JP2002139822A - Photographic processing composition containing bistriazinyl arylenediamine derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing composition for a silver halide color photo graphic material which diminishes stain due to the residual sensitizing dye of a processed sensitive material and does not form a precipitate in storage at a low temperature. SOLUTION: The processing composition for a sliver halide photographic material contains a bis[2,6-diaminotriazin-4-yl]arylenediamine derivative having at least one of sulfonic acid, carboxyl and hydroxyl groups in each molecule. The processing composition is applicable to a color developer, a bleaching agent, a fixing agent, a bleach-fixing agent, a stabilizer, etc., and to a processing solution, a concentrated processing agent, a solid processing agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition for a silver halide color photographic light-sensitive material, and more particularly to a processing composition having an excellent effect of reducing stain caused by residual sensitizing dye of the light-sensitive material after processing. The present invention relates to a composition which does not produce a precipitate when stored at a low temperature.

[0002]

2. Description of the Related Art With the remarkable progress of digital cameras and color printers, in processing silver halide color photographic light-sensitive materials, it is desired to promptly provide high-quality images to customers. However, if the conventional processing method simply shortens the time, the processing is completed before the sensitizing dye in the photosensitive material is sufficiently washed out. The highlight and the background are colored, making it difficult to appreciate. Also, in a color negative film, an increase in the density of the minimum density portion causes a loss of color balance, which may cause a situation in which an appropriate print cannot be provided.

In recent years, the use of tabular silver halide grains has become an important basic technique in high-sensitivity photographic materials, and this technique can increase the amount of sensitizing dye used per unit volume. Thus, while providing the advantage of improving the sensitivity and the sensitivity-granularity ratio, it also has the disadvantage of increasing the amount of sensitizing dye remaining in the processed photographic material. Depending on the processing conditions, the increase in the amount of the residual sensitizing dye cannot be ignored, causing phenomena such as a loss of color balance due to an increase in the density of the minimum density portion of the color negative film and coloring of the highlight image portion of the color reversal film. .

As an example of a method for removing residual color due to a sensitizing dye, Research Disclosure No. 20733 discloses a method using a bistriazinylaminostilbene disulfonic acid compound. It has been widely used in processing. JP-A-6-329936 also discloses a bistriazinylaminostilbene disulfonic acid compound which is excellent in solubility and can reduce the residual color even in a process in which time is shortened.

On the other hand, the processing of the photographic light-sensitive material is accelerated, and the processing composition of the processing composition is reduced for reasons such as reduction of waste containers of processing agents, improvement of recyclability, transportation of processing agents and processing chemicals, and reduction of storage costs. Further enrichment is also desired,
Therefore, the additive for the purpose of reducing the residual color as described above needs to be adaptable to concentration. However, a compound having a residual color reduction effect showing a sufficient effect even in a treatment in which the time is reduced when the compound is used at a concentration lower than the solubility and stably dissolved even under a concentrated high salt concentration has not been found. .

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and specifically, to reduce the stain caused by the residual sensitizing dye of a photographic material after processing. It is an object of the present invention to provide a processing composition for a silver halide color photographic light-sensitive material which is achieved and does not produce a precipitate when the processing composition is stored at a low temperature.

[0007]

The above object has been attained by the following inventions. That is, (1) a processing composition for a silver halide photographic light-sensitive material, comprising a compound represented by the following general formula (I). General formula (I)

[0008]

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In the general formula (I), R¹¹, R¹²,
R¹³, R¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And R ^{twenty four}Is a hydrogen atom,
L represents an alkyl group, an aryl group or a heterocyclic group;
Represents a phenylene group or a naphthylene group;¹¹And R
¹²And / or R¹³And R¹⁴And / or R^{twenty one}And R
^{twenty two}And / or R^{twenty three}And R^{twenty four}And bond together to form a ring
It may be formed. However, in the molecule -SO_ThreeM, -CO_TwoM
Or at least one group represented by -OH,
Where M is hydrogen atom, alkali metal, alkaline earth gold
Genus, ammonium or pyridinium. Also,
R¹¹, R¹², R¹³, R ¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}
Three or more of the groups are not aryl groups;
R¹¹, R¹², R¹³And R¹⁴At least one of R^{twenty one},
R^{twenty two}, R^{twenty three}And R^{twenty four}At least one of
It does not form a ring. Further, the above-mentioned general formula
The group does not contain a group represented by -N = N-.

(2) An image forming method using the processing composition for a silver halide photographic light-sensitive material according to (1).

(3) A compound represented by the following general formula (I). General formula (I)

[0012]

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In the general formula (I), R¹¹, R¹²,
R¹³, R¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And R ^{twenty four}Is a hydrogen atom,
L represents an alkyl group, an aryl group or a heterocyclic group;
Represents a phenylene group or a naphthylene group;¹¹And R
¹²And / or R¹³And R¹⁴And / or R^{twenty one}And R
^{twenty two}And / or R^{twenty three}And R^{twenty four}And bond together to form a ring
It may be formed. However, in the molecule -SO_ThreeM, -CO_TwoM
Or at least one group represented by -OH,
Where M is hydrogen atom, alkali metal, alkaline earth gold
Genus, ammonium or pyridinium. Also,
R¹¹, R¹², R¹³, R ¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}
Three or more of the groups are not aryl groups;
R¹¹, R¹², R¹³And R¹⁴At least one of R^{twenty one},
R^{twenty two}, R^{twenty three}And R^{twenty four}At least one of
It does not form a ring. Further, the above-mentioned general formula
The group does not contain a group represented by -N = N-.

The above compounds of the present invention not only provide a means for solving the above problems, but also have the following excellent properties. That is, since the compound of the present invention does not emit fluorescence,
When used together with a bis (triazinylamino) stilbene disulfonic acid compound in the processing of a color pudding material, it is possible to independently control the fluorescent whitening property and the reduction in stain derived from the sensitizing dye. Therefore, it can be preferably used for the processing of a color negative film or a color reversal film which does not require the fluorescent whitening property of the processed light-sensitive material. In addition, since the stability in the bleach-fixing composition or the fixing composition is higher than that of the bis (triazinylamino) stilbene disulfonic acid compound and does not deteriorate with time, it is not affected by fluctuations in processing operation conditions such as daily processing amount. It contributes to maintaining stable processing performance.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the formula (I) will be described in detail. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² ,
R ²³ and R 1 to 20 carbon atoms as the alkyl group represented by ^24, preferably 1-8, more preferably 1-4
A substituted or unsubstituted alkyl group such as methyl group, ethyl group, i-propyl group, n-propyl group, n
-Octyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2
-(2-hydroxyethoxy) ethyl group, 2- [2-
(2-hydroxyethoxy) ethoxy] ethyl group, 2-
(2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl group, 2,3-dihydroxypropyl group,
3,4-dihydroxybutyl group, 2,3,4,5,6-
A pentahydroxyhexyl group.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R
^The aryl group represented by ²³ and R ²⁴ has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 20 carbon atoms.
8 substituted or unsubstituted aryl groups such as phenyl, naphthyl, 3-carboxyphenyl,
-Carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, and 4-sulfophenyl group. R ¹¹ , R ¹² ,
The heterocyclic group represented by R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ is preferably a substituted group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Or a monovalent group obtained by removing one hydrogen atom from an unsubstituted 5- or 6-membered aromatic or non-aromatic heterocyclic compound, such as a 2-furyl group, a 2-thienyl group,
-Pyrimidinyl group and 2-benzothiazolyl group.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ²¹ , R ²² , R
²³ and R ²⁴ are preferably a hydrogen atom, an alkyl group and an aryl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group,
-Hydroxyethyl group, 3-hydroxypropyl group, 2
-Hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy]
Ethyl group, 2,3-dihydroxypropyl group, 3,4-
Dihydroxybutyl, phenyl, 3-carboxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methoxyphenyl, 2-sulfophenyl, and 4-sulfophenyl are more preferred. Represents a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group,
-(2-hydroxyethoxy) ethyl, 2,3-dihydroxypropyl, phenyl, 3-carboxyphenyl, 4-carboxyphenyl, 2-sulfophenyl, 4-sulfophenyl, and more preferably Represents a hydrogen atom, a methyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group, a 2- (2-hydroxyethoxy) ethyl group, a 2,3-dihydroxypropyl group, a phenyl group, and a 4-sulfophenyl group. .

The phenylene or naphthylene group represented by L has 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
5, more preferably 6-11 substituted or unsubstituted phenylene groups or naphthylene groups, for example, 1,4-
Phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy-1,
3-phenylene, 3-sulfo-1,4-phenylene, 5
-Sulfo-1,3-phenylene, 2,5-dimethoxy-1,4-phenylene, 2,6-dichloro-1,4-phenylene.

L is preferably 1,4-phenylene,
1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, 5-
Sulfo-1,3-phenylene, and more preferably 1,4-phenylene and 1,3-phenylene.

The ring formed by combining R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ²¹ and R ²² , and R ²³ and R ²⁴ is preferably a 5- or 6-membered ring. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring.

Of the alkali metals and alkaline earth metals represented by M, particularly preferred are Na and K.
Examples of the ammonium group include an ammonium group, a triethylammonium group, and a tetrabutylammonium group. Most preferred as M are Na and K.

The following are specific examples of the compound of the present invention, but the present invention is not limited to these.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The compound represented by the general formula (I) is described in, for example, Koji Matsui, Journal of Organic Synthetic Chemistry, Vol. 17, p. 528 (1
959) and Japanese Patent No. 2,618,748. That is, a method is preferred in which cyanuric chloride is first reacted with a phenylenediamine derivative or a naphthalenediamine derivative, and then amines are sequentially reacted. Alternatively, it is also preferable to react the phenylenediamine derivative or the naphthalenediamine derivative in the second or last step. Examples of the solvent used in this reaction include water and organic solvents such as alcohols, ketones, ethers, and amides. Water and a water-soluble organic solvent are preferable, and a mixed solvent thereof may be used. Among them, a mixed solvent system of water and acetone is most preferable. Examples of the base used include organic bases such as triethylamine, pyridine, and 1,8-diazabicyclo [5,4,0] -7-undecene; sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and hydrogen hydrogen carbonate. And inorganic bases such as potassium. Of these, inorganic bases are preferred, with sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate being particularly preferred. The reaction temperature can be in the range of -20C to 150C, preferably in the range of -10C to 100C. More specifically, the first stage is preferably -10 to 10C, the second stage is preferably 0 to 40C, and the third stage is preferably 40 to 100C.

Synthesis Example 1 The exemplified compound (A-
2) was synthesized.

[0034]

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(Synthesis of Compound 3) In a three-necked flask, 37.6 g of Compound (1) and 280 mL of acetone were placed, and while stirring in an ice-acetone bath, Compound (2) 1 was added thereto.
A solution consisting of 0.8 g and 50 ml of acetone was heated to -7.
The solution was added dropwise over 10 minutes while maintaining the temperature at ２2 ° C. After completion of the dropwise addition, a solution composed of 10.6 g of sodium carbonate and 100 ml of water was added dropwise over 10 minutes. At this time, the internal temperature is 2-7 ° C
Met. After completion of the dropwise addition, the ice-acetone bath was removed, stirring was continued for 30 minutes, and the precipitated crystals were filtered by suction to obtain the desired compound (3) as a crude product. This was directly used in the next step.

(Synthesis of Compound 5) 25.0 g of Compound (4) and 250 ml of water were placed in a three-necked flask, and 21.2 g of sodium carbonate was added and dissolved therein with stirring.
Subsequently, the compound (3) obtained above was added, and the mixture was stirred at an internal temperature of 85 ° C. for 5 hours. After completion of the stirring, the mixture was cooled to room temperature, and the precipitated crystals were filtered by suction to obtain the desired compound (5) as a crude product. This was directly used in the next step.

