JP2002323741A - Stabilizing solution for silver halide color photographic sensitive material and processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizing solution for a silver halide color photographic sensitive material which suppresses head clogging, generates little scum and ensures little stain of a silver halide color photographic sensitive material even in processing under low replenishment and to provide a processing method for a silver halide color photographic sensitive material. SOLUTION: The stabilizing solution contains a compound of the formula RO(AO)n (BO)m H and at least one compound selected from the formula (2)-(5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stable silver halide color photographic light-sensitive material in which head clog is hardly generated, scum is less generated, and the residual dye is improved in the silver halide color photographic light-sensitive material. The present invention relates to a method for processing a liquid and a silver halide color photographic material.

[0002]

2. Description of the Related Art Processing of a silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) basically comprises two steps of a color development step and a desilvering step, and the desilvering step is a bleaching step and a fixing step. Alternatively, the process comprises a bleach-fixing step, followed by a stabilizing step, a washing step, and the like for the purpose of washing out and cleaning the fixing agent and the bleaching agent from the photosensitive material.

[0003] In recent years, from the viewpoint of global environment protection and effective use of resources, a method of performing a low replenishment amount processing of a photographic processing solution has been performed for each processing step. For the stabilizer,
For example, JP-A-5-232660 and JP-A-5-232660
Techniques have been studied which make it possible to reduce the replenishment of the stabilizing solution by using a specific compound as described in the specification of 19435 and the like.

In recent years, a transparent magnetic layer is provided on the back surface of a photosensitive material such as a color negative film to record and use information such as type information of the photosensitive material, maker information, customer information, print condition information and photographing condition information. A for performing development processing and color printing more efficiently or with high accuracy
A system called an advanced photo system (PS) has begun to be widely used. As a photosensitive material used in the APS, for example, US Pat.
7,196 and WO 90/04245.
As described in the specification, a method of providing a magnetic layer containing magnetic particles capable of magnetic recording on the back surface of a photosensitive material may be mentioned.

When a photosensitive material having such a magnetic layer on the back surface is developed, a magnetic head called head clog is stained and a problem which hinders reading of magnetic information is likely to occur. A technique of adding a surfactant having a specific structure therein is disclosed in, for example,
As disclosed in the specification of Japanese Patent No. 281677, it has been found that when a low replenishment treatment is performed, only some of the surfactants of the compounds disclosed in the specification exert this effect.

Further, when the replenishment of the stabilizing solution is carried out, a problem that scum tends to be generated in the stabilizing solution and a dye residue such as a sensitizing dye used in a photographic material (also referred to as a dye stain) are generated. It turned out that there was also a problem that became easier. In particular, when the stabilizing solution treatment process is rapidly performed, these problems have become more prominent and have been at a level that cannot be solved by conventional techniques. Regarding these additional effects, see the above-mentioned JP-A-9-281.
No. 677, the stabilizing solution for silver halide color photographic light-sensitive material and the processing method of silver halide color photographic light-sensitive material provided in the present application can simultaneously achieve these effects. It becomes possible.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and a first object of the present invention is to provide a silver halide color photographic light-sensitive photosensitive material in which a head clog hardly occurs even when low replenishment processing is performed. A second object is to provide a stabilizing solution for a silver halide color photographic light-sensitive material and a stabilizer for the silver halide color photographic light-sensitive material with less scum. An object of the present invention is to provide a method for treating a material. A third object is to provide a stabilizing solution for a silver halide color photographic light-sensitive material in which a sensitizing dye or the like of the processed silver halide color photographic light-sensitive material is small and a method for processing a silver halide color photographic light-sensitive material. On offer. Other objects of the present invention will become apparent from the following description.

[0008]

The above object of the present invention has been attained by the following constitutions.

1. A stabilizer for a silver halide color photographic light-sensitive material, comprising a compound represented by the general formula (1) and at least one compound selected from the general formulas (2) to (5). .

[0010] 2. A stabilizer for a silver halide color photographic light-sensitive material contains a compound represented by the general formula (1) and at least one compound selected from the general formulas (6) to (8); Replenishment amount of stabilizer is 150-800
ml / m ² , a method for processing a silver halide color photographic light-sensitive material.

3. In a method for processing a silver halide color photographic light-sensitive material, in which processing is performed in a stabilizing solution tank after a processing tank having a fixing ability, the stabilizing solution in the stabilizing solution tank contains a compound represented by the general formula (1). And a method of processing a silver halide color photographic light-sensitive material, wherein a part or all of the overflow of the stabilizing solution is added to a processing tank having the immediately preceding fixing ability.

4. In a method for processing a silver halide color photographic light-sensitive material, in which processing is performed in a stabilizing solution tank after a processing tank having a fixing ability, the stabilizing solution in the stabilizing solution tank contains a compound represented by the general formula (1). And a method for processing a silver halide color photographic light-sensitive material, wherein 0 to 50 mol% of all cations in the processing solution having the fixing ability is ammonium.

