing composition, a stabilizing solution having the following composition (also referred to as a water-washing alternative stabilizing solution) was prepared, and 10% of the bleach-fixing solution used in Example 3 was added to generate a floating substance due to sulfurization. The preventive effect was tested. Stabilizer 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.5g 2-octyl-4-isoazoline-3-one 0.01g benzo Triazole 1.2 g Ammonia water (28%) 3.0 ml Make up to 1 liter with water and p with potassium hydroxide and 20% sulfuric acid.
Adjusted to H8.0.

Of the above-mentioned stabilizing solutions, the same ones were used for comparison, and some of the exemplified compounds (I-1) and (I-
3), (I-6), (I-8), (I-14) and (I-
20) was added at a rate of 3.5 g / l to make 6 kinds of samples.

These stabilizing solutions were adjusted to pH 8.0 with KOH or 20% sulfuric acid, and 100 ppm of calcium ion was added to each solution and allowed to stand. As a result, in the comparative sample to which nothing was added, precipitation occurred in 2 days and a floating substance was generated on the surface, but the exemplified compounds (I-1), (I-3),
No abnormality was observed even after 10 days in the products to which (I-6), (I-8), (I-14) and (I-20) were added. Furthermore, the effect was recognized also with respect to the occurrence of odor. Example 7 Chelating agents generally known to be used for photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), exemplified compounds (I-1), (I-
For 3) and (I-8), 301C modified MITI test (I) of the OECD test guideline for chemicals (May 12, 1981)
The degree of biodegradability was determined according to (adopted daily).

The results are shown in Table 9.

[0199]

[Table 9]

From Table 9 above, the chelating agent of the present invention has extremely good biodegradability, while EDTA and DTP
A hardly decomposes, and it is understood that the chelating agent of the present invention is extremely preferable from the standpoint of protecting the global environment. Example 8 The organic ferric complex salt in the bleach-fix solution in Example 1 is shown in Table 10.
And a compound was prepared in the same manner as in Example 1 except that the amount of addition was changed to 0.13 mol, the pH of the bleach-fix solution was changed to 7.2, and the pH of the replenisher was changed to 6.0, instead of the compounds shown in Table 11. went. (Evaluation criteria are the same as in Example 1) The results are shown in Tables 10 and 11.

[0201]

[Table 10]

[0202]

[Table 11]

In Tables 10 and 11 and the table below, ED
TA / Fe is ethylenediaminetetraacetic acid ferric complex salt, PDTA / Fe
Is 1,3-propylenediaminetetraacetic acid ferric complex, DTPA / Fe
Is diethylenetriaminepentaacetic acid ferric iron complex salt, NTA.Fe is nitrilotriacetic acid ferric iron complex salt, (NMPDA) Fe is nitrilomonopropionic acid diacetic acid ferric iron complex salt, and (II-1) .Fe is the exemplified compound (II- 1) the ferric iron complex salt, (II-2) .Fe is the ferric iron complex salt of the exemplified compound (II-2), and (II-3) .Fe is the ferric iron complex salt of the exemplified compound (II-3). Represent Others are the same.

From Table 10 and Table 11 above, when the ferric organic acid complex salt of the present invention was used, the amount of residual silver was small, the edge contamination was good, and the bleach-fixing solution had good storage stability. I understand. Further, when the ratio of ammonium ions to all cations in the bleach-fixing solution is 50 mol% or less, the above effect is better, when it is 30 mol% or less, it becomes particularly good, and 10 mol% or less is the best. I know there is. Further, the bleach-fixing solution pH in this experiment is 7.0, and in this pH region, NMPDA.Fe is inferior in oxidizing power, which is not preferable because it leads to desilvering failure. Example 9 In Example 2, the organic acid ferric salt in the bleaching tank liquid was displayed.
12, samples were prepared in the same manner as in Example 2 except that the compounds shown in Table 13 were changed to 0.36 mol and the amount of glacial acetic acid was changed to 27 ml, and the same evaluation was performed.

The results are shown in Tables 12 and 13.

[0206]

[Table 12]

[0207]

[Table 13]

From Tables 12 and 13 above, it can be seen that when the ferric iron complex salt of the organic acid of the present invention is used, the amount of residual silver is small and the magenta transmission density in the unexposed area is small. Furthermore, when the ratio of ammonium ions to the total cations in the bleaching solution is 50 mol% or less, the above effect is better, and when it is 30 mol% or less, it is particularly good, and 10 mol% or less is the best. I know there is. Further, when NMPDA-Fe was used as a bleaching agent, the bleaching fog increased, which was an unfavorable result. Example 10 A color developing solution having the following composition was prepared as a photographic processing solution.

Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 3.0 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 10.00 with potassium hydroxide or 20% sulfuric acid.

Sample (A) was prepared from the above developing solution, and sample (B) was prepared by adding the exemplified compound (II-1) at a rate of 2 g / l. 2 g / l of the similar exemplified compound (II-2)
The added sample (C), (II-3) added with 2 g of (D), (II-4) added with 2 g of (E), (II
-11) was added (F), (II-12) was added 2g (G), sodium hexametaphosphate (abbreviated as HMP) 2g / l was added as sample (H), 1 -60% of hydroxyethylidene-1,1-diphosphonic acid (abbreviated as HEDP)
The solution to which 3.3 g / l was added was sample (I), and the one to which ethylenediaminetetraacetic acid (abbreviated as EDTA) was added 2 g / l was sample (J) and nitrilotrimemethylenephosphonic acid (abbreviated as NTP) was 2 g / l. Seven kinds of samples were prepared by adding 1 to the sample (K).

Since the pH of each sample changed depending on the substance added, the pH was adjusted to 10.2 using potassium hydroxide or dilute sulfuric acid, and the following experiments were conducted.
The results of each experiment are shown together at the end.

Experiment 1 The above developer samples (A) to (K) were added with ferric ion of 1,5 p
After adding pm and copper ion of 0.6 ppm respectively and leaving it to stand at 35 ° C. for 8 days, hydroxylamine was quantitatively analyzed to determine the reduction rate.

Experiment 2 The same light-sensitive material as that used in Example 2 was subjected to white stepwise exposure using a sensitometer and then left for 7 days in Experiment 1 to obtain developer samples (A) to (K). Each of these was used to perform color development processing according to the following steps.

[0214] Treatment process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 45 seconds 38 ℃ Stationary 1 minute 30 seconds 38 ℃ Stabilization 50 seconds 38 ℃ Dry 1 minute 40-70 ℃ The composition of the treatment liquid used in the above steps is as follows.

Bleaching solution 1.3-Propylenediaminetetraacetic acid diiron ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Water was added to make 1 liter, and the pH was adjusted to 4.4 with ammonia water or glacial acetic acid. Adjust to.

Fixer and Stabilizer Same as used in Example 2. After completion of the color development process, the fog density of the blue reflection density in the unexposed area was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

Experiment 3 Calcium ion was added to each of the developer samples (A) to (K).
Add 200ppm and 3200ppm sodium ion, and add 6 at room temperature.
After standing for a day, the occurrence of precipitation was observed.

The results of Experiments 1 to 3 above are summarized in Table 14.

[0219]

[Table 14]

(Note) In Experiment 3, ◯ indicates that no precipitation occurred, and the larger the number x, the more precipitation occurred.

As shown by the results in the above table, the developer samples (B) to (G) according to the present invention show less decomposition of hydroxylamine, less fog, and no precipitation due to the presence of metal ions.

On the other hand, the comparative sample (I) has some effect on the inhibition of the decomposition of hydroxylamine and the occurrence of fog, but has no effect on the occurrence of precipitation due to the presence of metal ions and cannot be used.

Further, the comparative sample (J) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but it accelerates the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Samples (A), (H) and (K) are not suitable for practical use because they decompose hydroxylamine to generate fog and also have a weak ability to prevent precipitation due to the presence of metal ions. Example 11 As a photographic processing composition, a first developing solution (black and white developing solution) for reversal film having the following composition was prepared.

[0224]   Potassium sulfite (50% solution) 45.0 ml   Sodium bromide 2.0g   Sodium thiocyanate 1.1g   3.0 mg potassium iodide   Diethylene glycol 20.0 ml   1-phenyl-3-pyrazolidone (phenidone trade name) 0.58g   Hydroquinone 6.2g   28.2g potassium carbonate   Potassium hydroxide 2.8g Make up to 1 liter with water.

Sample (L) was prepared by adding the above developing solution to sample (L) and adding ethylenediaminetetraacetic acid (abbreviated as EDTA) at a rate of 2 g / l. Similarly, the exemplified compound (II-
1) was added at a rate of 2 g / l as a sample (N), and ethylenediaminetetramethylenephosphonic acid (abbreviated as EDTP) was added at 2 g /
The sample to which 1 was added was used as the sample (O), and a total of 4 types of samples were prepared. Each sample uses potassium hydroxide or 20% sulfuric acid,
The pH was adjusted to 9.90.

To each of the above samples, 3.0 ppm of ferric ion and 200 ppm of calcium ion were added and stored at 35 ° C. for 8 days, and then quantitative analysis was carried out to measure the reduction rate of phenidone and the occurrence of precipitation. I observed the situation.

The results obtained are shown in Table 15.