(Synthesis of Exemplified Compound A-2) Into a three-necked flask were placed 45.6 g of the compound (5) and the compound (6) obtained above and 200 ml of water, and the mixture was heated with stirring at an internal temperature of 85 ° C. for 10 hours. Thereafter, the mixture was concentrated with a rotary evaporator, and crystals obtained by adding 500 ml of ethanol were subjected to suction filtration.
111.2 g of the target Exemplified Compound A-2 was obtained. The purity of the product was determined by liquid chromatography and found to be 64.5% (yield 98%). The conditions of the liquid chromatography were as follows. Column: TSK-gel ODS-80TM (manufactured by Tosoh Corporation) Eluent: A solution 20 ml of PIC A reagent (Waters) added to 1 liter of water B solution PIC A reagent (Waters Inc.) mixed with 800 ml of methanol and 200 ml of water 20 ml was added. A gradient was applied so that solution A / solution B = 50/50 (0 min.) → 0/100 (35 min.). Detection wavelength: 254 nm The purity was determined from the area of the peak recorded on the chart under the above conditions.

Synthesis Example 2 The exemplified compound (A-
3) was synthesized.

[0039]

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(Synthesis of Exemplified Compound 9) In a three-necked flask, 37.6 g of the compound (1) and 280 ml of acetone were placed.
Stir in an ice-acetone bath. Here compound (4) 2
A solution composed of 5.0 g, 21.2 g of sodium carbonate and 250 ml of water was added dropwise at an internal temperature of −7 to −2 ° C. over 15 minutes. After completion of the dropwise addition, the ice-acetone bath was removed, and stirring was continued for 30 minutes in the ice-cooled bath. Further here, compound (8) 10.
A solution of 8 g in 100 ml of acetone was added dropwise over 10 minutes, and 10.6 g of sodium carbonate was added to 30 m of water.
1 was added dropwise over 5 minutes. Thereafter, the ice bath was removed, stirring was continued for 3 hours, and the precipitated crystals were filtered by suction to obtain the desired compound (9) as a crude product. This was directly used in the next step.

(Synthesis of Exemplified Compound A-3) Into a three-necked flask were placed 45.6 g of the compound (9) and the compound (6) obtained above and 200 ml of water, and the mixture was heated and stirred at an internal temperature of 85 ° C. for 5 hours. Thereafter, 150 ml of water was distilled off using a rotary evaporator, and 600 ml of methanol was added thereto. Further, 50 ml of water was added to the crystals to dissolve them by heating, and then 600 ml of methanol was added thereto.
Was obtained 89.0 g. The purity of the product was determined by liquid chromatography and found to be 58.0% (yield 7).
1%). The conditions for liquid chromatography were the same as in Synthesis Example 1.

Synthetic Example 3 The exemplified compound of the present invention (A-2)
3) was synthesized.

[0043]

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(Synthesis of Compound 12) 37.6 g of Compound (1) and 280 ml of acetone were placed in a three-necked flask and stirred in an ice-acetone bath. Here compound (10) 2
A solution consisting of 1.0 g, 10.6 g of sodium carbonate and 250 ml of water was added dropwise over 15 minutes while maintaining the internal temperature at -7 to 0 ° C. After the completion of the dropwise addition, the ice-acetone bath was removed, and stirring was continued for 30 minutes in an ice-cooled bath. Then, 18.2 g of compound (6) was obtained.
Was dissolved in 100 ml of acetone over 10 minutes, and a solution of 10.6 g of sodium carbonate dissolved in 30 ml of water was added dropwise over 5 minutes. Thereafter, the ice bath was removed, stirring was continued for 3 hours, and the precipitated crystals were filtered by suction to obtain the desired compound (12) as a crude product. This was directly used in the next step.

(Synthesis of Exemplified Compound A-23) Compounds (12) and (13) obtained above in a three-necked flask
After 6 g and 300 ml of water were added and heated and stirred at an internal temperature of 85 ° C. for 5 hours, 250 ml of water was distilled off with a rotary evaporator, and 600 ml of methanol was added thereto, and the precipitated crystals were filtered by suction. Add 60 ml of water to the crystals
Was added and heated to dissolve, and then 600 ml of methanol was added, and the precipitated crystals were collected by suction filtration to obtain 58.7 g of the intended Exemplified Compound A-23. The purity of the product was determined by liquid chromatography and found to be 72.0% (yield 61%). The conditions for liquid chromatography were the same as in Synthesis Example 1.

When the compound of the present invention has a plurality of asymmetric carbon atoms in the molecule, a plurality of stereoisomers exist for the same structure, but the present invention shows all possible stereoisomers. In addition, only one of a plurality of stereoisomers can be used, or some of them can be used as a mixture.

In the treatment composition of the present invention, one kind of the compound of the formula (I) may be used alone, or two or more kinds thereof may be used in combination. The number of the compounds to be used and the kind of the treatment composition to be contained are arbitrarily selected. be able to. Further, the compound of the present invention may be used in combination with one or more bis (triazinylamino) stilbene disulfonic acid compounds. Also at this time, the number of compounds used and the type of treatment composition to be contained can be arbitrarily selected.

As the bis (triazinylamino) stilbene disulfonic acid compound used in combination with the compound of the present invention, a known or commercially available diaminostilbene-based fluorescent whitening agent can be used. As the known bistriazinyldiaminostilbene disulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625 or JP-A-10-104809 are preferable. Commercially available compounds are described, for example, in "Dyeing Note", 19th edition (Shirosen Co., Ltd.), p. 165-P. 168,
Among the products listed in it, Blanko
phor BSUliq, REU or Hakkol
BRK is preferred.

Further, as the compound of the present invention, a compound having a triazine ring other than the bis (triazinylamino) stilbene disulfonic acid compound may be used in combination. This can further improve the solubility and the residual color reduction effect. The concentration of the bis (triazinylamino) stilbene disulfonic acid compound in the working solution is 0.05 to 20 mmol / L, preferably 0.1 to 10 mmol / L, more preferably 0.2 to 10 mmol / L. It is. When the compound of the present invention is used after being diluted with water, the concentration in the treatment composition is a value obtained by multiplying the concentration in the working solution by the concentration ratio.
The concentration of the compound having a triazine ring of the bis (triazinylamino) stilbene disulfonic acid compound or less is 0.01 to 10 mmol / L, preferably 0.05 to 5 mmol / L, more preferably 0.05 to 5 mmol / L in the working solution. 0.1 ~
5 mmol / L. When the compound of the present invention is used after being diluted with water, the concentration in the treatment composition is a value obtained by multiplying the concentration in the working solution by the concentration ratio. Compound to be used in combination is 1
Species or two or more species may be arbitrarily combined. Examples of the compound used in combination include the following compounds, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Next, the treatment composition of the present invention will be described in detail. The processing composition in the present invention means a processing composition required for processing for forming an image of a silver halide color photographic light-sensitive material, and specifically, a color developing composition, a bleaching composition, a bleach-fixing composition , A fixing composition, a washing composition and a stabilizing composition, and may be a black-and-white developing composition, a reversing composition and a pre-bleaching composition. These treatment compositions may be prepared at a working solution concentration as a tank solution or a replenisher, or may be prepared as a concentrate.
When the treatment composition of the present invention is a concentrated solution, it is mixed with water at a predetermined ratio at the time of use and used as a replenisher or a tank solution. Although the compound of the present invention is characterized by having excellent precipitation stability in a composition in a solution state, the compound of the present invention may be used in a granular, tablet, powder or slurry treatment composition.

The composition of the present invention may be an additive composition. The additive composition has a function of adjusting photographic performance by adding to a tank solution or a replenisher required for processing for forming an image of a silver halide color photographic light-sensitive material before or during processing. A composition.

In the treatment composition of the present invention, the concentration of the compound of the general formula (I) is 0.05 to 20 in the working solution.
mmol / L, preferably 0.15 to 15 mmol
1 / L, more preferably 0.2 to 10 mmol / L. When the treatment composition of the present invention is used after being diluted with water or another treatment composition, the concentration in the treatment composition is a value obtained by multiplying the concentration in the liquid used by the concentration ratio.
In the present specification, the “concentration ratio” refers to the ratio between the component concentration in the processing agent composition and the component concentration in the processing solution used, as is generally used in the industry. .

The image forming method of the present invention uses the processing composition of the present invention in at least one of the processing steps. The treatment composition of the present invention may be used in a plurality of steps or all steps.

Although there are several methods for producing the treatment composition of the present invention, the following three methods give good results. However, the method of manufacturing the present invention is not limited to the following three methods. [Method A] A method in which a small amount of water is introduced into a mixing tank in advance, and constituent chemicals are sequentially charged therein while stirring. [Method B] A method in which constituent chemicals are previously mixed in a mixing tank, and a small amount of water is poured into the mixing tank at a stretch. [Method C] A method of dividing constituent chemicals into appropriate groups in advance, dissolving each in water or a hydrophilic organic solvent to form a concentrated solution, and then mixing the concentrated solutions. A manufacturing method that partially incorporates each method.

Next, the processing composition of the present invention comprises a developing composition,
For a bleaching composition, a bleach-fixing composition, a fixing composition, a washing composition and a stabilizing composition, an additive composition,
Each composition will be described.

The color developing composition of the present invention contains a color developing agent, and is preferably a known aromatic primary amine color developing agent, particularly preferably a p-phenylenediamine derivative. Representative examples are shown below, but the present invention is not limited to these. In recent years, among black-and-white light-sensitive materials, couplers have been added so as to develop black, and there are also those which form black-and-white images using a general-purpose color developing solution. It is also applied to some kinds of photosensitive materials.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N
-Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β
-Hydroxyethyl) aniline 6) 4-amino-3-methyl-N-ethyl-N- (3
-Hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4
-Hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N- (β
-Methanesulfonamidoethyl) -aniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N-
(Β-methoxyethyl) -aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethyl-aniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl) -N-n-propyl-aniline 13) 4-amino-3-methyl-N- (4-carbamoylbutyl) -N-n-propyl-aniline 14) N- (4-amino-3-methylphenyl) -3
-Hydroxypyrrolidine 15) N- (4-amino-3-methylphenyl) -3
-Hydroxymethylpyrrolidine 16) N- (4-amino-3-methylphenyl) -3
-Pyrrolidine carboxamide

Among the p-phenylenediamine derivatives, the exemplified compounds 5), 6), 7), 8) and 12) are preferred, and 5) and 8) are particularly preferred. These p
The phenylenediamine derivative is usually a sulfate, hydrochloride, p-toluenesulfonate, naphthalenedisulfonic acid salt, N, N-bis (ethyl sulfonate) hydroxylamine salt in the solid state. Further, it may be added as a free form having no counter salt. The concentration of the aromatic primary amine developing agent is 4 to 100 mm in the working solution.
ol / L, preferably 6 to 50 mmol / L, and more preferably 8 to 25 mmol / L.

The color developing solution of the present invention may contain a compound for preventing precipitation of a color developing agent, and examples thereof include polyethylene glycols, arylsulfonic acids, alkylsulfonic acids, and urea compounds described in JP-A-11-174643. Can be Among them, diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and salts thereof, linear alkylsulfonic acids having 5 to 9 carbon atoms and salts thereof, and ethylene urea, which have particularly small and good effects on photographic properties, are particularly preferred. preferable.

The color developing composition of the present invention preferably contains a compound for preventing deterioration of the color developing agent due to air oxidation, that is, a preservative. Sulfites and hydroxylamines are preferred as inorganic preservatives, which exhibit remarkable preservative action, and are also preferably used in combination with organic preservatives. Sulfite and hydroxylamine may adversely affect the photographic properties in the color development process depending on the target photographic material, so if only one of them is contained, or only the organic preservative is substantially not contained. Sometimes used.