5. The stabilizer is represented by the general formula (6)
5. The method for processing a silver halide color photographic light-sensitive material according to the above item 3 or 4, comprising at least one compound selected from (8).

6. The stabilizer is represented by the general formula (2)
(5) The method for processing a silver halide color photographic light-sensitive material as described in (3) or (4) above, which comprises at least one compound selected from (5).

Hereinafter, the present invention will be described in detail. The present invention is characterized in that the stabilizer contains the compound represented by the general formula (1).

The details of the compound represented by formula (1) will be described below. In the general formula (1),
R represents 5 carbon atoms which may have a saturated or unsaturated substituent;
And A and B each represent an optionally substituted alkylene group having 2 or 3 carbon atoms. n and m each represent 0 or an integer of 4-33, and n and m are not 0 at the same time.

In the general formula (1), R is preferably an alkyl group having 10 to 20 carbon atoms, and examples of the substituent include a hydroxyl group and a carboxyl group. Further, n and m are preferably such that m is 0 and n is an integer of 6 to 25.

Hereinafter, specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0019]

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The invention according to claims 1 and 6 is characterized in that the stabilizing solution contains at least one compound selected from the general formulas (2) to (5).

Hereinafter, the compounds represented by formulas (2) to (5) will be described. In the above general formula (2), carbon number 2 to 6 represented by X
An alkylene group having 1 to 5 carbon atoms represented by B ¹ and B ²
May be a linear alkylene group or a branched alkylene group, and includes those having a substituent. Examples of the substituent include an OH group. In the general formula (5), a divalent aliphatic group represented by X ₁ and X ₂ , a divalent aromatic group or a divalent linking group composed of an aliphatic group and an aromatic group is substituted. Those having a group are also included, and examples of the substituent include a carboxyl group and a pyridyl group.

Hereinafter, specific examples of the compounds represented by formulas (2) to (5) are shown below, but the present invention is not limited thereto.

[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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In the above compounds, potassium salts, sodium salts and ammonium salts may be used.

Among these, preferred compounds are exemplified compounds 2-1, 2-3, 3-2, 4-4, 5-1, and 5
-4, and particularly preferably Exemplified Compound 2-1.

The compound represented by the general formula (2) of the present invention includes optical isomers [R, R], [S, S], [S, R] and [R, S]. For example, Exemplified Compound 2-1 has three optical isomers [R, R], [S, S] and [S, R], which may be used individually or as a mixture. Good. However, in the present invention, the [S, S] form is preferably used.

The compound represented by the general formula (5) is
h. Obshch. Khim. 49,659 (197
9), and can be synthesized by a generally known method described in JP-A-6-95319.

The invention according to claims 2 and 5 is characterized in that the stabilizing solution contains at least one compound selected from the general formulas (6) to (8).

First, the general formula (6) will be described in detail. In the general formula (6), A _{1 to} A ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, or a pyridyl group. m represents 0 or 1.

Examples of the salt of the compound represented by the general formula (6) include an inorganic acid salt such as hydrochloride, sulfate and nitrate; an organic acid salt such as phenol salt; a double salt or complex salt with a metal salt; And internal salts.

The compound represented by the general formula (6) is specifically described in Beilsteins: Beilsteins Hanmie (Beilsteins Han).
dbuch der Organishen Chem
ie, the compounds described in the second supplement, volume 26, pp. 200-212. Among them, those soluble in water are preferred in the present invention. The following are representative examples.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The amount of the compound represented by the general formula (6) is preferably 0.1 to 20 g per liter of the stabilizing solution.

Next, the compound represented by formula (7) will be described. In the general formula (7), Z ₄ represents a group of atoms necessary to form a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocyclic ring. It may be a ring, and preferably, Z ₄ is an aromatic carbocyclic or heterocyclic ring having a substituent. The substituent of Z ₄ is an aldehyde group,
A hydroxyl group, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), a halogen atom,
Nitro group, sulfo group, carboxy group, amino group (for example, N, N-dimethylamino, N-ethylamino, N-
Phenylamino, etc.), hydroxyalkyl group, aryl group (eg, phenyl, p-methoxyphenyl, etc.), cyano group, aryloxy group (eg, phenoxy, p-
Carboxyphenyl), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (for example,
N-ethylsulfamoyl, N, N-dimethylsulfamoyl and the like), carbamoyl group (for example, carbamoyl,
It is preferably N-methylcarbamoyl, N, N-tetramethylenecarbamoyl and the like or a sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and the like).

The carbon ring represented by Z ₄ is preferably a benzene ring, and the hetero ring represented by Z ₄ is preferably a 5- or 6-membered heterocyclic ring.
The membered ring includes thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimide, triazole, tetrazole and the like, and the six-membered ring includes pyridine, pyrimidine, triazine, thiadiazine and the like.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole, quinoline and the like.