[0228]

[Table 15]

(Note) In the table, ○ indicates that no precipitation occurred at all,
The larger the number x, the more precipitation is generated. As shown by the above results, the comparative sample (M) effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of the developing agent phenidone.

On the other hand, the comparative samples (L) and (O) have little or no effect on the decomposition of phenidone, and have little effect on the prevention of precipitation. On the contrary, it can be seen that the sample (N) containing the chelating agent used in the present invention effectively prevents the occurrence of precipitation and also suppresses the decomposition of phenidone well. Example 12 As a photographic processing composition, a fixing solution and a bleach-fixing solution having the following compositions were prepared, and the effects of the exemplified compounds on the occurrence of precipitation due to metal ions were tested for both solutions. Fixing solution Ammonium thiosulfate 200g Ammonium sulfite 20g Potassium metabisulfite 5g Make up to 1 liter with water. Bleach-fixing solution Ammonium iron (III) diamine tetraacetate 60 g Ammonium sulfite (40% solution) 20 ml Ammonium thiosulfate (70% solution) 180 ml Ammonia water (28% solution) 30 ml Water-making 1 liter of the above fixing solution and bleach-fixing solution For the above, the same compounds were used for comparison, and some of the exemplified compounds (II-1) and (II-
2), (II-3), (II-4), (II-11) and (II-
12) was added at a rate of 4 g / l for each to make 8 kinds of samples. These solutions use ammonium water or acetic acid, pH 6.8 for fixers and pH for bleach-fixers.
It was adjusted to H7.1 and 200 ppm of calcium ion was added to each solution.

When left undisturbed, both the fixing solution and the bleach-fixing solution of the comparative one, to which nothing was added, caused remarkable precipitation, but the exemplified compounds (II-1), (II-2), (II
-3), (II-4), (II-11) and (II-12) were added, no precipitation occurred. Example 13 As a photographic processing composition, a stabilizing solution having the following composition (also referred to as a water-washing alternative stabilizing solution) was prepared, 10% of the bleach-fixing solution used in Example 3 was added, and floating substances due to sulfurization were generated. The preventive effect was tested. Stabilizer 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.5g 2-octyl-4-isoazolin-3-one 0.01g benzo Triazole 1.2 g Ammonia water (28%) 3.0 ml Make up to 1 liter with water and p with potassium hydroxide and 20% sulfuric acid.
Adjusted to H8.0.

Of the above stabilizers, the same ones were used for comparison, and some of the exemplified compounds (II-1) and (II-
2), (II-3), (II-4), (II-11) and (II-
12) was added at a rate of 3 g / l to make 3 kinds of samples.

These stabilizing solutions were adjusted to pH 8.0 with KOH or 20% sulfuric acid, and 100 ppm of calcium ion was added to each solution and allowed to stand. As a result, in the comparative sample to which nothing was added, precipitation occurred and a floating substance was generated on the surface in 2 days, but the exemplary compounds (II-1), (II-2),
No abnormality was observed even after 10 days in the products to which (II-3), (II-4), (II-11) and (II-12) were added. Furthermore, the effect was recognized also with respect to the occurrence of odor. Example 14 Chelating agents commonly known for use in photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), exemplified compounds (II-1), (II-2)
For (II-12) and (II-12), the degree of biodegradability was determined according to the 301C modified MITI test (I) of the OECD Test Guideline for Chemicals (adopted May 12, 1981).

The results are shown in Table 16.

[0235]

[Table 16]

From Table 16 above, the chelating agent of the present invention has extremely good biodegradability, whereas EDTA and DTPA hardly decompose, and the chelating agent of the present invention is extremely preferable from the standpoint of global environmental protection. It turns out that Example 15 In Example 1, the amount of triethanolamine added in the color developing solution was 8.0 g, the amount of potassium sulfite added was 6 × 10 ^-4 mol, triethanolamine 12.0 g in the color developing replenisher, in the bleach-fixing solution. The ferric acid complex salt of organic acid was replaced with the compounds shown in Table 16 and Table 17, the addition amount was 0.19 mol and the pH of the bleach-fix solution
6.8, pH of bleach-fix replenisher 5.7, 1-hydroxyethylidene-1,1-diphosphonic acid (60% in stabilizer and replenisher)
A sample was prepared in the same manner as in Example 1 except that the addition amount of (solution) was changed to 1.5 g, and the same evaluation was performed. (Evaluation criteria are the same as in Example 1) The results are shown in Tables 17 and 18.