Examples of the organic preservative include hydroxyamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammoniums, Nitroxy radicals, alcohols,
Oximes, diamides, condensed amines, cyclic amides, salicylic acids, polyethyleneimines, alkanolamines and aromatic polyhydroxy compounds are effective. Among the organic preservatives, JP-A-3-56456
And the hydroxylamine derivatives described in JP-A-3-33845 and JP-A-3-33846 and JP-A-6-148841.
Are particularly preferred.

It is preferable to use a hydroxylamine derivative in combination with an alkanolamine from the viewpoint of improving the stability of the color developing solution in continuous processing. Particularly preferred compounds used in combination with hydroxylamines include triisopropanolamine and triethanolamine.
It is also preferable to use the compound in combination with a cyclic amide compound, and among them, ε-caprolactam is particularly preferable.

The pH of the color developing composition of the present invention is from 9.5 to 9.5.
13.5 is preferred and the color developer prepared therefrom has a pH of 9.0 to 12.2, preferably a pH of 9.9.
１11.2. A buffer is preferably added to maintain the pH, and the buffer is preferably a potassium salt or a sodium salt of an inorganic salt such as carbonate, bicarbonate, phosphate, borate and tetraborate. . Organic compounds such as 5-sulfosalicylic acid, β-alanine, proline, and trishydroxyaminomethane are also preferably used, but the present invention is not limited to these compounds. The concentration of the buffer was 0.1 mol as the concentration of the color developing replenisher.
1 / L or more, especially 0.1 to 0.4 mol / L.

The color developing composition of the present invention comprises
Various chelating agents which are precipitation inhibitors such as magnesium can be added. One or more chelating agents may be used. Preferred compounds include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, ethylenediaminesuccinic acid (s, s-isomer), 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid and the like. The amount of the chelating agent may be an amount sufficient to mask the metal ions in the color developer, and is usually 0.1 g / L.
-10 g / L.

An optional development accelerator can be added to the color developing composition of the present invention, if necessary. Examples of the development accelerator include polyalkylene oxides, 1-phenyl-3-pyrazolidones, alcohols, carboxylic acids and the like.

An optional antifoggant can be added to the color developing composition of the present invention, if necessary. Examples of the antifoggant include metal halides such as sodium chloride, potassium bromide, and potassium iodide, and organic antifoggants represented by a nitrogen-containing heterocyclic compound. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
-Chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, adenine and the like. Also other alkyl carboxylic acids,
Aryl carboxylic acids and saccharides may be added as necessary.

In the case of a color print photosensitive material in the color development applied to the present invention, the processing temperature is 30 to 55 ° C., preferably 35 to 50 ° C., more preferably 38 to 50 ° C.
45 ° C. The development time is 5 to 90 seconds, preferably 8 seconds to 60 seconds, more preferably 10 seconds to 45 seconds. It is preferable that the replenishing amount is small, but 15 to 200 mL is suitable for 1 m ^{2 of the} photographic material, and preferably 20 to 200 mL.
It is 120 mL, more preferably 30 to 60 mL.

In the case of a color negative film, the processing temperature is 30 to 55 ° C., preferably 35 to 50 ° C., more preferably 38 to 45 ° C. Development time is 4
The duration is 5 seconds to 5 minutes, preferably 60 seconds to 4 minutes, and more preferably 90 seconds to 3 minutes 15 seconds. It is preferable that the replenishment amount is small, but 24 exp. 10-200m per one
L is appropriate, preferably 12 to 60 mL, more preferably 15 to 30 mL.

In the case of a color reversal film, the processing temperature is from 32 to 45 ° C., preferably from 35 to 40 ° C., more preferably from 36.5 to 39.5 ° C. The development time is 4 minutes to 8 minutes, preferably 5 minutes to 7 minutes, and more preferably 5 minutes 30 seconds to 6 minutes 30 seconds. Replenishment rate is desirably small but per the photosensitive material 1 m ^2, 1000
3,000 mL is suitable, preferably 1500-2.
It is 800 mL, more preferably 2000-2400 mL.

JP-A-11-174643, JP-A-11-11746
The color developing compositions obtained by concentrating replenishers described in JP-A-194461 and JP-A-11-194462 are examples of preferred embodiments.

As the bleaching agent used in the bleaching composition and the bleach-fixing composition of the present invention, known bleaching agents can be used. In particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids or citric acid) Complex salts of organic acids such as tartaric acid and malic acid), persulfates, hydrogen peroxide and the like. Also, two or more bleaching agents may be used as a mixture.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoints of rapidity and prevention of environmental pollution. Iron (II
Listed below are aminopolycarboxylic acids or salts thereof useful for forming the organic complex salt of I), such as biodegradable ethylenediamine succinic acid (s, s-form), N- (2-
(Carboxylate ethyl) -L-aspartic acid, β-
Including alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,
Examples thereof include compounds such as 3-propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, and glycol etherdiaminetetraacetic acid. These compounds may be any of the sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediamine succinic acid (s, s-form),
In addition to N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-propylenediaminetetraacetic acid have their iron (II)
I) It is preferable because the photographic properties of the salt are good. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt,
For example, ferric sulfate, ferric chloride, ferric nitrate, ferric nitrate ammonium, ferric phosphate and the like to form a ferric ion complex salt in a solution as a chelating agent such as aminopolycarboxylic acid. You may. Further, the chelating agent may be used in excess of the amount required for the formation of the ferric complex salt. The bleaching agent concentration in the bleaching solution or bleach-fixing solution is 0.01 to 1.0 in the working solution.
mol / L, preferably 0.05 to 0.5 mol / L,
More preferably, it is 0.1 to 0.5 mol / L.

It is also preferable to add a buffer to the bleaching solution or the bleach-fixing solution. The buffer is selected depending on the intended pH, but preferred compounds include succinic acid, maleic acid,
Organic acids such as glycolic acid, malonic acid, fumaric acid, succinic acid, sulfosuccinic acid and acetic acid, or organic bases such as imidazole and dimethylimidazole;
The general formula (Aa) and the general formula (B) described in No. 11819
-B). The amount of these compounds added is 0.005 mol / L or more in the working solution.
3.0 mol / L is preferred, and more preferably 0.0 mol / L.
5 mol / L to 1.5 mol / L. Bleach pH
The range is preferably pH 2-7, particularly preferably pH 3-6. In the case of bleach-fixing, pH 3 to 8 is preferable, and pH 4 to 7
Is more preferred.

In the bleach-fixing of the color print photographic material applied to the present invention, the processing temperature is 30 to 55 ° C., preferably 35 to 50 ° C., more preferably 38 to 45 ° C.
It is. The bleach-fixing time is from 5 to 90 seconds, preferably from 8 to 60 seconds, more preferably from 10 to 45 seconds. It is preferable that the replenishing amount is small, but ²⁰ to 200 mL is suitable for 1 m ^{2 of the} light-sensitive material, and preferably 25 to 200 mL.
It is 120 mL, more preferably 30 to 50 mL.

In the bleaching of a color negative film, the processing temperature is 30 to 55 ° C., preferably 35 to 5 ° C.
The temperature is 0 ° C, more preferably 38 to 45 ° C. The bleaching time is 12 seconds to 2 minutes, preferably 15 seconds to 1 minute 1
5 seconds, more preferably 18 seconds to 60 seconds. It is preferable that the replenishment amount is small, but 24 exp. Per one,
2.5 to 50 mL is suitable, preferably 3 to 25 m
L, more preferably 4 to 12 mL.

In the bleaching of the color reversal film, the processing temperature is 30 to 45 ° C., preferably 33 to 4 ° C.
The temperature is 0 ° C, more preferably 37 to 39 ° C. The bleaching time is 4 minutes to 8 minutes, preferably 5 minutes to 7 minutes, more preferably 5 minutes 30 seconds to 6 minutes 30 seconds. It is preferable that the replenishing amount is small, but 160 m ² per 1 m ^{2 of the} photosensitive material.
~ 400 mL is suitable, preferably 180-300
mL, more preferably 200-250 mL.

The fixing agent used in the bleach-fixing composition and the fixing composition of the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, and thiocyanates such as sodium thiocyanate and ammonium thiocyanate. Acid salt, ethylenebisglycolic acid,
3,6-dithia-1,8-octanediol and
Thioether compounds and thioureas described in JP-A-317055;
It is a water-soluble silver halide dissolving agent such as a mesoionic compound described in No. 230749, and these can be used alone or in combination of two or more. As the fixing agent, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The fixing agent concentration in the fixing solution or the bleach-fixing solution is 0.3 to 2 mo.
1 / L is preferable, and more preferably 0.5 to 1.5 m
ol / L.

It is preferable to add a buffer to the bleach-fixing composition or the fixing composition. Preferred buffers include heterocyclic organic bases such as imidazole and dimethylimidazole, aminoalkylenesulfonic acids such as taurine, and dibasic acids such as succinic acid, maleic acid and malonic acid. The pH is preferably from 3 to 8, and more preferably from 4 to 7.

The bleach-fixing composition and fixing composition of the present invention preferably contain, as a preservative, a compound capable of releasing a sulfite ion, that is, a sulfite, a bisulfite, a metabisulfite and the like. It is preferably added as a salt, sodium salt or ammonium salt.
It is also preferable to contain an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid. These compounds are used in an amount of 0.02 to 1.0 mol /
L is preferably contained. As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct or carbonyl compound may be added.

In the bleach-fixing composition and fixing composition of the present invention, mercaptotriazole, aminomercaptotriazole, and N
Bisamidines, bisguanidines or monoamidines described in JP-A-5-303185, which promote washing out of mercapto-containing heterocyclic compounds such as -methylmercaptoimidazole and developing agents.
In addition, polymers such as polyethylene glycol and polyvinylpyrrolidone, a chelating agent, an antifoaming agent, a fungicide, and the like may be added to the bleach-fixing composition and the fixing composition of the present invention as needed.

The processing temperature, the bleach-fixing time and the replenishment amount in the bleach-fixing of the color print photographic material applied to the present invention are as described above. In fixing a color negative film, the processing temperature is from 30 to 55C, preferably from 35 to 50C, more preferably from 38 to 45C. The bleaching time is 20 seconds to 2 minutes, preferably 30 seconds.
Seconds to 1 minute and 40 seconds, more preferably 35 seconds to 1 minute and 20 seconds. It is preferable that the replenishment amount is small, but 24 exp. 1
4 to 60 mL is appropriate per book, preferably 5 to 60 mL.
It is 40 mL, more preferably 6 to 30 mL.

In fixing a color reversal film, the processing temperature is 30 to 45 ° C., preferably 33 to 4 ° C.
The temperature is 0 ° C, more preferably 37 to 39 ° C. The fixing time is 2 minutes to 6 minutes, preferably 3 minutes to 5 minutes, more preferably 3 minutes 30 seconds to 4 minutes 30 seconds. It is preferable that the replenishing amount is small, but 800 m ² per m ^{2 of the} photosensitive material.
2,000 mL is suitable, preferably 900-15.
00 mL, more preferably 1000-1250 mL.

In the water-washing composition and the stable composition of the present invention, formalin, acetaldehyde, pyruvaldehyde and formaldehyde bisulfite described in US Pat. An adduct or an N-methylol compound described in JP-A-5-34889 may be added. Further, it is preferable to contain an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid. A surfactant may be added as a draining agent, a chelating agent as a water softener, a buffer for adjusting pH, an antifoaming agent, an antifungal agent, a bactericide, and the like, if necessary. The preferred pH is 4-10, more preferably 5-8.
The temperature can be variously set depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C.