Preferred examples of the compound represented by the general formula (7) are shown below, but the present invention is not limited thereto.

[0049]

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The exemplified compounds 7-1 to 7-77 are obtained by inserting various substituents into 1 to 6 in the above structure as shown below.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Among the specific examples of the compound represented by the general formula (7), more preferred compounds are exemplified compounds 7-2, 7-3, 7-4, 7-6, 7-23, and 7-2.
4, 7-52, and most preferably Exemplified Compound 7-3.

The compound represented by the general formula (7) can be easily obtained as a commercial product. The addition amount of the compound represented by the general formula (7) is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, per liter of the stabilizing solution.
Particularly preferably, it is in the range of 0.5 to 10 g.

Next, details of the compound represented by formula (8) will be described below. Among the N-methylol compounds represented by the general formula (8), the following general formula (8a)
Is more preferable.

[0059]

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Wherein Za is -N =, -CH = or -C
(R ₂ ) =. R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a nitro group, a cyano group, a sulfo group, a carboxyl group, a phospho group ,
Represents an acyl group, a sulfonyl group, a sulfinyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an amino group, or -YRa. Here, -Y represents -O- or -S-, and Ra represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. These groups may be further substituted with a similar group, a hydroxy group, or the like. R ₁ and R ₂ or R ₂ and R ₃ may be bonded to each other to form a 5- to 7-membered ring.

In general formula (8a), R ₁ ,
R ₂ and R ₃ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, n-propyl, butyl, cyclopropyl, hydroxymethyl, methoxymethyl), an alkenyl group (eg, allyl), an aryl group (eg, phenyl) , 4-tert-butylphenyl), a heterocyclic group (eg, 5-pyrazolyl, 4-pyrazolyl), a halogen atom (eg, chlorine, bromine, fluorine), a nitro group, a cyano group, a sulfo group, a carboxyl group, a phospho group An acyl group (eg, acetyl, benzoyl, propanoyl), a sulfonyl group (eg, methanesulfonyl, octanesulfonyl, toluenesulfonyl), a sulfinyl group (eg, methanesulfinyl), an acyloxy group (eg,
Acetoxy), an alkoxycarbonyl group (eg, methoxycarbonyl, butoxycarbonyl), a carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl), a sulfamoyl group (eg, sulfamoyl, N
-Ethylsulfamoyl), an amino group (eg, amino, diethylamino, acetylamino, methanesulfonamino, methylureido, N-methylsulfamoylamino, methoxycarbonylamino), an alkoxy group (eg, methoxy, ethoxy), alkylthio Group (e.g., methylthio, octylthio), aryloxy group (e.g., phenoxy), arylthio group (e.g., phenylthio), heterocyclic oxy group (e.g., 1-phenyltetrazol-5-oxy), heterocyclic thio group ((e.g., , Benzothiazolylthio).

In the general formula (8a), R ₁ , R ₂ and R ₃
Is preferably a hydrogen atom, an alkyl group, an alkenyl group, a halogen atom, a sulfo group, a carboxyl group, an acyloxy group, an amino group, an alkoxy group and an alkylthio group, respectively, a hydrogen atom, an alkyl group, a halogen atom, an acyloxy group, an amino group, an alkoxy group. Groups and alkylthio groups are more preferred, and hydrogen atoms, alkyl groups, amino groups, alkoxy groups and alkylthio groups are even more preferred. In particular, in the general formula (8a), R ₁ , R ₂ and R ₃ are selected from the viewpoints of thermal fading of a cyan image or prevention of yellow stain.
A hydrogen atom or an unsubstituted alkyl group having 1 to 3 carbon atoms is preferred. More preferably, at _{least one} of R ₁ , R ₂ and R ₃ is a methyl group, and the other is a compound having a hydrogen atom. Preferably, all are compounds of a hydrogen atom.

Hereinafter, specific examples of the compound represented by formula (8) will be shown, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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The compound represented by the general formula (8) can be easily synthesized by reacting an amine compound such as pyrazole, 1,2,4-triazole or a derivative thereof with formaldehyde or paraformaldehyde. These synthesis methods include, for example, U.S. Pat. No. 2,883,392 and Chem. ber. , 85,8
20 ('52), J. Am. Org. Chem. , 15,12
85 ('50), EP 60,222, Kh
im. Geterotsikl. Soedin. ,
(2), 251 ('80) [Chemical Abst
tracts, 93: 46530W]. On the other hand, pyrazole derivatives are available from The Chemistry of Hetero.
R. cyclic Compounds, Vol. H. Wiley "Pyrazoles, Pyraz
olines, Pyrazolidines, Inda
zolesand Condensed Ring ”,
INTERSCIENCE PUBLISHERS ('
67) or a method analogous thereto.