[0237]

[Table 17]

[0238]

[Table 18]

In Tables 17 and 18 and the table below, ED
TA / Fe is ethylenediaminetetraacetic acid ferric complex salt, PDTA / Fe
Is 1,3-propylenediaminetetraacetic acid ferric complex, DTPA / Fe
Is diethylenetriamine pentaacetic acid ferric iron complex salt, NTA.Fe is nitrilotriacetic acid ferric iron complex salt, (III-1) .Fe is ferric iron complex salt of the exemplified compound (III-1), (III-4) .Fe is Ferric Complex Salt of Exemplified Compound (III-4) Hereinafter, the ferric complex salt of Exemplified Compound is similarly represented. Example 16 In Example 2, the amount of hydroxylamine sulfate added to the color developing solution was 2.4 g, the amount of hydroxylamine sulfate added to the color developing replenisher was 3.4 g, and ferric organic acid in the bleaching tank solution was used. The complex salt was changed to the compound described in Table 19 and Table 20, the addition amount was 0.37 mol, and the addition amount of ethylenediaminetetraacetic acid was 3
g, 1.0 mol of bromide salt, 25 m of glacial acetic acid
A sample was prepared in the same manner as in Example 2 except that the pH of the bleaching replenisher was 3.7, and the same evaluation was performed. The results (the evaluation method is the same as in Example 2) are shown in Tables 19 and 20.

[0240]

[Table 19]

[0241]

[Table 20]

From Tables 17 and 18 above, when the ferric organic acid complex salt of the present invention was used, the amount of residual silver was small, the edge contamination was good, and the bleach-fixing solution had good storage stability. I understand. Further, when the ratio of ammonium ions to all cations in the bleach-fixing solution is 50 mol% or less, the above effect is better, when it is 30 mol% or less, it becomes particularly good, and 10 mol% or less is the best. I know there is.

From Tables 19 and 20 above, it is understood that when the ferric iron complex salt of an organic acid of the present invention is used, the amount of residual silver is small and the magenta transmission density in the unexposed area is small. Furthermore, when the ratio of ammonium ions to the total cations in the bleaching solution is 50 mol% or less, the above effect is better, and when it is 30 mol% or less, it is particularly good, and 10 mol% or less is the best. I know there is. Example 17 A color developing solution having the following composition was prepared as a photographic processing solution.

Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulphate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Chelating agent (listed in Table 21) 2.0g Add water to make 1 liter and add pH 10 with potassium hydroxide or 20% sulfuric acid. Adjusted to .05, the following experiments were conducted.

Experiment 1 To the developer samples (17-1) to (17-11) described above, 1,5 ppm of ferric ion and 0.7 ppm of copper ion were added, respectively, and the mixture was heated at 33 ° C.
After leaving it for 10 days, quantitatively analyze hydroxylamine,
The reduction rate was calculated.

Experiment 2 The same light-sensitive material as that used in Example 2 was subjected to white stepwise exposure using a sensitometer and then left for 10 days in Experiment 1 to obtain developer samples (17-1) to (17-1)-( 17-11) was used to carry out color development processing according to the following steps.

[0247] Treatment process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 45 seconds 38 ℃ Stationary 1 minute 30 seconds 38 ℃ Stabilization 50 seconds 38 ℃ Dry 1 minute 40-70 ℃ The composition of the treatment liquid used in the above steps is as follows.

Bleaching solution 1.3-Propylenediaminetetraacetic acid diiron ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Water was added to make 1 liter and pH was adjusted to 4.4 with ammonia water or glacial acetic acid. Adjust to.

Fixer and Stabilizer Same as used in Example 2. After completion of the color development process, the fog density of the blue reflection density in the unexposed area was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

Experiment 3 Calcium ion 190 ppm and sodium ion 2800 ppm were respectively added to the developer samples (17-1) to (17-11),
After standing at room temperature for 10 days, the occurrence of precipitation was observed.

The results of Experiments 1 to 3 are summarized in Table 21.

[0252]

[Table 21]

In Table 21, HMP is sodium hexametaphosphate and HEDP is 1-hydroxyethylidene-1,1-.
Diphosphonic acid, EDTA represents ethylenediaminetetraacetic acid, and NTP represents nitrilotrimethylenephosphonic acid.

(Note) In Experiment 3, ◯ indicates that no precipitation occurred, and the larger the number of x, the more precipitation occurred.

As shown by the results in the above table, the developer samples (17-2) to (17-7) according to the present invention show less decomposition of hydroxylamine, less fog and no precipitation due to the presence of metal ions. I understand.

On the other hand, in the comparative sample (17-8),
Although it has some effect on the inhibition of hydroxylamine decomposition and the generation of fog, it has no effect on the occurrence of precipitation due to the presence of metal ions and cannot be used.