The additive composition of the present invention preferably comprises the compound of the present invention and water. If necessary, a water-soluble aliphatic compound, a bis (triazinylamino) stilbene disulfonic acid compound, a chelating agent, Inorganic salts and the like may be added. Preferred compounds as the water-soluble aliphatic compound are diethylene glycol and polyethylene glycol 300.
(Average molecular weight: 300) and alkanolamines such as triethanolamine and triisopropanolamine, and diethylene glycol is particularly preferable. The additive composition of the present invention can be added to any processing bath or replenisher required for processing for forming an image of a silver halide color photographic light-sensitive material. The compound of the present invention is preferably concentrated in the additive composition, and the concentration ratio to the working solution is 50 to 4000 times, preferably 100 to 2000 times, and more preferably 200 to 1000 times. It is. One preferred embodiment is a method of adding the additive composition of the present invention to a fixing bath and / or a fixing replenisher in a color reversal process, but the present invention is not limited to this.

The photographic elements processed using the present invention can be prepared by using conventional silver halide as a light-sensitive material such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and mixtures thereof. And the like. In one embodiment, the photosensitive material in the photographic element comprises at least 50 mol
% Or more silver chloride, more preferably at least 90 mol
% Of silver chloride, and is often used, for example, for color printing.

In another embodiment, at least one emulsion in the light-sensitive material is mainly silver bromide (at least 50 mol% silver bromide). Most preferably, the photographic element has one or more color records, each color record having one or more predominantly silver bromide emulsions such as those used in color negative films and color reversal films. Photographic elements containing the light-sensitive material processed according to the present invention can be single color elements or multicolor elements. The photographic element can also have a magnetic recording layer as known in the art.

Details of individual photographic elements are described in, for example, Research Disclosure (hereinafter abbreviated as RD), RD17643, pp. 23-27, RD187.
16647-650 pages, RD307105 866
~ 868 pages, 873 ~ 879 pages, RD3654
4 pages 501 to 541. These are useful silver halide emulsions (negative or positive type) and their preparation methods, various sensitizers, dye-forming couplers, image dye stabilizers, dyes, ultraviolet absorbers, filters, binders, hardeners, plasticizers. Lubricants, coating aids, surfactants, antistatic agents, matting agents, paper and film supports, or various image forming methods for negative and positive image forming color elements.

The processing composition of the present invention is advantageously in a form in which all the components contained in the working solution are contained in one composition, that is, in a single-part composition. However, the color developing composition and the bleach-fixing composition When it is not desirable to keep the constituents in contact with each other for a long period of time, the constituents may be separated into two or more liquid preparations or solid mixtures to form a two-part or three-part treatment composition. Such a processing agent composition is usually 1, according to the name of the international standard ISO5989 (term of preparation processing agent),
It is called a two or three part configuration. By dividing the treatment composition of the present invention into parts, the effects and features of the present invention are not lost. Among them, the color developing composition preferably has a one-part structure.

For the container of the treatment composition of the present invention, a known material depending on the contents can be used. Even if the container is made of a single material, a composite material such as a material having high gas permeability can be used. It may be made of a composite material made of a material having high alkali stability. It is preferable that the container is made of a single material from the viewpoint of reuse and recyclability.
Materials used for the container include polyester resin, polyolefin resin, acrylic resin, ABS resin, epoxy resin, polyamide resin such as nylon, polyurethane resin, polystyrene resin, polycarbonate resin, PV
A, polyvinyl chloride, polyvinylidene chloride, polyethylene resin, among them, polyethylene terephthalate, polyester resin such as polyethylene naphthalate,
A container composed of a single material of a polyolefin resin such as polyethylene or polypropylene is preferable. Among them, a polyethylene resin is preferable, and a high-density polyethylene resin (HDPE) is more preferable as a container material.

The container material used in the present invention may contain carbon black, titanium white, pigment, calcium carbonate, a plasticizer compatible with the material, and the like as long as the treatment composition is not affected. The material of the container is preferably a material having a polyethylene ratio of 85% or more and containing no plasticizer, and more preferably a material having a polyethylene ratio of 95% or more and containing no plasticizer.

The shape and structure of the container filled with the treatment composition of the present invention can be arbitrarily designed according to the purpose.
In addition to the fixed bottles, a flexible type described in JP-A-1-235950, a container with a flexible partition described in JP-A-62-134626, and the like can be used. The container described in JP-A-11-282148 is particularly preferable as a container of the treatment composition of the present invention from the viewpoint of capacity, space efficiency, self-sustainability, shape preservation, and reuse and recycling.
A preferred embodiment is a kit in which a plurality of compositions of the invention are filled into containers made of a single component material having the same shape and volume, and the containers are incorporated into a single cartridge. The cartridge described in JP-A-2000-3014 can be mentioned as an example. The combination of the treatment compositions in the cartridge can be arbitrarily selected. JP-A-11-295858, JP-A-11-295858
The cartridge described in 1-288068 is a preferred embodiment in which a developing composition, a bleaching composition, and a fixing composition are incorporated.

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The following examples, including the demonstration of the stability and photographic properties of the processing compositions of the present invention against precipitation,
Further, the present invention will be described in detail, but the present invention is not limited thereto.

Example 1 (1) Preparation of Color Developing Composition A color developing composition of the concentrated liquid type having the following composition was prepared. Compound of the present invention or comparative compound See Table 1. Fluorescent brightener (FL-1, below) 1.75 g triisopropanolamine 34.0 g ethylenediaminetetraacetic acid 15.0 g sodium sulfite 0.80 g polyethylene glycol (average molecular weight 300) 40. 0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonic acid 2.0 g Disodium-N, N-bis (sulfonateethyl) hydroxylamine 55.0 g 4-Amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline / 3/2 sulfate / monohydrate 55.0 g Potassium hydroxide 19.0 g Sodium hydroxide 24.0 g Potassium carbonate 100.0 g Water was added and the total amount was 1000 mL pH 13.2

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(2) Preparation of Photosensitive Material Sample A corona discharge treatment was applied to the surface of a support in which both sides of the paper were coated with a polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. From the layer to the seventh layer, a silver halide color photographic light-sensitive material P-1 having the following layer constitution was prepared. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC), color image stabilizer (Cp
d-1) 250 g, color image stabilizer (Cpd-14) 30
g, color image stabilizer (Cpd-15) 100 g, color image stabilizer (Cpd-16) 80 g, color image stabilizer (Cpd-17)
50 g and 10 g of a color image stabilizer (Cpd-18) are dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate, and this solution is emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 25 g of sodium dodecylbenzenesulfonate to emulsify. Dispersion C was prepared. On the other hand, silver chlorobromide emulsion C (cubic, a 5: 5 mixture (silver molar ratio) of large-size emulsion C having an average grain size of 0.40 μm and small-size emulsion C having an average grain size of 0.40 μm. The variation coefficient of the grain size distribution is 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was localized on a part of the grain surface based on the silver chloride emulsion.) This emulsion contains the red-sensitive sensitizing dyes G and H shown below in large-sized emulsion C per mole of silver.
Is added 12.0 × 10 ^-5 mol, respectively for each 9.0 × 10 ^-5 mol to the small size emulsion C for. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

(Preparation of Coating Solutions for Each Layer) The coating solutions for the first to fourth, sixth and seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The total amount of Ab-1, Ab-2, Ab-3 and Ab-4 was 15.0 mg / m ² , 6 in each layer.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 mg
/ M ² .

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(Spectral Sensitization) The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

Blue-sensitive emulsion layer

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(Sensitizing dyes A and C were added in an amount of 0.42 × 10 ^-4 mol per mol of silver halide and 0.50 × 10 ^-4 mol per mol of silver emulsion per mol of silver halide). (Sensitizing dye B was added in an amount of 3.4 × 10 ^-4 mol for a large-sized emulsion and 4.1 × 10 ^-4 mol for a small-sized emulsion per mol of silver halide.)

Green-sensitive emulsion layer

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(Sensitizing dye D was added in an amount of 3.0 × 10 ^-4 mol for a large-sized emulsion and 3.6 × 10 ^-4 mol for a small-sized emulsion per mol of silver halide. Sensitizing dye E was added in an amount of 4.0 × 10 ^-4 mol for a large-sized emulsion and 7.0 × 10 ^-5 mol for a small-sized emulsion per mol of silver halide. F per mol of silver halide, 2.0 ×
10 ^-4 mol was added, and 2.8 x 10 ^-4 mol was added to the small size emulsion. )

Red-sensitive emulsion layer

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(The sensitizing dyes G and H were used in an amount of 8.0 × 10 ^-5 mol per mol of silver halide per mol of silver halide emulsion,
10.7 × 10 ^-5 mol was added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

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1- (3-methylureidophenyl) -5 was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer.
-Mercaptotetrazole was added in an amount of 3.3 × 10 ^-4 mol, 1.0 × 10 ^-3 mol and 5.9 × 10 ^-4 mol per mol of silver halide, respectively. The second layer, the fourth layer, the sixth layer, and the seventh layer also have a concentration of 0.2 mg / m ² , 0.2, respectively.
mg / m ² , 0.6 mg / m ² , and 0.1 mg / m ² . For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide. In the red-sensitive emulsion layer, a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200000 to 400)
000) was added at 0.05 g / m ² . Catechol-3,5-disulfonate disodium 6 mg / m ² , 6 mg / m ² , 18 m respectively in the second, fourth and sixth layers
g / m ² . The following dyes (the amount in parentheses indicates the coating amount) was added to prevent irradiation.

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(Layer Structure) Each layer structure is shown below. The numbers indicate the coating amount (g / m ² ). The silver halide emulsion shows a silver coating conversion amount. Support Polyethylene resin laminated paper [white pigment (TiO ₂ : content 16% by weight, ZnO: content 4% by weight) on polyethylene resin on the first layer side] and fluorescent whitening agent (4,4′-bis (5- Methylbenzoxazolyl)
Stilbene content 0.03% by weight), including bluish dye (ultramarine)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, large-sized emulsion A having an average particle size of 0.74 μm and 0) 5: 5 mixture (silver molar ratio) with 0.65 μm small size emulsion A. Variation coefficients of grain size distribution are 0.08 and 0.10, respectively. 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) ) 0.04 Color image stabilizer (Cpd-3) 0.07 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color mixture prevention assistant (Cpd-5) 0.018 Stabilizer (Cpd-6) 0.13 Color mixture prevention Agent (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B with an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In both sizes, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0 .14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorber (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color mixing inhibitor (Cpd-4) 0.002 Stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color Image Stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color mixture prevention auxiliary (Cpd-5) 0.013 Stabilizer (Cpd-6) 0.10 Color mixture prevention Agent (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large-size emulsion A having an average grain size of 0.40 μm and small-size emulsion A of 0.30 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In both sizes, 0.5 mol% of silver bromide was contained locally on a part of the grain surface composed of silver chloride as a base.) 0 .20 gelatin 1.11 cyan coupler (ExC) 0.25 color image stabilizer (Cpd-1) 0.25 color image stabilizer (Cpd-14) 0.03 color image stabilizer (Cpd-15) 0.10 Color image stabilizer (Cpd-16) 0.08 Color image stabilizer (Cpd-17) 0.05 Color image stabilizer (Cpd-18) 0.01 Solvent (Solv-5) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-1) 0.14 Ultraviolet absorbing agent (UV-2) 0.05 Ultraviolet absorbing agent (UV-3) 0.04 Ultraviolet absorbing Agent (UV-4) 0.06 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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(3) Developing process The above photosensitive material sample P-1 was processed into a roll having a width of 127 mm, and the color balance was standardized with an average density of 0.7 using a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. The photosensitive material sample P-1 is imagewise exposed from a color negative film of a typical developed finish,
Continuous processing (running test) was performed until the volume of the color developing replenisher used in the following processing steps was 0.5 times the volume of the color developing tank.