The replenishment rate of the stabilizer according to claim 2 of the present invention is characterized in that it is used in the range of 150 to 800 ml / m ² , but the effect of the present invention is more remarkably exhibited.
The range is from 00 to 600 ml / m ² .

The replenishment amount of the stabilizing solution in the present invention refers to the total replenishment amount of the processing solution after the processing solution having a fixing ability such as a fixing solution or a bleach-fixing solution. Also included are those that are bistable and separated into two types. Further, the stabilizing solution of the present application includes a solution that replenishes only water, and is sometimes referred to as a rinse name.

The stabilizing solution treatment tank according to the present invention may be a single tank, but the number of tanks can be increased up to a range of 2 to 10 tanks. Increasing the number of tanks makes it possible to reduce the replenishment amount of the stabilizing solution. However, considering the compactness of the automatic developing machine, the range of 2 to 6 tanks is preferably used. Also, the stable replenisher may be replenished in several places,
Preferably, in view of the processing flow of the photosensitive material, replenishment is carried out in a later tank and its overflow (when the tanks are connected by a pipe located below the liquid level, when the processing liquid passes through the pipe, or when one end overflows) It is preferable to adopt a type in which a liquid is stored in a small storage tank, and a liquid that flows into the immediately preceding tank with a bellows pump or the like is flowed into the tank in front of the tank, that is, a counter current method (multistage countercurrent method). The method is included in one of them. The most preferable mode is a system in which a stable replenisher is replenished to the last tank with 2 to 4 stabilizer liquid tanks, and the overflow liquid is sequentially transferred to the previous tank and poured.

Further, in the invention according to claim 3,
It is characterized in that part or all of the stable liquid pumped out of the stable liquid tank is introduced into the processing liquid having the fixing ability immediately before, and is preferable from the viewpoint of the effects of the present invention and from the viewpoint of reducing the amount of waste liquid.

According to a fourth aspect of the present invention, in the method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed in a stabilizing solution tank after the processing tank having a fixing ability, the stabilizing solution is represented by the general formula (1). Is characterized in that 0 to 50 mol% of all cations in the processing solution containing the compound represented by the formula (1) and having a fixing ability are ammonium. Express. In particular, 0 to 2 of all cations in a processing solution having a fixing ability
The effect of the present invention is particularly preferably exhibited when 0 mol% is ammonium.

Further, in the treatment method according to claim 3 or 4, the stabilizing solution is characterized by containing at least one compound selected from the general formulas (6) to (8). Thereby, the intended effect of the present application is more remarkably exhibited.

Further, in the processing method according to the third or fourth aspect, the stabilizer is characterized in that the stabilizing solution contains at least one compound selected from the general formulas (2) to (5). Thereby, the intended effect of the present application is more remarkably exhibited.

The pH of the stabilizer according to the present invention is used in the range of 3-10, preferably in the range of 6-9.
Further, as the stabilizer of the present invention, an activator, a chelating agent, a buffer, a pH adjuster, a fungicide, a bactericide, and the like which are usually added to the stabilizer can be appropriately selected and used.

Next, preferred specific processing steps of the processing method according to the present invention will be described. (1) Color development → bleaching → fixing → washing with water (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Color developing → bleaching → fixing → first stable → first Bistability (5) Color development → bleach → bleach-fix → washing (6) Color development → bleach → bleach-fix → washing → stable (7) Color development → bleach → bleach-fix → stable (8) Color development → bleach → bleach-fix → First stable → Second stable (9) Color development → Bleaching → Bleaching and fixing → Fixing → Washing → Stable (10) Color developing → Bleaching → Bleaching and fixing → Fixing → First stable →
Second stability (11) Color development → bleach-fix → stable (12) Color development → bleach → first fix → second fix → stable (13) Color development → bleach → fix → first stable → second stable →
Third stable Among these steps, (3), (4), (7), (1)
0), (11) and (12) are preferable, and particularly (3),
(11) is preferred.

The light-sensitive material used in the present invention may be a silver halide color photographic light-sensitive material containing a silver chloride emulsion, and a high-sensitivity silver halide containing silver bromide or silver iodobromide. It is preferably a color photographic light-sensitive material.

The silver halide content of the light-sensitive material used in the present invention is preferably in the range of ^{3 to} 7 g / m ² . Further, it is more preferably 4 to 6 g / m ² .

The technology and inorganic / organic materials which can be used in the light-sensitive material of the present invention are described in European Patent No. 436,
No. 938A2, and in the patents cited below.