Further, the comparative sample (17-10) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but it promotes the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Samples (17-1), (17-8) and (17-11) are also not suitable for practical use because they decompose hydroxylamine to generate fog and also have a weak ability to prevent precipitation due to the presence of metal ions. Example 18 As a photographic processing composition, a first developer (black-and-white developer) for reversal film having the following composition (18-1) to (18)
-5) was adjusted.

Potassium sulfite (50% solution) 45.0 ml Sodium bromide 2.0 g Sodium thiocyanate 1.1 g Potassium iodide 3.0 mg Diethylene glycol 20.0 ml 1-Phenyl-3-pyrazolidone (phenidone trade name) 0.58 g Hydroquinone 6.0 g Potassium carbonate 28.2 g Potassium hydroxide 2.8 g Chelating agent (described in Table 22) 2.5 g Water was made up to 1 liter and adjusted to pH 9.9 with potassium hydroxide or 20% sulfuric acid.

In each of the above samples, ferric ions (secondary chloride
(Added as iron) 2.8ppm and calcium ion 200ppm
After adding and storing at 35 ° C. for 10 days, quantitative analysis was performed to measure the reduction rate of phenidone, and the occurrence of precipitation was observed.

The results obtained are shown in Table 22.

[0261]

[Table 22]

(Note) In the table, ○ indicates that no precipitation occurred at all,
The larger the number x, the more precipitation is generated. As shown by the above results, the comparative sample (18-2) effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of the developing agent phenidone.

One comparative sample (18-1) and (18-3)
Has little or no effect on the decomposition of phenidone,
It is not very effective in preventing precipitation. On the contrary, the samples (18-4) and (18-
It can be seen that 5) effectively prevents the occurrence of precipitation and also suppresses the decomposition of phenidone well. Example 19 As a photographic processing composition, a fixing solution and a bleach-fixing solution having the following compositions were prepared, and the effects of the exemplified compounds on the occurrence of precipitation due to metal ions were tested for both solutions. Fixing solution Ammonium thiosulfate 200g Ammonium sulfite 20g Potassium metabisulfite 5g Make up to 1 liter with water. Bleach-fix solution Ammonium iron (III) diamine tetraacetate 60 g Ammonium sulfite (40% solution) 20 ml Ammonium thiosulfate (70% solution) 180 ml Ammonia water (28% solution) 30 ml Make up to 1 liter with water.

Regarding the above-mentioned fixing solution and bleach-fixing solution, those as they are were used for comparison, and some of the exemplified compounds (III-
1), (III-11), (IV-1) and (IV-16) were added at a rate of 4 g / l to prepare 8 kinds of samples. These solutions were adjusted to have a pH of 6.8 for the fixer and a pH of 7.1 for the bleach-fixer using ammonium water or acetic acid, and 200 ppm of calcium ion was added to each solution.

When this was left to stand, the comparative ones to which nothing was added produced tremendous precipitation in both the fixer and the bleach-fixer, but the exemplified compounds (III-1), (III-2),
With (IV-1) and (IV-16) added, no precipitation occurred. Example 20 As a photographic processing composition, a stabilizing solution having the following composition (also referred to as a water washing substitute stabilizing solution) was prepared, 10% of the bleach-fixing solution used in Example 17 was added, and floating substances due to sulfurization were generated. The preventive effect was tested. Stabilizer 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.5g 2-octyl-4-isoazolin-3-one 0.01g benzo Triazole 1.2 g Ammonia water (28%) 3.0 ml Make up to 1 liter with water and p with potassium hydroxide and 20% sulfuric acid.
Adjusted to H7.8.

Of the above stabilizers, the same ones as they were were used for comparison, and some of the exemplified compounds (III-1) and (III-1
7) and (IV-16) were added at a rate of 3 g / l to make three samples each.

These stabilizing solutions were adjusted to pH 8.0 with KOH or 20% sulfuric acid, and 100 ppm of calcium ion was added to each solution and allowed to stand. As a result, in the case of the comparative sample to which nothing was added, precipitation occurred and a floating substance was generated on the surface in two days.
No abnormalities were observed even after 10 days in the cases of adding (IV-16) and (IV-16). Furthermore, the effect was recognized also with respect to the occurrence of odor. Example 21 Chelating agents commonly used for photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), Exemplified compound A-1) And A-
2 about 30 of the OECD chemical test guidelines
Biodegradability was determined according to the 1C modified MITI test (I) (adopted May 12, 1981).

At this time, the relative degree of decomposition was determined when the component solution of the exemplified compound (III-1) was 100, and the results are shown in Table 23.