Processing Step Temperature Time Replenishment Amount Color Development 38.5 ° C. 45 seconds 45 mL Bleaching and Fixing 38.0 ° C. 45 seconds 35 mL Rinse 1 38.0 ° C. 20 seconds-Rinse 2 38.0 ° C. 20 seconds-Rinse 338.0 ℃ 20 seconds-Rinse 4 38.0 ° C 20 seconds 121mL drying 80 ° C (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Attach a phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. to the rinse (3). Remove the rinse solution from the rinse (3) and send it to the reverse osmosis module (RC50D) by pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was of a four-tank countercurrent type from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] Water 800 mL Compound of the present invention or comparative compound 2 mmol Fluorescent brightener (FL-1) 0.35 g Triisopropanolamine 8.8 g Polyethylene glycol average molecular weight 300 10.0 g Ethylenediaminetetraacetic acid 4. 0 g Sodium sulfite 0.10 g Potassium chloride 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.50 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 4-amino-3 -Methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate 4.8 g Potassium carbonate 26.3 g Water was added and the total amount was 1000 mL pH (25 ° C., sulfuric acid and KOH 10.15 Color development replenisher contains (1 )), A solution obtained by diluting the color developing composition prepared in the above step 3.8 times with water was used.

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL m-Carboxybenzenesulfinic acid 8.3 g 16.5 g Ammonium iron (III) ethylenediaminetetraacetate 47. 0g 94.0g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0g 32.0g Potassium metabisulfite 23.1 46.2g Water And a total amount of 1000 mL 1000 mL pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.5

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity of 5 μs / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5

(4) Evaluation Stability against Precipitation Precipitation The prepared color developing composition was placed in a glass bottle, and -5
Stored at 4 ° C. and room temperature for 4 weeks. The evaluation of the test results was carried out by visually judging the liquid after a lapse of time, and the level at which significant precipitation occurred was XX, the level at which clear precipitation occurred was X, the level at which slight precipitation was observed was Δ, and no precipitation occurred. Was evaluated on a 5-point scale, where the level of turbidity was evaluated as ○, and no turbidity or precipitation was observed, and the level of completely transparent was evaluated as ◎. Photographic properties of color paper processing
U-3 manufactured by Hitachi, Ltd. equipped with a 50 mmΦ integrating sphere
Measure the reflection spectrum using a 500-type spectrophotometer,
The absorbance of 450nm was D _B. Next, heat each sample at 40 ° C.
The sample was washed with distilled water for 5 minutes, dried and dried. The same measurement was performed, and the absorbance at 450 nm was _DBW . ΔD _BW was determined based on the following formula, and the degree of stain caused by the residual sensitizing dye was evaluated. ΔD _B = D _B - D _BW results

[0135]

[Table 1]

Sample 1-2 Using Comparative Compound FL-2
(Comparative Example) shows that the stain caused by the residual sensitizing dye is at a level equivalent to or close to that of the compound of the present invention, but all precipitate with the aging of the treatment composition. In Sample 1-1 (Comparative Example), no precipitation occurs, and thus the precipitation is caused by the added compound. Sample 1-3 using comparative compound FL-3
(Comparative Example) shows that although the stability to precipitation is high as in the case of using the compound of the present invention, the stain is rather increased. Light-sensitive material was carried out development processing using the processing composition of the present invention is less colored small i.e. white portion is stain [Delta] D _B due to retained sensitizing dye. In addition, the treatment composition of the present invention is completely transparent at room temperature even after aging for 4 weeks, and is completely transparent or turbid even at a low temperature (-5 ° C), and does not cause precipitation. This indicates that the present invention is a composition excellent in the effect of reducing stain caused by the residual sensitizing dye of the light-sensitive material after processing, and which does not produce a precipitate during storage at a low temperature of the processing composition. .

[0137]

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Example 2 (1) Preparation of Color Developing Composition Compound of the Present Invention See Table 2 Fluorescent Whitening Agent (FL-4) 3.5 g Fluorescent Whitening Agent (FL-5) 3.5 g Triisopropanolamine 40 1.0 g ethylenediaminetetraacetic acid 15.0 g sodium sulfite 0.80 g sodium p-toluenesulfonate 75.0 g sodium 4,5-dihydroxybenzene-1,3-disulfonate 2.0 g disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 55.0 g 4-amino-3-methyl-N-ethyl-N-([beta] -methanesulfonamidoethyl) aniline / 3/2 sulfate monohydrate 85.0 g Potassium hydroxide 34.5 g Hydroxide 12. Sodium 25.0 g Potassium carbonate 100.0 g Water was added to make a total amount of 1000 mL pH 13.

[0139]

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(2) Preparation of Sample of Photosensitive Material The same photosensitive material as that of Example 1, that is, Sample P-1 was used. (3) Development processing Experimental processing in which the above photosensitive material sample P-1 was processed into a roll having a width of 127 mm, and a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified so that the processing time and processing temperature could be changed. The photosensitive material sample was subjected to imagewise exposure from a developed color negative film having an average density of 0.7 and a standard color balance using an apparatus, and the volume of the color developing replenisher used in the following processing steps was 0% of the volume of the color developing tank. Continuous processing (running test) was performed until the value became 0.5 times.

Processing Step Temperature Time Replenishment amount Color development 45.0 ° C. 15 seconds 45 mL Bleach-fix 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds-Rinse 2 40.0 ° C. 8 seconds-Rinse 3 40.0 8 ° C.-Rinse 4 38.0 ° C. 8 seconds 121 mL Drying 80 ° C. 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Attach Rinse Screening System RC50D manufactured by Fuji Photo Film Co., Ltd. to rinse (3) Then, the rinse liquid is taken out of the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was of a four-tank countercurrent type from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] Water 800 mL Compound of the present invention 4 mmol Fluorescent whitening agent (FL-4) 0.50 g Fluorescent whitening agent (FL-5) 0.50 g Triisopropanolamine 8.8 g p-toluene sulfone Sodium acid salt 20.0 g Ethylenediaminetetraacetic acid 4.0 g Sodium sulfite 0.10 g Potassium chloride 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.50 g Disodium-N, N-bis (sulfonate ethyl) Hydroxylamine 8.5 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate 10.0 g Potassium carbonate 26.3 g Add water Total volume 1000mL pH (adjusted with sulfuric acid and KOH at 25 ℃) 10.35 Color development The Takashieki was used a solution prepared by diluting with water to 3.8 times the color developing composition prepared in (1)

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL Succinic acid 29.5 g 59.0 g Ethylene (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5 g 35.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water is added and the total amount is added. 1000 mL 1000 mL pH (adjusted at 25 ° C. with nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity 5 μs / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5

(4) Evaluation The same evaluation as in Example 1 was performed on the processed photosensitive material sample. result

[0146]

[Table 2]

Even when a color developing composition in which the concentration of the developing agent is increased is prepared and the processing is carried out for a shortened time, the processing composition of the present invention can maintain the stain ΔD _B due to the residual sensitizing dye.
Gives a low finish, and is completely transparent at room temperature even after 4 weeks of aging, and does not cause any precipitation at low temperatures (-5 ° C). This indicates that the processing composition of the present invention has rapid processing suitability for color paper.

Example 3 (1) Preparation of Fixing Composition Compound of the Present Invention See Table 6 Ammonium bisulfite solution (65%) 65.0 g Ammonium thiosulfate aqueous solution (750 g / L) 840 mL Imidazole 40.0 g Ethylenediaminetetraacetic acid 10. 0 g water is added to make a total amount of 1000 mL pH 7.00

(2) Photosensitive material 1) Adjustment of emulsion The silver halide emulsions Em-A to Em-A were prepared by the following production method.
O was prepared. (Preparation of Em-A) 1200 m aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr
L was kept at 35 ° C. and stirred vigorously. 1.9 silver nitrate
30 mL of an aqueous solution containing 1.5 g of KBr and a molecular weight of 15
30m aqueous solution containing 0.7g of low molecular weight gelatin of 000
L was added for 30 seconds by the double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the mixture was heated to 75 ° C. and aged.
After ripening, 35 g of succinated gelatin was added. PH
Was adjusted to 5.5. Aqueous solution 150 containing 30 g of silver nitrate
mL and KBr aqueous solution were added by a double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of silver nitrate and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, Ag with a size of 0.03 μm
The I fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at -25 mV. 132 mL of aqueous solution containing 35 g of silver nitrate and KBr
The aqueous solution was added by the double jet method over 7 minutes. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 in terms of KI was added, and 64 mL of a 0.8 M aqueous sodium sulfite solution was further added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and maintained for 4 minutes to rapidly generate iodide ions. Then, the pH was returned to 5.5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition, 250 mL of an aqueous solution containing 70 g of silver nitrate and KB
The r aqueous solution was added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, the yellow blood salt was added in an amount of 1.0 to 1 mol of silver.
× 10 ^-5 mol was added. After washing with water, calcium concentration 1
80 g of lime-treated gelatin (ppm)
H was adjusted to 5.8 and pAg to 8.7.

[0150]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. The above emulsion was heated to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added in terms of Ag, and shelled. Next, sensitizing dyes 1, 2, and 3 were added in the form of solid fine dispersion in the form of 5.85 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, and 9.00 × 10 ^-6 mol, respectively, per mol of silver. did. Sensitizing dyes 1, 2,
The solid fine dispersion of No. 3 was prepared as follows. As shown in the preparation conditions in Table 3, after dissolving the inorganic salt in ion-exchanged water, adding a sensitizing dye, and dispersing the mixture at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C. Solid fine dispersions of dyes 1, 2, and 3 were obtained. When the sensitizing dye was added and the sensitizing dye adsorption reached 90% of the adsorption amount in the equilibrium state, calcium nitrate was added so that the calcium concentration became 250 ppm. The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea and compound 4
Was added for optimal chemical sensitization. N, N- ヂ methylselenourea was added in an amount of 3.40 × 10 ⁻⁶ mol per mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0152]

[Table 3]

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was converted to a trimellitization compound having a molecular weight of 100,000 and containing 35 μmol of methionine per gram. %
Compound 1 was replaced with KI
The amount of the sensitizing dye added before the chemical sensitization was 6.50 × 10 ^-4 mol, 3.40 × 10 ^-4 mol for sensitizing dyes 1, 2, and 3, respectively. ^-4 mol,
1.00 × 10 ^-5 mol and the amount of N, N- ヂ methylselenourea added during chemical sensitization was 4.00 × 10 ^-5 mol.
Em-A in the same manner as Em-A except that the amount was changed to 10 ^-6 mol.
-B was prepared.

[0160]

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g,
The succinated gelatin was replaced with phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram, and compound 1 was replaced with 7.1 g of compound 7 in terms of KI, and added before chemical sensitization. The amount of the sensitizing dye was 7.80 × 10 ^-4 mol, 4.08 × 10 ^-4 mol, 1.2 with respect to the sensitizing dyes 1, 2, and 3, respectively.
The amount was changed to 0 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was 5.00 × 10 ^−6.
Em-C was prepared in the same manner as Em-A, except that it was changed to mol.

[0162]

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(Adjustment of Em-E) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of silver nitrate and 30 mL of an aqueous solution containing 1.5 g of KBr and 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 15 g of succinated gelatin and 20 g of the above-mentioned trimellitated gelatin were added. pH
Was adjusted to 5.5. Aqueous solution 150 containing 30 g of silver nitrate
mL and KBr aqueous solution were added by a double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of silver nitrate and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, Ag with a size of 0.03 μm
I fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content was 3.8%, and the silver potential was -25 mV.
Kept. 132 mL of aqueous solution containing 35 g of silver nitrate and KB
The aqueous solution of r was added by the double jet method over 7 minutes.
The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. KBr was added and the potential was -60 m
V, 1 m of sodium benzenethiosulfonate
g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of addition, molecular weight 150
A low molecular weight gelatin aqueous solution, a silver nitrate aqueous solution, and a KI aqueous solution were mixed in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570 to prepare a sphere-equivalent diameter immediately before addition. While continuously adding 8.0 g of a 0.008 μm AgI fine grain emulsion in terms of KI, 250 mL of an aqueous solution containing 70 g of silver nitrate and KB
The r aqueous solution was added over a period of 20 minutes while maintaining the potential at -60 mV. At this time, the yellow blood salt was added in an amount of 1. mol per mol of silver.
0 × 10 ^-5 mol was added. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and the pAg was adjusted to 8.7 at 40 ° C. The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, which was 15 ppm, 2 ppm and 1 ppm, respectively.

Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6
The chemical sensitization was carried out in the same manner as in Em-A except that the amounts were changed to 7.73 × 10 ^-4 mol, 1.65 × 10 ^-4 mol, and 6.20 × 10 ^-5 mol, respectively. Do, Em-
E was prepared.

[0165]

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[0166]

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[0167]

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(Preparation of Em-F) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously.
30 mL of an aqueous solution containing 1.9 g of silver nitrate, 1.5 mL of KBr
g and 30 mL of an aqueous solution containing 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After aging, 20 g of succinated gelatin and 15 g of phthalated gelatin were added. The pH was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of silver nitrate and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of silver nitrate and KBr
The final flow rate of the aqueous solution is 1.
The flow rate was accelerated so as to be doubled, and added over 15 minutes. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at −25 mV. 132 mL of an aqueous solution containing 35 g of silver nitrate and an aqueous KBr solution were added by a double jet method over 7 minutes. After adjusting the potential to −60 mV by adding an aqueous KBr solution, an AgI fine grain emulsion having a size of 0.03 μm was converted into 9.2 in terms of KI.
g was added. 1m sodium benzenethiosulfonate
g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition is completed, add 70% of silver nitrate.
g of an aqueous solution of 250 mL and an aqueous KBr solution at a potential of 60
The addition was performed over 20 minutes while maintaining the mV. At this time,
Yellow blood salt was added in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and pAg at 40 ° C.
Was adjusted to 8.7. The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy.
ppm and 1 ppm. Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the added amount was 8.
50 × 10 ⁻⁴ mol, 1.82 × 10 ⁻⁴ mol, 6.82 ×
Em-F was prepared by performing chemical sensitization in the same manner as in Em-B except that the amount was 10 ^-5 mol.

(Preparation of Em-G) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of silver nitrate, 1.5 g of KBr
And 30 mL of an aqueous solution containing 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 1.5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After the ripening, 15 g of the above-mentioned trimellitized gelatin and 20 g of the above-mentioned phthalated gelatin were added. p
H was adjusted to 5.5. Aqueous solution 15 containing 30 g of silver nitrate
0 mL and the aqueous KBr solution were added by the double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of silver nitrate and an aqueous KBr solution were added over a period of 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the size of A
The gI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content was 3.8%, and the silver potential was -25 m
Kept at V. 132 mL of aqueous solution containing 35 g of silver nitrate and K
The aqueous Br solution was added by the double jet method over 7 minutes. The addition of the aqueous KBr solution was adjusted so that the potential became -60 mV. 7.1 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition, 250 mL of an aqueous solution containing 70 g of silver nitrate and KB
The r aqueous solution was added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, the yellow blood salt was added in an amount of 1.0 to 1 mol of silver.
× 10 ^-5 mol was added. After washing with water, calcium concentration 1
80 g of lime-treated gelatin at 40 ° C.
H was adjusted to 5.8 and pAg to 8.7. The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, which was 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount of each was 1.00 × 10 ⁻³ mol, 2.15 × 10 ^−4.
The chemical sensitization was carried out in the same manner as in Em-C except that the molar amount was 8.06 × 10 ⁻⁵ mol to prepare Em-G.

(Preparation of Em-J) In the preparation of Em-B, the sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^-4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

[0171]

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[0172]

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(Preparation of Em-L) (Preparation of Silver Bromide Seed Emulsion) An average sphere-equivalent diameter of 0.6 μm, an aspect ratio of 9.0, and a bromide containing 1.16 mol of silver and 66 g of gelatin per kg of emulsion. A silver tabular emulsion was prepared. (Growth Step 1) 0.3 g of modified silicone oil was added to 1250 g of an aqueous solution containing 1.2 g of potassium bromide and succinated gelatin having a succination ratio of 98%. After adding an equivalent of 0.086 mol silver of the above silver bromide tabular emulsion, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and 5.4 mol of silver to which silver iodide fine particles having an equivalent sphere diameter of 0.037 μm were added were added. Further, at this time, the pAg of the aqueous potassium bromide solution was 8.times.
It was added while adjusting to be 1.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 mg of thiourea dioxide were added. Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous potassium bromide solution were added over 66 minutes while accelerating with a double jet. At this time, silver iodide fine particles having an equivalent sphere diameter of 0.037 μm were added in an amount of 7.0 mol based on silver to be added. At this time, the pAg is 8.
The amount of potassium bromide in the double jet was adjusted so as to be 1. After the addition was completed, 2 mg of sodium benzenethiosulfonate was added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous potassium bromide solution were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9. (Addition of poorly soluble silver halide emulsion 4) After adjusting the above host grains to 9.3 with an aqueous potassium bromide solution, 25 g of the above silver iodide fine grain emulsion having an equivalent sphere diameter of 0.037 μm was added within 20 seconds. Was added rapidly.

(Formation of outermost shell layer 5) 34.9 g of silver nitrate
Was added over 22 minutes. This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol%.

(Chemical sensitization) After washing with water, the succinization ratio was 98.
% Succinated gelatin and calcium nitrate at 40 ° C
PH, adjusted to 5.8, pAg, 8.7. The temperature was raised to 60 ° C., and a silver bromide fine grain emulsion of 0.07 μm was added to 5 × 10 ^−3.
After 20 minutes, sensitizing dyes 9, 10, and 11 were added. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added, and the mixture was optimally chemically sensitized. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization is 1/100.
The sensitizing dye and each compound were added in an amount of 10 ^-1 to 1 per mol of silver halide so that the sensitivity at the time of exposure was the highest.
It means that it was selected from the added amount range of 0 ^-8 mol.

[0178]

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[0179]

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[0180]

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[0181]

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was maintained at 70 ° C. An aqueous silver nitrate solution 27
6 mL (containing 12.0 g of silver nitrate) equimolar KB
The r aqueous solution was added by a controlled double jet addition method over 7 minutes while maintaining the pAg at 7.26.
Then, the temperature was lowered to 68 ° C., and 7.6 mL of 0.05% by mass thiourea dioxide was added. Subsequently, an aqueous solution of silver nitrate was added to 592.
9 mL (containing 108.0 g of silver nitrate) and equimolar K
A mixed aqueous solution of Br and KI (KI was 2.0 mol%) was added by a controlled double jet addition method over 18 minutes and 30 seconds while maintaining the pAg at 7.30. Also,
Five minutes before the end of the addition, 0.1% by mass of thiosulfonic acid was added to 1%.
8.0 mL was added. The obtained particles had a sphere equivalent diameter of 0.1.
The particles were cubic grains having a size of 9 μm and an average silver iodide content of 1.8 mol%. Em-O was re-dispersed by desalting and washing with a normal flocculation method, and then adjusted to pH 6.2 and pAg 7.6 at 40 ° C.

Subsequently, Em-O was subjected to the following spectral sensitization and chemical sensitization. First, sensitizing dye 10,
Each of 11.11 and 12 was 3.37 × 10
^-4 mol / mol, KBr is 8.82 × 10 ^-4 mol / mol,
Sodium thiosulfate was added at 8.83 × 10 ⁻⁵ mol / mol, potassium thiocyanate was added at 5.95 × 10 ⁻⁴ mol / mol and potassium chloroaurate was added at 3.07 × 10 ⁻⁵ mol / mol, and added at 68 ° C. Aged. The aging time is 1/1
The sensitivity of the exposure for 00 seconds was adjusted to be the highest.

[0184]

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D and H,
I and K contain optimum amounts of Ir and Fe. Emulsions M and N were subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

[0186]

[Table 4]

[0187]

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[0188]

[Table 5]

In Table 5, dislocation lines as described in JP-A-3-237450 are observed in tabular grains using a high-pressure electron microscope.

2) Support The support used in this example was prepared by the following method. 2-1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 2.66 × 10
Pa, partial pressure of water vapor in atmospheric gas 75%, discharge frequency 3
0 kHz, output 2500 W, processing intensity 0.5 kV ・ A ・
A glow discharge treatment was performed at a rate of min / m ² . On this support,
For the first layer, a coating solution having the following composition was used.
The coating was performed at a coating amount of 5 mL / m ² by using the bar coating method described in Japanese Patent Application Laid-Open No. H10-260,036. Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0. 5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 part by mass Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and heat-treated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, heat-treated and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method. Gelatin 1.01 part by mass Salicylic acid 0.30 part by mass Resorcin 0.40 part by mass Poly (polymerization degree 10) oxyethylene nonylphenyl ether 0.11 part by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-propanol 10 0.08 parts by mass Further, a second layer and a third layer described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side to form a silver halide emulsion layer. To produce a transparent magnetic recording medium.

2-2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, SBET: 39 m ^{2 /} g, Hc: 6.56 × 104 A
/ M, σs: 77.1 Am ² / kg, σr: 37.4 A
m2 / kg) 1100 parts by mass, water 220 parts by mass, and silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165
The resulting mixture was kneaded with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heated at 110 ° C. for 1 hour to produce surface-treated magnetic particles. Further, the mixture was kneaded again with an open kneader for 4 hours according to the following formulation. The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the mixture was finely dispersed at 2,000 rpm for 4 hours by a sand mill (1/4 G sand mill) according to the following formulation. As the medium, glass beads having a diameter of 1 mm were used. The above kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g

Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation. Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g And stirred to produce a “magnetic substance-containing intermediate liquid”.

Preparation of Sumicorundum AA-1.5 (Average Primary Particle Diameter 1.5 μm, Specific Surface Area 1.3 m ² / g) Particle Dispersion Preparation of α-Alumina Abrasive Dispersion of the Present Invention According to the Following Formulation did. Sumicorundum AA-1.5 152g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) 0.48g Diacetylcellulose solution 227.52g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) In, the sand mill (1 /
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used. Preparation of Colloidal Silica Particle Dispersion (Fine Particles) “MEK-ST” manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [Dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone) / Cyclohexanone = 1/1) 170 g of methyl ethyl ketone 170 g of cyclohexanone The coating solution obtained by mixing and stirring the above was applied with a wire bar so as to have an application amount of 29.3 mL / m ² . Drying is 1
Performed at 10 ° C. The thickness as a magnetic layer after drying is 1.0
μm.

2-3) Third Layer (Higher Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, and dispersed with a high-pressure homogenizer. A dispersion stock of a slip agent was prepared. Solution A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by mass n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 parts by mass Liquid Cyclohexanone 8600 parts by mass.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation. 93.54 parts by mass of isopropyl alcohol Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by mass Compound 8 2 .93 parts by mass

[0198]

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88.00 parts by mass of Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.). After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by mass of diacetone alcohol While cooling the above solution with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1 / 1) While cooling with ice and stirring, ultrasonic homogenizer “SONI”
The dispersion was performed for 2 hours using FIER450 (manufactured by BRANSON Corporation) to complete a spherical organic polymer particle dispersion c2.

Preparation of Third Layer Coating Solution A third layer coating solution was prepared by adding the following to 542 g of the above-mentioned slip agent dispersion stock solution. Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above sea hosta KEP50 dispersion [c1] 53.1 g The above spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (manufactured by 3M Corporation, solid 50%, solvent: ethyl acetate) BYK310 5.3 g (manufactured by BYK Chemi-Japan Co., Ltd., solid content 25%) 10.35 mL / m ^{2 of the} above third layer coating solution on the second layer
And dried at 110 ° C.
After a minute, it was dried.

3) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film. (Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener (specific compounds are listed below, followed by a number followed by a number, followed by a chemical formula). The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExM-1 0.066 ExC-1 0.002 ExC -3 0.002 Cpd-2 0.001 F-8 0.010 HBS-1 0.005 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 F-8 0.012 Solid disperse dye ExF-7 0.120 HBS-1 0.074

Third layer (intermediate layer) ExC-2 0.050 Cpd-1 0.090 Polyethyl acrylate latex 0.200 HBS-1 0.100 Gelatin 0.700 Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-4 0.121 ExC-5 0.010 ExC-6 0.007 ExC-8 0.050 ExC-9 0.020 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 ExC-8 0.016 ExC-9 0.005 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.129 Gelatin 1.086 6th Layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 ExC-8 0.110 ExC-9 0.020 Cpd-20 0.064 Cpd-4 0.077 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245

Seventh layer (intermediate layer) Cpd-1 0.094 Cpd-6 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886 Eighth Layer (layer giving a multilayer effect to the red sensitive layer) Em-J silver 0.293 Em-K silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExM-4 0.026 ExY-1 0.016 ExY-4 0.036 ExC-7 0.026 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 ExC-7 0.007 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470 10th layer (medium sensitivity green) Sensitive emulsion layer) Em-F silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-3 0.007 ExC-6 0.010 ExC-7 0.012 ExC-8 0.010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446

Eleventh Layer (High Sensitive Green Sensitive Emulsion Layer) Em-E Silver 0.794 ExC-6 0.002 ExC-8 0.010 ExM-1 0.013 ExM-2 0.011 ExM-30 030 ExM-4 0.017 ExY-3 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939 12th layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-6 0.010 HBS-1 049 gelatin 0.630

13th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExC-7 0.013 ExY-1 0.002 ExY-2 0.890 ExY-4 0.058 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058 14th layer (high sensitivity blue Emulsion-sensitive layer) Em-L silver 0.714 ExY-2 0.211 ExY-4 0.068 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 Gelatin 0.678

Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984 16th layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) ) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S-1 0.200 Gelatin 0.750

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17 and lead salts, platinum salts, iridium salts, and rhodium salts. Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method. ExF-2 wet cake (containing 17.6 wt% water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31 wt% aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg water 4 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, the peripheral speed was 10 m / min using an agitator mill LMK-4.
s, a discharge rate of 0.6 kg / min, a filling rate of zirconia beads having a diameter of 0.3 mm of 80%, and an absorbance ratio of the dispersion of 0.29.
To obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm. Similarly, E
A solid dispersion of xF-4 and ExF-7 was obtained. The average particle diameter of the fine dye particles is 0.28 μm and 0.49 μm, respectively.
m. ExF-5 is disclosed in European Patent No. 549,489A.
Microprecipitation described in Example 1 of
It was dispersed by a dispersion method. The average particle size was 0.06 μm. The compounds used for each layer are shown below.

[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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The above silver halide color photographic light-sensitive material was designated as Sample N-1. Sample N-1 was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

(3) Development Processing Continuous processing was carried out using a minilab film processor FP363SC manufactured by Fuji Photo Film Co., Ltd. until the color developing replenisher used in the following processing step became 0.5 times the color developing tank capacity ( Running test).

Processing Step Temperature Time Replenishment Amount Tank Capacity Color Development 38.0 ° C. 3 minutes 5 seconds 15 mL 10.3 L Bleaching 38.0 ° C. 50 seconds 5 mL 3.6 mL Fixing (1) 38.0 ° C. 50 seconds-3.6 mL Fixing (2) 38.0 ° C 50 seconds 7.5 mL 3.6 mL Stable (1) 38.0 ° C 20 seconds-1.9 mL Stable (2) 38.0 ° C 20 seconds-1.9 mL Stable (3) 38. 0 ° C 20 seconds 30mL 1.9mL Drying 60 ° C 1 minute 30 seconds * Replenishment amount per 35mm width 1.1m of photosensitive material (equivalent to 24Ex. 1 bottle) Stabilizing solution is (3) → (2) → (1) It is a countercurrent method,
The fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 mL of the tank liquid of the stabilizing solution (2) is supplied to the fixing solution (2), corresponding to a replenishing amount of 15 mL. Further, the color developing solution is replenished by dividing the replenishing solution of the color developing solution (A) and the replenishing solution of the color developing solution (B) having the following formulas into 12 mL and 3 mL, respectively, corresponding to the replenishment amount, to a total of 15 mL. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 mL per 1.1 m width of 35 mm photosensitive material.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process.

[Color developing solution A] [Tank solution] [Replenisher] Water 800 mL 800 mL Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Di Sodium-N, N-bis (sulfonatoethyl) hydroxylamine 10.0 g 15.0 g Sodium sulfite 4.0 g 9.0 g Potassium bromide 1.4 g-Diethylene glycol 10.0 g 17.0 g Ethylene urea 3.0 g 5.5 g 2 -Methyl-4- [N-ethyl-N- (β-hydroxyethyl)] aniline sulfate 4.7 g 11.0 g Potassium carbonate 39.0 g 59.0 g Water was added and the total amount was 1000 mL 1000 mL pH (25 ° C., sulfuric acid (Adjust with KOH) 10.05 10.50 The above tank liquid is as follows The composition of the liquid B) during mixing (color developing solution A).

[Color developing solution B] [Tank solution] [Replenisher] Hydroxylamine sulfate 2.0 g 4.0 g Water is added to the total amount 1000 mL 1000 mL pH (adjusted at 25 ° C., sulfuric acid and KOH) 10.05 4. 0 The above-mentioned tank liquid shows the composition of (color developing solution B) at the time of mixing the above (color developing solution A).

[Bleaching solution] [Tank solution] [Replenisher] Water 800 mL 800 mL 1,3-Diaminopropanetetraacetic acid ferric ammonium salt-water salt 120 g 180 g Ammonium bromide 50.0 g 70.0 g Succinic acid 30.0 g 50.0 g Maleic acid 40.0 g 60.0 g Imidazole 20.0 g 30.0 g Water is added to the total volume 1000 mL 1000 mL pH (25 ° C., adjusted with aqueous ammonia and nitric acid) 4.60 4.00

[Fixing solution] [Tank solution] Compound of the present invention 2 mmol Ammonium thiosulfate (750 g / L) 280 mL Aqueous ammonium bisulfite solution (72%) 20.0 g Imidazole 35.0 g Ethylenediaminetetraacetic acid 8.0 g 1,000 mL pH (adjusted at 25 ° C. with ammonia water and nitric acid) 7.00 As the fixing replenisher, a solution prepared by diluting the fixing composition prepared in (1) with water 1.2 times was used.

[Stabilizer] [Common to tank and replenisher] Water 800 mL Sodium p-toluenesulfinate 0.03 g p-Nonylphenylpolyglycidol (glycidol average polymerization degree 10) 0.40 g Disodium ethylenediaminetetraacetate 0. 05g 1,2,4-triazole 1.3g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75g 1,2-benzoisothiazolin-3-one 0.10g Water was added. Total volume 1000 mL pH (adjusted at 25 ° C with ammonia water and nitric acid) 7.00

(4) Evaluation Stability against precipitation The same evaluation as in Example 1 was performed. Photographic Characteristics in Color Negative Film Processing Unexposed photosensitive material sample N-1 was developed, transmission absorption spectrum was measured using a U-3500 type spectrophotometer manufactured by Hitachi, Ltd., and absorbance at 540 nm was measured. Was _designated as DG. Next, the sample 29 without the added compound was washed with distilled water at 30 ° C. for 3 minutes, dried, and subjected to the same measurement. The absorbance at 540 nm was defined as D _G0 . Seeking [Delta] D _G based on the following equation, to evaluate the stain caused by residual sensitizing dye. ΔD _G = D _G - D _G0 results

[0231]

[Table 6]

Sample 3 Using Compounds FL-2 and FL-3
-2 and 3-3 (Comparative Examples) are effective in reducing the stain caused by the residual sensitizing dye, but all precipitate with the aging of the processing composition. In Sample 3-1 (Comparative Example), no precipitation occurs, and thus precipitation is caused by the added compound. The photosensitive material that has been subjected to development processing using the processing composition of the present invention is effective in reducing stain caused by the residual sensitizing dye,
And even if the treatment composition is aged for 4 weeks, it is completely transparent at room temperature,
Even at low temperatures (−5 ° C.), they are completely transparent or turbid, and do not cause precipitation. Thus, even when the present invention is a fixing composition, the composition is excellent in the effect of reducing stain caused by the residual sensitizing dye of the light-sensitive material, and does not generate precipitates when the processing composition is stored at a low temperature. It was shown that.

Example 4 (1) Preparation of Color Developing Composition Water 800 mL Compound of the Invention See Table 4 9.0 g of diethylenetriaminepentaacetic acid 9.0 g of sodium 4,5-dihydroxybenzene-1,3-disulfonate 8.0 g of disodium- N, N-bis (sulfonatoethyl) hydroxylamine 12.0 g Sodium sulfite 14.0 g Diethylene glycol 22.5 g Ethylene urea 7.5 g 4-Amino-3-methyl- [N-ethyl-N- (β-hydroxyethyl)] aniline Sulfate 15.0 g Potassium carbonate 100 g Water is added to the total volume 1000 mL pH (25 ° C., adjusted with sulfuric acid and KOH) 12.25

(2) Photosensitive Material The same sample as in Example 3 was used. (3) Developing process Minilab film processor FP36 manufactured by Fuji Photo Film Co., Ltd.
The color developing replenisher used in the following processing steps was used in an experimental processing apparatus modified from 3SC to reduce the capacity of the color developing tank to 0.
The continuous processing (running test) was performed until the value became 5 times.

Processing Step Temperature Time Replenishment Amount Tank Capacity Color Development 41.0 ° C 2,000 seconds 12mL 10.3L Bleaching 41.0 ° C 20 seconds 5mL 3.6mL Fixing (1) 41.0 ° C 20 seconds-3.6mL Fixing (2) 41.0 ° C 20 seconds 7.5 mL 3.6 mL Stable (1) 41.0 ° C 130 seconds-1.9 mL Stable (2) 41.0 ° C 13 seconds-1.9 mL Stable (3) 41. 0 ° C for 14 seconds 25mL 1.9mL Drying 60 ° C for 30 seconds * Replenishment amount is 35mm of photosensitive material per 1.1m width (equivalent to 24Ex. 1 bottle). Stabilizing solution is (3) → (2) → (1) Method
The fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 mL of the tank liquid of the stabilizing solution (2) is supplied to the fixing solution (2), corresponding to a replenishing amount of 15 mL. Further, the color developing solution is replenished by dividing the replenishing solution of the color developing solution (A) and the replenishing solution of the color developing solution (B) having the following formulas into 12 mL and 3 mL, respectively, corresponding to the replenishment amount, to a total of 15 mL. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 mL per 1.1 m width of 35 mm photosensitive material.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process.

[Color developing solution A] [Tank solution] Water 800 mL Compound of the present invention 4 mmol Diethylenetriaminepentaacetic acid 2.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.4 g Disodium-N, N- Bis (sulfonate ethyl) hydroxylamine 10.0 g Sodium sulfite 4.0 g Potassium bromide 1.4 g Diethylene glycol 10.0 g Ethylene urea 3.0 g 4-Amino-3-methyl- [N-ethyl-N- (β-hydroxyethyl) ] Aniline sulfate 5.7 g Potassium carbonate 39.0 g Water was added to make the total volume 1000 mL pH (adjusted at 25 ° C with sulfuric acid and KOH) 10.10 The above tank solution was mixed with the following (color developer B) (color developer B) The composition of A) is shown.