1. 1. Layer structure: page 146, line 34 to page 147, line 25 Silver halide emulsion: page 147, line 26 to 148
Page 12 line 3. Yellow coupler: page 137, line 35 to 146
Page 33, line 149, lines 21-23. Magenta coupler: page 149, lines 24 to 28 and EP 421,453A1, page 3 line 5 to
Page 25, line 55 5. Cyan coupler: page 149, lines 29 to 33 and EP 432,804A2, page 3, line 28 to
Page 40, second line. Polymer coupler: page 149, lines 34-38 and EP 113,334 A2, page 113, 39.
Line-page 123, line 37 7. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3 and EP 3,435,334 A2, page 3 line 1 to line 3. 2
Page 9, line 50 9. Antiseptic / antifungal agent: page 150, lines 25-28. 10. Formalin scavenger: page 149, lines 15-17. Other additives: page 153, lines 38 to 47, and EP 421,453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, 4
Line 0 12. 12. Dispersion method: page 150, lines 4 to 24 Support: page 150, lines 32 to 34 14. Film thickness / film physical properties: page 150, lines 35 to 49 15. Color development step: page 150, line 50 to page 151, line 47 Desilvering step: page 151, line 48 to page 152, 53
Line 17. Automatic developing machine: page 152, line 54 to page 153, 2
Line

[0082]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of silver halide color photographic light-sensitive material sample with magnetic recording medium >> [Preparation of support] 100 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 55 parts by mass of ethylene glycol as transesterification catalyst 0.1 parts by mass of calcium acetate hydrate was added, and a transesterification reaction was performed according to a conventional method.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.04 parts by mass of phosphoric acid trimethyl ester was added.
Then, the temperature was gradually increased and the pressure was reduced, and 290 ° C., 6.67 Pa
Polymerization was performed under the conditions described above to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.58.

This was vacuum-dried at 150 ° C. for 8 hours, melt-extruded in a layer form from a T-die at 300 ° C., brought into close contact with a cooling drum at 50 ° C. while applying static electricity, cooled and solidified, and an unstretched sheet was obtained. Obtained. This unstretched sheet was stretched 3.5 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. at a total transverse stretching ratio of 3. The film was stretched four times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction, to obtain a polyethylene naphthalate film having a thickness of 90 μm.

This is wound around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to produce a support.

On both sides of this support, 12 W / m ² / min
Of the undercoating coating solution B-1
Is applied so as to have a dry film thickness of 0.5 μm.
A corona discharge treatment of ² W / m ² / min was performed, and a subbing coating solution B-2 was applied to a dry film thickness of 0.05 μm.

On the other surface subjected to the corona discharge treatment at 12 W / m ² / min, the undercoating coating solution B-3 was dried to a dry film thickness of 0.1 W / m ² / min.
25 μm, and 12 W / m ² /
The undercoat coating solution B-4 was applied so as to have a dry film thickness of 0.25 μm.

Each layer was dried at 90 ° C. for 10 seconds after the application, and after applying the four layers, heat treatment was performed at 110 ° C. for 2 minutes, followed by cooling at 50 ° C. for 30 seconds.

(Undercoat Coating Solution B-1) A copolymer latex liquid of 30% by mass of butyl acrylate, 20% by mass of t-butyl acrylate, 25% by mass of styrene and 25% by mass of 2-hydroxyethyl acrylate (solid content: 30% 120 g Compound (UL-1) 0.45 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finished with water 1000 ml (Subbing coating solution B-2) Hydroxidation of styrene-maleic anhydride copolymer Sodium aqueous solution (solid content 6%) 50 g Compound (UL-1) 0.5 g Compound (UL-2) 0.1 g Silica particles (average particle size 3 μm) 0.2 g Finish with water 1000 ml (Subbing coating solution B-3) ) 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 2-hydroxy acrylate 25 wt% of the copolymer latex solution (solid content 30%) 50 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethyleneurea) 1000 ml finish in 1.0g water

[0091]

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(Subbing coating solution B-4) Dicarboxylic acid component: 60 mol% of dimethyl terephthalate, 30 mol% of dimethyl isophthalate, 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, ethylene glycol 50 as glycol component Mol% and 50 mol% of diethylene glycol were copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by mass aqueous dispersion A.

Aqueous dispersion of tin oxide-antimony oxide composite fine particles (average particle size: 0.2 μm) (solid content: 40%) 110 g Aqueous dispersion A 70 g Finished with water 1000 ml [Coating of magnetic recording layer] After applying the undercoating coating solution B-4 on the support, the coating solution for the magnetic recording layer having the following composition was dried with a precision extrusion coater to a dry film thickness of 0.8.
The magnetic material was oriented in the direction of application in an orientation magnetic field while the coating film was not dried at the same time as drying, so that high output during magnetic recording and reproduction was achieved.