[0269]

[Table 23]

From Table 23 above, the chelating agent of the present invention has extremely good biodegradability, while EDTA and DTP
A hardly decomposes, and it is understood that the chelating agent of the present invention is extremely preferable from the standpoint of protecting the global environment. Example 22 In Example 1, the addition amount of the color developing agent in the color developing solution was 5.7 g, and the addition amount of potassium sulfite in the color developing replenisher solution was 6 g.
^{X10 -4} mol, the ferric organic acid complex salt in the bleach-fixing solution was changed to the compounds shown in Tables 24 and 25, and the addition amount was 0.17 mol / l, and the addition amount of thiosulfate was 0.52 mol. A sample was prepared in the same manner as in Example 1 except that the addition amount of ethylenediaminetetraacetic acid in the replenisher was changed to 3.2 g, and the same evaluation was performed.

The results are shown in Tables 24, 25 and 26 below.
(Evaluation criteria are the same as in Example 1)

[0272]

[Table 24]

[0273]

[Table 25]

[0274]

[Table 26]

In Table 24, Table 25 and Table 26 and the following table, EDTA.Fe is ethylenediaminetetraacetic acid ferric complex salt, PD
TA / Fe is 1,3-propylenediaminetetraacetic acid ferric complex, DT
PA / Fe is diethylenetriaminepentaacetic acid ferric complex, NTA
-Fe is a ferric nitriclotriacetic acid ferric complex salt, (V-1) -Fe is a ferric iron complex salt of the exemplified compound (VI-1), (VI-4) -Fe is a second ferric compound of the exemplified compound (VII-2). Iron complex salt, and so on () ・
Fe represents a ferric iron complex salt of the exemplified compound ().

From Tables 24, 25 and 26 above, when the ferric organic acid complex salt of the present invention was used, the amount of residual silver was small,
It can be seen that the edge contamination is also good, and the storage stability of the bleach-fix solution is also good. Further, when the ratio of ammonium ions to all cations in the bleach-fixing solution is 50 mol% or less, the above effect is better, when it is 30 mol% or less, it becomes particularly good, and 10 mol% or less is the best. I know there is. Example 23 In Example 2, the amount of hydroxylamine sulfate added to the color developing solution was 2.3 g, the amount of hydroxylamine sulfate added to the color developing replenisher was 3.3 g, and the ferric organic acid complex salt in the bleaching tank solution was used. Was changed to the compounds shown in Table 27, Table 28 and Table 29, the addition amount of the compound was 0.32 mol, the addition amount of ethylenediaminetetraacetic acid was 7 g, the addition amount of the bromide salt was 1.1 mol and the addition amount of glacial acetic acid. A sample was prepared in the same manner as in Example 2 except that the amount was changed to 45 ml, and the same evaluation was performed. The results (the evaluation method is the same as in Example 2) are shown in Tables 27, 28 and 29 below.

[0277]

[Table 27]

[0278]

[Table 28]

[0279]

[Table 29]

From Tables 27, 28 and 29 above, it is found that when the ferric organic acid complex salt of the present invention is used, the residual silver amount is small and the magenta transmission density in the unexposed area is small. . Furthermore, when the ratio of ammonium ions to the total cations in the bleaching solution is 50 mol% or less, the above effect is better, and when it is 30 mol% or less, it is particularly good, and 10 mol% or less is the best. I know there is. Example 24 A color developing solution having the following composition was prepared as a photographic processing solution.

Potassium carbonate 30.0 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.2 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulphate 2.7 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulphate 4.3g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Chelating agent (listed in Table 30) 2.0g Add water to make 1 liter and add pH 10 with potassium hydroxide or 20% sulfuric acid. After adjusting to 0.00, the following experiments were conducted.

The results of each experiment are shown together at the end. Experiment 1 Ferric ion 1,5 ppm and copper ion 0.4 ppm were added to the developer samples (24-1) to (24-18), respectively, and the mixture was allowed to stand at 36 ° C for 7 days, and then hydroxylamine was quantified. Analyze
The reduction rate was calculated.

Experiment 2 The same light-sensitive material as that used in Example 2 was subjected to white stepwise exposure using a sensitometer and then left for 10 days in Experiment 1 to obtain developer samples (24-1) to (24-1). 24-18) was used to carry out color development processing according to the following steps.

Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleach 45 seconds 38 ° C Settling 1 minute 30 seconds 38 ° C Stabilization 50 seconds 38 ° C Drying 1 minute 40 to 70 ° C For the above steps The composition of the treated liquid is as follows. Bleaching solution 1.3-Propylenediaminetetraacetic acid diiron ammonium 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Add water to make 1 liter and adjust to pH 4.4 with ammonia water or glacial acetic acid. .

Fixer and Stabilizer Same as used in Example 2. After completion of the color development process, the fog density of the blue reflection density in the unexposed area was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

Experiment 3 Calcium ion 180 ppm and sodium ion 3000 ppm were added to each of developer solution samples (24-1) to (24-18),
After standing at room temperature for 7 days, the occurrence of precipitation was observed.