As the replenisher for the color developing solution A, a solution obtained by diluting the color developing composition prepared in (1) 2.1 times with water was used. [Color developing solution B] [Tank solution] [Replenisher] Hydroxylamine sulfate 2.0 g 4.0 g Water is added to the total amount 1000 mL 1000 mL pH (25 ° C., adjusted with sulfuric acid and KOH) 10.10 4.0

[Bleaching solution] [Tank solution] [Replenisher] Water 800 mL 800 mL 1,3-diaminopropanetetraacetic acid ferric ammonium salt-water salt 150 g 200 g Ammonium bromide 50.0 g 70.0 g Succinic acid 50.0 g 80.0 g Imidazole 50.0 g 80.0 g Water is added to the total amount 1000 mL 1000 mL pH (25 ° C., adjusted with aqueous ammonia and nitric acid) 4.20 3.80

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate (750 g / L) 280 mL 745 mL Aqueous ammonium bisulfite solution (72%) 20.0 g 80.0 g Imidazole 12.0 g 35.0 g 1-Mercapto-2 -(N, N-dimethylaminoethyl) tetrazole 0.6 g 1.8 g Ethylenediaminetetraacetic acid 3.0 g 9.0 g Water was added to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with ammonia water and nitric acid) 7.00 7.0. 00

[Stabilizer] [Common to tank solution and replenisher] Water 800 mL Sodium p-toluenesulfinate 0.03 g p-Nonylphenyl polyglycidol (glycidol average polymerization degree 10) 0.40 g Ethylenediaminetetraacetic acid disodium salt 05g 1,2,4-triazole 1.3g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75g 1,2-benzoisothiazolin-3-one 0.10g Water was added. Total volume 1000 mL pH (adjusted at 25 ° C with ammonia water and nitric acid) 7.00

(4) Evaluation Stability against precipitation The same evaluation as in Example 1 was performed. Photographic properties in color negative film processing The unexposed sample (photosensitive material sample N-1) was subjected to development processing, and the transmission absorption spectrum was measured using a U-3500 type spectrophotometer manufactured by Hitachi, Ltd. the absorbance of 540nm was D _G. Next, the sample 37 without the added compound was heated at 30 ° C.
Of distilled water and washed with water for 3 minutes using a performs the same measurement after drying, the absorbance of 540nm in this case was D _G0. ΔD _G0 was determined based on the following formula, and the stain resulting from the residual sensitizing dye was evaluated. ΔD _G = D _G - D _G0 results

[0242]

[Table 7]

Sample 4 Using Compounds FL-2 and FL-3
-2 and 4-3 (Comparative Examples) are effective in reducing the stain caused by the residual sensitizing dye, but both precipitate with the aging of the processing composition. In Sample 4-1 (Comparative Example), no precipitation occurs, and thus precipitation is caused by the added compound. The photosensitive material that has been subjected to development processing using the processing composition of the present invention is effective in reducing stain caused by the residual sensitizing dye,
And even if the treatment composition is aged for 4 weeks, it is completely transparent at room temperature,
Even at low temperatures (−5 ° C.), they are completely transparent or turbid, and do not cause precipitation. Thus, when a color negative film having a reduced processing time is processed using the color developing composition of the present invention, it is excellent in the effect of reducing the stain caused by the residual sensitizing dye of the light-sensitive material, and at a low temperature of the processing composition. It was shown that the composition did not produce a precipitate during storage.

Example 5 (1) Preparation of additive composition An additive composition for adding a fixing solution was prepared as shown in Table 8.

[0245]

[Table 8] * In Table 8, DEG indicates diethylene glycol.

[0246]

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(2) Photosensitive Material Sample A commercially available color reversal film shown below was used. Sample A: Fuji Photo Film, Fujichrome Provia (Serial No. 156004) Sample B: Eastman Kodak, Ektachrome
E-100S (Production number 1411)

(1) Developing Process The above photosensitive material sample which was gray-exposed to an average density was subjected to a continuous process (running test) until the first black and white developer reached 0.5 round in the following processing steps. Sample A and Sample B
Was used in a ratio of 4: 1. The development processing was performed by a method of transporting the sample by hanging it on a hanger. Processing Step Temperature Time Tank capacity Replenishment amount * First black and white development 38.0 ° C 6 minutes 12L 2200mL First water washing 38.0 ° C 2 minutes 4L 7500mL Inversion 38.0 ° C 2 minutes 4L 1100mL Color development 38.0 ° C 6 minutes 12L 2200 mL Pre-bleach 38.0 ° C. 2 minutes 4 L 1100 mL Bleaching 38.0 ° C. 6 minutes 2 L 220 mL Fixing 38.0 ° C. 4 minutes 8 L 1100 mL Second water wash 38.0 ° C. 6 minutes 8 L 7500 mL Final rinse 25.0 ° C. 1 minute 2 L 1100 mL (Note) * replenishment amount per photosensitive material 1m ²

The composition of each processing solution was as follows. [First black and white developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Thiocyanic acid Potassium 1.2g 1.2g Potassium iodide 2.0mg-Diethylene glycol 13g 15g Water is added and the total amount is 1000mL 1000mL pH (25 ° C, adjusted with sulfuric acid and KOH) 9.60 9.60

[Inversion liquid] [Tank liquid] [Replenishment liquid] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p -Amino phenol 0.1 g Sodium hydroxide 8 g Propionic acid 15 mL Water is added to the total volume 1000 mL pH (adjusted at 25 ° C with acetic acid and KOH) 6.00

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate -12-hydrate salt 36 g 36 g sodium bromide 0.7 g-potassium iodide 40 mg-sodium hydroxide 3.0 g 3.0 g citrazic acid 0.5 g 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3 -Methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Water was added and the total amount was 1000mL 1000mL pH (25 ° C, sulfuric acid and KOH Adjustment) 11.80 12.00

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Sodium formaldehyde sodium bisulfite adduct 20 g 25 g Methanol 2 g 2 g Water is added to the total volume 1000 mL 1000 mL pH (25 ° C., adjusted with acetic acid and NaOH) 6.30 6.10

[Bleaching Solution] [Tank Solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g bromide Potassium 100g 200g Ammonium nitrate 10g 20g Water is added to the total amount 1000mL 1000mL pH (25 ° C, adjusted with nitric acid and NaOH) 5.70 5.50

[Fixing solution] [Tank solution] [Replenisher] Same as the additive composition in Table 8 or no addition 1 mL tank solution 80 g of ammonium thiosulfate 5.0 g of sodium sulfite 5.0 g of sodium bisulfite 5.0 g pH (adjusted at 25 ° C with acetic acid and aqueous ammonia) 6.60

[Stabilizing solution] [Tank solution] [Refill solution] 2-Benzoisothiazolone-3-one 0.02 g Same as tank solution Dipropylene glycol 0.3 g Organosilicon surfactant 0.2 g Water is added to the total volume 1000 mL pH (25 ° C) 7.0

(4) Evaluation Stability against Precipitation Precipitation The same evaluation as in Example 1 was performed only at -5 ° C. Sample 5
-1, 5-2 were not evaluated because they become suspensions during preparation. Photographic properties in color reversal film processing 1 mL of the additive composition was added to 1 L of the tank solution and 1 L of the replenisher in the fixing process, and the solution was continuously processed. Conduct,
The transmission absorption spectrum was measured by U-35 manufactured by Hitachi, Ltd.
It measured using the 00 type spectrophotometer. 570 of the sample
The absorbance at nm was D _G. Next, after continuous processing was performed using a non-added fixing solution, similar development processing and absorption spectrum measurement were performed. 5 of the photosensitive material sample at this time
ΔD _G was determined based on the following equation, with the absorbance at 70 nm being D _G0 , and the stain reducing effect of the fixer additive composition due to the residual sensitizing dye was evaluated. ΔD _G = D _G - D _G0 then after continuous processing is completed, after the treatment step was stopped 60 hours,
The same absorption spectrum was measured using the photosensitive material obtained by performing the developing process again, and the stain reducing effect was evaluated.

[0257]

[Table 9]

In Table 8, when Compound FL-6 was used, the solubility of the compound was low, and in order to obtain a uniform composition, as in Sample 5-3 (Comparative Example), 100 equivalents or more of diethylene glycol was used as a dissolution aid. Had to be used. The compounds of the present invention can provide a homogeneous additive composition without the use of a solubilizing agent, and the composition is stable when stored at low temperatures and does not produce precipitated precipitates.

As shown in Table 9, when the sample 5-3 (Comparative Example) was used, if the continuous processing was stopped for a certain period of time and the processing was restarted, the stain reducing effect was reduced. On the other hand, the additive composition of the present invention can exhibit stable photographic performance in which the minimum density does not fluctuate without reducing the stain reducing effect even after the continuous processing is stopped and restarted.

[0260]

According to the present invention, by using the processing composition of the present invention containing a bistriazinyl arylenediamine derivative for development processing, the residual color of the residual sensitizing dye can be obtained not only in normal processing but also in rapid processing. It is possible to keep the stain in the highlights at a low level and the compound has a high solubility in the composition. . When this compound is used in combination with a fluorescent whitening agent, the fluorescent whitening effect and the coloring stain prevention effect can be independently controlled. The above effects are observed not only when this compound is added to a color developing composition, but also when it is used in other processing compositions such as a fixing composition and a bleaching composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/42 G03C 7/42 11/00 11/00 501 501 (72) Inventor Katsushi Ogiyama Minamiashigara, Kanagawa 210 Nakanuma Fuji Photo Film Co., Ltd. F-term (reference) 2H016 AE00 AF00 AF01 AF04 BK03 BL01 BL02 BL03 BL04 BL05

Claims (3)

[Claims] (1) A compound represented by the following general formula (I):
For silver halide photographic materials characterized by containing
Treatment composition. General formula (I)Where R¹¹, R¹², R¹³, R¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And
And R^{twenty four}Represents a hydrogen atom, an alkyl group, an aryl group or
L represents a phenylene group or a naphthylene group
And R¹¹And R¹²And / or R¹³And R¹⁴When,
And / or R^{twenty one}And R^{twenty two}And / or R^{twenty three}And R^{twenty four}And
It may combine with each other to form a ring. However, in the molecule-
SO_ThreeM, -CO_TwoA group represented by M or -OH
Contains at least one, where M is a hydrogen atom, an alkali gold
Genus, alkaline earth metal, ammonium or pyridinium
Represents a system. Also, R¹¹, R¹², R¹³, R¹⁴, R^{twenty one}, R
^{twenty two}, R ^{twenty three}And R^{twenty four}At least three are aryl groups
And R¹¹, R¹², R¹³And R¹⁴Less of
One and R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}At least one of
The two do not combine with each other to form a ring. Further above
In the molecule of the above formula, a group represented by -N = N- is contained.
do not do. 2. An image forming method comprising using the processing composition for a silver halide photographic light-sensitive material according to claim 1. 3. A compound represented by the following general formula (I). General formula (I)Where R¹¹, R¹², R¹³, R¹⁴, R^{twenty one}, R^{twenty two}, R^{twenty three}And
And R^{twenty four}Represents a hydrogen atom, an alkyl group, an aryl group or
L represents a phenylene group or a naphthylene group
And R¹¹And R¹²And / or R¹³And R¹⁴When,
And / or R^{twenty one}And R^{twenty two}And / or R^{twenty three}And R^{twenty four}And
It may combine with each other to form a ring. However, in the molecule-
SO_ThreeM, -CO_TwoA group represented by M or -OH
Contains at least one, where M is a hydrogen atom, an alkali gold
Genus, alkaline earth metal, ammonium or pyridinium
Represents a system. Also, R¹¹, R¹², R¹³, R¹⁴, R^{twenty one}, R
^{twenty two}, R ^{twenty three}And R^{twenty four}At least three are aryl groups
And R¹¹, R¹², R¹³And R¹⁴Less of
One and R^{twenty one}, R^{twenty two}, R^{twenty three}And R^{twenty four}At least one of
The two do not combine with each other to form a ring. Further above
In the molecule of the above formula, a group represented by -N = N- is contained.
do not do.