(Preparation of Coating Solution for Magnetic Recording Layer) Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ₂₊ / Fe ₃₊ = 0.2, specific surface area 40 m ² / g, Hc = 750 Oe) 12 parts by mass Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 4 parts by mass Diacetylcellulose (manufactured by Teijin Limited) 150 parts by mass Polyurethane (N3132, manufactured by Nippon Polyurethane Co., Ltd.) 16 parts by mass Stearic acid 2 parts by mass Cyclohexanone 940 parts by mass Acetone 940 parts by mass After thoroughly mixing the above compounds and dispersing them with a sand mill, Coronate-3041 of polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd., solid content 50% ) Was added, and the mixture was sufficiently stirred and mixed to prepare a coating solution for the magnetic recording layer.

[Coating of Lubricating Layer] On the magnetic recording layer,
A lubricant coating liquid (wax liquid described below) dispersed in a water / methanol mixed solution containing 0.1% of carnauba wax was prepared and applied so that the coating amount of carnauba wax was 15 mg / m ² . The coated raw material was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry it, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of wax liquid) 5 parts by weight of polyoxyethylene lauryl ether was mixed with 100 parts by weight of water heated to 90 ° C., and 45 parts by weight of carnauba wax separately melted at 90 ° C. were added thereto. After that, the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a carnauba wax dispersion (WAX1).

Next, 990 parts by mass of water, 910 parts of methanol
Parts by mass and propylene glycol monomethyl ether 1
Then, 5 parts by weight of the above-mentioned WAX1 was added thereto and stirred to prepare a wax liquid.

Next, photographic constituent layers having the compositions shown in the following Tables 1 to 4 were sequentially provided on the subbed surface opposite to the surface on which the magnetic recording layer was provided, and a halogen with a magnetic recording medium was provided. A silver halide color photographic light-sensitive material sample was prepared. In addition, the addition amount of each compound described in the table is represented by the number of grams per 1 m ² . However, silver halide and colloidal silver were converted to the amount of silver, and each sensitizing dye (indicated by SD) was shown in moles per mole of silver.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

Incidentally, in addition to each of the above-mentioned compositions, a coating aid SU
-1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and Weight average molecular weight: 100,000 two kinds of polyvinylpyrrolidone (AF-2), inhibitors AF-3, AF-4, AF-5,
Hardeners H-1, H-2 and preservative Ase-1 were added.

The specific structure of each compound used in the above sample preparation is shown below. Table 5 shows the characteristics of each silver iodobromide used in the above sample preparation. The above emulsions except for silver iodobromide j were added with the above-mentioned sensitizing dyes, ripened,
Triphosphine selenide, sodium thiosulfate, chloroauric acid, potassium thiocyanate is added, according to a conventional method,
Chemical sensitization was performed so that the relationship between the fog density (minimum density) and the sensitivity was optimized.

[0105]

[Table 5]

[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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The sample prepared as described above was used for 2.54
The recording medium was cut into pieces each having a width of cm (1 inch) and a length of 300 m. A square wave signal of 6 kHz was recorded on the magnetic recording layer by a magnetic writing head at a transport speed of 100 mm / s (model magnetic recording), and wound on a reel. Was.

<< Exposure and Development Processing >> The above-prepared sample was loaded into a commercially available APS compatible camera, and outdoor and indoor scenery were photographed. Then, the following processing 1 was performed using an automatic developing machine.
-1 to 1-19 were performed.

(Processing conditions) Table 6 shows the processing time, processing temperature and replenishment amount of each processing step.

[0118]

[Table 6]

The fixing step is a two-tank countercurrent method, and the stabilizing step is a three-tank countercurrent method. In the fixing and stabilizing steps, each replenisher was replenished to the final tank, and the replenisher was successively flowed into the preceding bath.

(Composition of Processing Solution) In each of the above processing steps,
The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

<Color developing solution and color developing replenishing solution> Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 40 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.2 g Potassium iodide 1.2 mg-hydroxylamine sulfate 2.5 g 4.0 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 7 2.8 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and use potassium hydroxide or 20% sulfuric acid to adjust the color developing solution to pH 10.06 and replenisher to 1 liter. Adjust to pH 10.43.

<Bleaching Solution and Bleaching Replenisher> Bleaching Solution Replenishing Solution Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 70 g 100 g glacial acetic acid 40 g 56 g of water was added to make up 1 liter, and the bleaching solution was adjusted to pH 4 with ammonia water or glacial acetic acid. Adjust to 0 and the replenisher to pH 3.5.

<Fixing Solution and Fixing Replenisher> Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used to adjust the pH of the fixing solution to 6.5. Then, after adjusting the pH of the replenisher to 7.2, water is added to make up to 1 liter.

<Stabilizing Solution and Stabilizing Replenisher (Common)> Stabilizing Solution and Stabilizing Replenisher Water 800 ml Surfactant (details are described in Table 7) 0.5 g Additive (details are described in Table 7) 0 g 1,2-benzisothiazolin-3-one 0.1 g Water was added to make up to 1 liter, and the pH was adjusted to 8.2 using potassium hydroxide or 20% sulfuric acid. -19 was prepared.