The results of Experiments 1 to 3 above are summarized in Table 30.

[0288]

[Table 30]

In Table 30 below, HMP is sodium hexametaphosphate, HEDP is 1-hydroxyethylidene-1,1-diphosphonic acid, EDTA is ethylenediaminetetraacetic acid, NTA is nitrilotriacetic acid, PDTA is trimethylene. Represents diamine tetraacetic acid.

(Note) In Experiment 3, ◯ indicates that no precipitation occurred, and the larger the number x, the more precipitation occurred.

As shown by the results in the above table, the developer samples (24-2) to (24-13) according to the present invention show less decomposition of hydroxylamine, less fog and no precipitation due to the presence of metal ions. I understand.

On the other hand, in the comparative sample (24-15),
Although it has some effect on the inhibition of hydroxylamine decomposition and the generation of fog, it has no effect on the occurrence of precipitation due to the presence of metal ions and cannot be used.

Further, comparative samples (24-16) and (24-18)
Has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but accelerates the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Sample (24-1),
(24-14) and (24-17) are also not suitable for practical use because they decompose hydroxylamine to generate fog and also have a weak effect of preventing the occurrence of precipitation due to the presence of metal ions.

Example 25 As a photographic processing composition, a first developing solution (black and white developing solution) for reversal films having the following composition (25-1) to (25)
-8) was adjusted.

Potassium sulfite (50% solution) 40.0 ml Sodium bromide 2.0 g Sodium thiocyanate 1.1 g Potassium iodide 3.0 mg Diethylene glycol 20.0 ml 1-Phenyl-3-pyrazolidone (phenidone trade name) 0.61 g Hydroquinone 5.8 g Potassium carbonate 28.0 g Potassium hydroxide 2.8 g Chelating agent (described in Table 31) 2.0 g Water was made up to 1 liter and adjusted to pH 9.90 with potassium hydroxide or 20% sulfuric acid.

To each of the above samples, 2.5 ppm of ferric ion and 180 ppm of calcium ion were added and stored at 35 ° C. for 7 days, and then quantitative analysis was performed to measure the reduction rate of phenidone and the occurrence of precipitation. I observed the situation.

The results obtained are shown in Table 31.

[0298]

[Table 31]

(Note) In the table, ○ indicates that no precipitation occurred at all,
The larger the number x, the more precipitation is generated. As the above results show, the comparative sample (25-8) effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of the developing agent phenidone.

One comparison sample (25-1) and (25-7)
Has little or no effect on the decomposition of phenidone,
It is not very effective in preventing precipitation. On the contrary, the samples (25-2) and (25-
It can be seen that 6) effectively prevents the occurrence of precipitation and also effectively suppresses the decomposition of phenidone. Example 26 As a photographic processing composition, a fixing solution and a bleach-fixing solution having the following compositions were prepared, and the effects of the exemplified compounds on the occurrence of precipitation due to metal ions were tested for both solutions. Fixing solution Ammonium thiosulfate 200g Ammonium sulfite 20g Potassium metabisulfite 5g Make up to 1 liter with water. Bleach-fix solution Ammonium iron (III) diamine tetraacetate 60 g Ammonium sulfite (40% solution) 20 ml Ammonium thiosulfate (70% solution) 180 ml Ammonia water (28% solution) 30 ml Make up to 1 liter with water.

Regarding the above-mentioned fixing solution and bleach-fixing solution, those as they are were used for comparison, and some of the exemplified compounds (II-
1), (III-2), (VI-1) and (VI-14) were added at a rate of 4 g / l to make 8 kinds of samples. These solutions were adjusted to have a pH of 6.8 for the fixer and a pH of 7.1 for the bleach-fixer using ammonium water or acetic acid, and 200 ppm of calcium ion was added to each solution.

When left undisturbed, both the fixing solution and the bleach-fixing solution of the comparative one, to which nothing was added, caused remarkable precipitation, but the exemplified compounds (V-1), (V-2), (VI −
No precipitation occurred at all with the additions of 1) and (VI-14). Example 27 As a photographic processing composition, a stabilizing solution having the following composition (also referred to as a washing-replacement stabilizing solution) was prepared, 10% of the bleach-fixing solution used in Example 3 was added, and floating substances due to sulfurization were generated. The preventive effect was tested. Stabilizer 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.5g 2-octyl-4-isoazolin-3-one 0.01g benzo Triazole 1.2 g Ammonia water (28%) 2.5 ml Make up to 1 liter with water and p with potassium hydroxide and 20% sulfuric acid.
Adjusted to H7.8.