[0125]

[Table 7]

The details of the comparative additives described in Table 7 are as follows. Surfactant A: Polyethylene glycol monooctylphenyl ether (n = 20) Surfactant B: Sodium lauryl sulfate EDTA: Ethylenediaminetetraacetic acid DTPA: Diethylenetriaminepentaacetic acid (Treatment method) Processes 1-1 to 1-19 were performed while changing only the composition.

In the processing, the exposed sample was subjected to continuous processing by an automatic developing machine in accordance with the above processing steps and using a processing solution having the above composition. The continuous treatment was performed until the stabilizing solution turned 3 times over 10 days. One rotation in the present invention means that an amount of photosensitive material necessary to replenish the amount of the stable replenisher corresponding to the volume of the stabilization tank is processed.

(Evaluation of each characteristic) After performing the continuous treatment of three rotations as described above, the generation of scum in the stabilization treatment tank,
The magenta transmission density of the unexposed portion of each processed sample after the head clog evaluation and the continuous processing was evaluated according to the method described below.

<Evaluation of Scum> The scum was evaluated by visual observation of the state of the stabilizing solution in the stabilization tank after three consecutive rotations in accordance with the following criteria.

：: No scum was observed in the stable solution at all. Δ: Slight scum was observed in the stable solution. ×: Level of occurrence of scum clearly in the stable solution and adhering to the sample surface and causing failure. <Evaluation of head clog> Using a magnetic read head, a square wave signal was read from the information magnetically recorded on the sample at a transport speed of 100 mm / sec.
The point at which the level dropped by dB or more was defined as a head clog generation point, and the degree of head clog generation was evaluated based on the read length (m) from the start of reading. In addition, the smaller the numerical value, the more head clog occurs at a shorter distance, which means that it is not preferable. In addition, in head clog evaluation,
The display of "300 to" indicates that the generation of the head clock was not recognized even at a distance of 300 m or more.

<Evaluation of Stain after Continuous Processing> The magenta transmission density of the unexposed part (minimum density part) of each processed sample at the start of the three-rotation continuous processing and after the end of the continuous processing was determined by X-rit.
Measured using the transmission densitometer of Company e, and the difference in density (ΔD)
Was determined as the stain concentration.

Table 7 also shows the results obtained as described above. As is clear from Table 7, by using a stable liquid in which the compound represented by the general formula (1) according to the present invention and the compound selected from the general formulas (2) to (5) are used, a comparative example was obtained. On the other hand, it can be seen that the generation of head clog is small, the generation of scum in the stabilizing solution is good, and the generation of magenta stain due to the residual dye in the continuously processed sample is also slight.

Example 2 Example 1 was repeated except that the type of the surfactant, the type of the additive, and the replenishment amount of the stabilizer were changed as shown in Table 8 in the stabilizer 1-2 prepared in Example 1. Exposure and continuous processing were performed in the same manner as described above, and scum evaluation, head clock evaluation, and stain evaluation were performed according to the method described in Example 1. The results obtained are also shown in Table 8.

[0134]

[Table 8]

The surfactants A and B described in the table are
It has the same meaning as that used in Example 1, and formalin used a 37% aqueous solution of formaldehyde.

As is clear from Table 8, a replenishing amount of a stabilizer prepared by combining the compound represented by the general formula (1) according to the present invention with the compound selected from the general formulas (6) to (8) was used. When used in the range of 150 to 800 ml / m ² , the occurrence of head clog was small, the occurrence of scum in the stabilizing solution was good, and the magenta stain caused by the residual dye in the continuously processed sample was smaller than that of the comparative example. It can be seen that the occurrence was slight.

Example 3 Using the stabilizing solutions 2-1 and 2-2 prepared in Example 2, the stable solution in the foremost tank was poured into the processing tank in the fixing step, which is the immediately preceding processing step, at a flow rate of 250 ml / m ² . The fixer replenishment rate was changed to 2 times the fixer replenisher.
Exposure and continuous processing were performed in the same manner as in Example 1 except that the amount was changed to 50 ml / m ² , and scum, head clock, and stain were evaluated in accordance with the method described in Example 1. The results obtained are also shown in Table 9.

[0138]

[Table 9]

As is clear from Table 9, the compound represented by the general formula (1) according to the present invention is added to the stabilizing solution, and a part of the stabilizing solution is added to the fixing bath which is the immediately preceding processing bath. This shows that the head clog is also improved, the generation of scum in the stabilizing solution is also good, and the generation of magenta stain due to the residual dye in the continuously processed sample is also small.

Example 4 Process 4 was carried out in the same manner as in process 2-2 of example 2 except that the ratio of the amount of ammonium ions to the total amount of cations in the fixing solution was changed as shown in Table 10.
1 to 4-6 were performed. In addition, in order to change the ratio of the amount of ammonium ions, the ratio was adjusted appropriately using ammonium thiosulfate and sodium thiosulfate, and ammonium thiocyanate and sodium thiocyanate.

Except for the above, exposure and continuous processing were performed in the same manner as in Example 1, and scum evaluation, head clock evaluation, and stain evaluation were performed in accordance with the method described in Example 1 to obtain the results. The results are also shown in Table 10.

[0142]

[Table 10]

As is clear from Table 10, the head was prepared by adding the compound represented by the general formula (1) to the stabilizing solution and adjusting the ratio of ammonium to all cations in the fixing solution to 50 mol% or less. It can be seen that the clog was improved, the generation of scum in the stabilizing solution was also good, and the generation of magenta stain due to the residual dye in the continuously processed sample was also slight.

[0144]

According to the present invention, even when low replenishment processing is performed, head clog hardly occurs, scum is less generated,
In addition, a stabilizing solution for the silver halide color photographic light-sensitive material and a method for processing the silver halide color photographic light-sensitive material can be provided which have little residual sensitizing dye or the like in the processed silver halide color photographic light-sensitive material.

Claims (6)

[Claims] 1. A silver halide color photographic photosensitive material comprising a compound represented by the following general formula (1) and at least one compound selected from the following general formulas (2) to (5): Stabilizer for materials. General formula (1) RO (AO) _n (BO) _m H wherein R represents a C 5 to C 25 alkyl group which may have a saturated or unsaturated substituent, and A and B are Each represents an alkylene group having 2 or 3 carbon atoms which may have a substituent. n and m each represent 0 or an integer of 4-33, and n and m are not 0 at the same time. [Formula 1] [In the general formula (2), A ¹ , A ² , A ³ and A ⁴ each represent —CH ₂ OH, —PO ₃ (M) ₂ or —COOM, and M represents a hydrogen atom or an atom forming a salt. Represent. X is an alkylene group having 2 to 6 carbon atoms ^{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 8, and B ¹ and B ² each represent an alkylene group having 1 to 5 carbon atoms. In the general formula (3), n1 represents 1 or 2, A is -COOM ^3, -O
It represents H, -NH ₂ or -PO ^₃ (M _{3) 2.} M ¹ , M ² , M
³ represents a hydrogen atom or an atom forming a salt, respectively. In the general formula (4), n2 and n3 each represent 1 or 2, and B represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. M ⁴ and M ⁵ each represent a hydrogen atom or an atom forming a salt. In the general formula (5), A ⁵ and A ⁶ are each-
COOM ⁷ , —PO ₃ (M ⁷ ) ₂ , —SO ₃ M ⁷ , a hydroxyl group or a mercapto group, and M ⁶ and M ⁷ each represent a hydrogen atom or a salt-forming atom. R represents a hydrogen atom, an aliphatic group or an aromatic group; X ₁ and X ₂ each represent a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of an aliphatic group and an aromatic group; Represents ] 2. A stabilizing solution for a silver halide color photographic light-sensitive material, comprising a compound represented by the general formula (1) and at least one compound selected from the following general formulas (6) to (8): And the replenishment amount of the stabilizer is 150 to 800 m
1 / m ^{2. A} method for processing a silver halide color photographic material. Embedded image [In the general formula (6), A _{1 to} A ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, or a pyridyl group. m is 0 or 1
Represents In the general formula (7), Z ₄ represents an atom group necessary for forming a hydrocarbon ring or a hetero ring, X represents an aldehyde group, and (In the formula, R ₄₁ and R ₄₂ each represent a lower alkyl group.)
And n represents an integer of 1 to 4. In the general formula (8), X represents a 1H-pyrazole ring or 1 together with a nitrogen atom.
Represents a group of non-metallic atoms necessary for forming an H-1,2,4-triazole ring. ] 3. A method for processing a silver halide color photographic light-sensitive material, in which processing is performed in a stabilizing solution tank following a processing tank having a fixing ability, wherein the stabilizing solution in the stabilizing solution tank is represented by the general formula (1). A method for processing a silver halide color photographic light-sensitive material, which comprises adding a part or all of the overflow solution of the stabilizing solution to a processing tank having the immediately preceding fixing ability. 4. A method for processing a silver halide color photographic light-sensitive material, in which processing is performed in a stabilizing solution tank subsequent to a processing tank having a fixing ability, wherein the stabilizing solution in the stabilizing solution tank is represented by the general formula (1). A method for processing a silver halide color photographic light-sensitive material, characterized in that 0 to 50 mol% of all cations in the processing solution having the fixing ability contain ammonium. 5. The method according to claim 1, wherein the stabilizing liquid is a compound represented by the following general formula (6):
5. The method for processing a silver halide color photographic light-sensitive material according to claim 3, comprising at least one compound selected from (8). 6. The stable liquid according to the general formula (2)
5. The method for processing a silver halide color photographic light-sensitive material according to claim 3, comprising at least one compound selected from (5).