The above stabilizers were used as they were for comparison, and some of the exemplified compounds (V-1), (V-2) and (VI-1) were added in an amount of 3 g / l. Three samples each were made.

These stabilizing solutions were adjusted to pH 8.0 with KOH or 20% sulfuric acid, and 200 ppm of calcium ion was added to each solution and allowed to stand. As a result, in the comparative product to which nothing was added, precipitation occurred and a floating substance was generated on the surface in 2 days, but the exemplary compounds (V-1), (V-2) and (VI-1) were added. No abnormalities were observed even after 10 days. Furthermore, the effect was recognized also with respect to the occurrence of odor. Example 28 Chelating agents commonly used for photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), exemplified compounds (V-1) ), (V-
For 2), (VI-1) and (VII-2), OECD
301C modified MITI test (I) of chemical test guideline
The degree of biodegradability was determined according to (Adopted May 12, 1981).

At this time, the relative resolution was calculated when the component solution of the exemplified compound (V-2) was 100, and the results are shown in Table 32.

[0306]

[Table 32]

From Table 32 above, while the chelating agent of the present invention has extremely good biodegradability, EDTA, DTP
A hardly decomposes, and it is understood that the chelating agent of the present invention is extremely preferable from the standpoint of protecting the global environment.

[0308]

INDUSTRIAL APPLICABILITY The photographic processing agent composition and processing method of the present invention have rapid desilvering property, no edge stains, excellent liquid storage stability, and presence of metal ions. It is suitable for protection of the global environment because a stable processing solution can be obtained without sedimentation and sludge generation due to, and the processing solution for photography is excellent in biodegradation.

Front page continuation (51) Int.Cl. ⁷ identification code FI G03C 11/00 501 G03C 11/00 501 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/42 G03C 5/29 G03C 5/38 G03C 5/44 G03C 7/407 G03C 11/00

Claims (6)

(57) [Claims] 1. The following general formulas [V], [VI] and [VI]
A silver halide photographic processing composition comprising at least one selected from the compounds represented by the formula [I]. General formula [V] (R ₁ ) (R ₂ ) N- (C = X ₁ ) -W- (C =
X ₂ ) -N (R ₃ ) (R ₄ ) [In the formula, R _{1 to} R ₄ are each a hydrogen atom or-(C
H ₂₎ m ₃ -CH [(CH ₂₎ m ₂ -Z _2] - (CH ₂₎ m ₁
It represents a -Z _1. Z ₁ and Z ₂ are a hydrogen atom, —COOM (M represents a hydrogen ion, an alkali metal ion or another cation), —OH or —NH ₂ , and m _{1 to} m ₃ are 0 to 2.
Represents the integer. However, not all of R _{1 to} R ₄ are hydrogen atoms. W is a substituted or unsubstituted alkylene group having 1 to 5 carbon _{atoms, - (D 1 O) m} 4 -D 2 or -O- (D ₃₎
m ₅ -O- (D ₁ ~D ₃ represents a methylene chain of 1 to 3 carbon atoms). Further, m _4, m ₅ represents an integer of 1 to 3. X
₁ and X ₂ represent an oxygen atom or a sulfur atom. ] Formula _{[VI] (R 1) (} R 2) N- (C = X 1) - (R 3) wherein each same meaning of each R ₁ to R ₃ and X ₁ is the general formula [V] Is. However, not all of R _{1 to} R ₃ are hydrogen atoms. ] Formula _{[VII] (R 1) N} - [(C = X ₁₎ -R _2] -
[(C = X ₂ ) -R ₃ ] [In the formula, R _{1 to} R ₃ and X ₁ and X ₂ are respectively synonymous with the general formula [V]. However, not all of R _{1 to} R ₃ are hydrogen atoms. ] 2. A ferric complex salt of at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII], wherein the silver halide photographic processing composition is a ferric complex salt. A silver halide photographic processing composition according to claim 1, which is a bleaching solution or a bleach-fixing solution. 3. A developer containing the silver halide photographic processing composition containing at least one compound selected from the compounds represented by the above formulas [V], [VI] and [VII]. The silver halide photographic processing composition according to claim 1, wherein 4. A fixing solution in which the silver halide photographic processing composition contains at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII]. The silver halide photographic processing composition according to claim 1, wherein 5. A stabilizing solution in which the silver halide photographic processing composition contains at least one compound selected from the compounds represented by the general formulas [V], [VI] and [VII]. The silver halide photographic processing composition according to claim 1, wherein 6. A silver halide photographic light-sensitive material is imagewise exposed and then color-developed, and then bleaching or bleach-fixing is selected from compounds represented by the above formulas [V], [VI] and [VII]. And a ferric complex salt of at least one compound described above.