JPH02280150A - Color developing solution for silver halide color photographic sensitive material and method for processing the same by using the developing solution - Google Patents

Abstract

PURPOSE:To obtain always stable photographic characteristics even at the time of using a color developing solution for a long time by using a processing solution containing a specified amount of a specified color developing agent and at least one of polystyrenesulfonic acid derivatives. CONSTITUTION:The color developing solution contains at least one of the polystyrenesulfonic acid derivatives and at least 1.3X10<-2>mol/l of the color developing agent represented by formula I in which R<1> is H, halogen, or alkyl; each of R<2> and R<3> is H, alkyl, or aryl, and at least one of them is an alkyl group substituted by a water-soluble group or a group of formula II; R<4> is H or alkyl; and each of m and n is an integer of 1-5, thus permitting the color developing solution to be remarkably enhanced in stability, accordingly, the obtained color image to be conspicuously restrained in occurrence of stains due to residual dyes even at the time of using a processing solution used for a long time, and also prevented from magenta staining and sufficient in dye stuff density.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic materials, and more specifically to a method for improving residual color staining and obtaining stable photographic properties over a long period of time. This invention relates to a method for processing silver halide color photographic materials.

[Background of the invention]

In recent years, processing times for silver halide photographic materials are becoming faster in response to user needs, and color photographic materials are no exception.

Particularly in the field of minilabs and news photography, rapid processing has become a slogan.

Manufacturers are trying to improve developability by changing the silver halide composition of photosensitive materials, as well as increasing the processing temperature and stirring speed, and changing the type and concentration of developing agents. , or the use of a development accelerator.

However, there are many problems associated with speeding up the processing, such as concentration due to evaporation of the processing solution due to high temperatures, scratches on the photosensitive material due to stronger stirring, and even further problems with the processing solution. The activation of quinone diimine tends to cause many problems such as fogging due to the generation of large amounts of quinone diimine.

In particular, when the processing time is about 10-odd seconds, dyes added to silver halide photographic materials, specifically spectral sensitizing dyes, or colored organic compounds such as anti-irradiation dyes and filter dyes, are removed. decomposes in the treatment bath,
This results in insufficient time for elution from the photosensitive material.

Therefore, the result of coloring the white background part of the obtained image,
This residual color contamination is a fatal drawback for color paper, which requires the highlight areas of the image to be finished whiter and clearer.

Another problem caused by rapid processing is that when relatively small amounts of development are continued over a long period of time, the color developing solution becomes unstable due to magenta color contamination caused by the oxide of the main ingredient due to the low renewal rate. Therefore, it is not possible to obtain a high-density color image.

It has been found that the color staining occurs not only during color development but also during subsequent bleaching or bleach-fixing.

For example, Japanese Patent Application Laid-open No. 30641/1983 is known to have a structure that allows pigments and dyes to be easily eluted against such phenomena. Regarding the stabilization of color developing solutions, for example, Japanese Patent Application Laid-Open No. 48-90983, U.S. Patent No. 3.994
．． Many techniques have been disclosed, such as Japanese Patent No. 730. However, these conventional techniques still have problems such as insufficient effects, expensive compounds, and technical difficulties in practical application. A solution was strongly desired.

As a result of extensive studies, the present inventors have achieved the present invention using a color developing solution that combines a specific color developing agent and a polystyrene sulfonic acid derivative.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a color developing solution for silver halide color photographic light-sensitive materials and a processing method thereof, which can always provide stable photographic performance even without long-term processing.

The second object of the present invention is that even in rapid color development processing,
The object of the present invention is to provide a color developing solution for silver halide color photographic light-sensitive materials without residual color staining, and a processing method thereof.

Other purposes will become clear in the following specification.

[Structure of the invention]

The above object is such that when a silver halide color photographic light-sensitive material is rapidly processed using a color developer after exposure, the color developer contains at least 1.0% of the color developing agent represented by the following general formula (1). This was achieved by a developer for a silver halide color photographic light-sensitive material and a processing method thereof, characterized in that it contains 3 x 10-'' mol/l and at least one selected from polystyrene sulfonic acid derivatives.

In the formula, R1 represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group is a linear or branched carbon number 1
-5 alkyl group, which may have a substituent. R2 and R3 represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. At least one of R2) and R3 is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or -F-(Cl(→-0+-R'). Yes, this alff
l (1 The kill group may further have a substituent.

In addition, R1 represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m and n are integers of 1 to 5, C, H, \/C, H , OH.

Next, the general formula List the compounds shown by but, It is not limited to these.

N.H.

preferred for the present invention Commonly used general formulas Specific examples of color developing agents are shown below.

c, o, \/C2H40CHs to Exemplary color developing agents ■ C2H,\/C,H,NHSO□CH.

C,)I,\/c3Hsso31( ■ ■ CH,\/C2H,OH NH2 N.H.

■ ■ HOH4C,\/C,)1. OH C, H, \/(CH2CHzO)2cHi■ ■ C,H,\/caHssOxH C, H, \/ (CHzCHzO)scHsNil□ ■ ■ H C,\/C5HsS (hH C, +1. \/(CH2Cl, O), C, H.

■ ■ HN3 CH* C0OH C,H,\/(CHzCH20)*C2H5(I -
15) C2H,\,yCzHsNH3O2CHs"'\/
02H408 Among the color developing agents exemplified above, exemplification No. and CI are preferable for use in the present invention because they cause less fogging.
-1), (I-2), (1-3), (1-4), (I-
6), (I-7) and (I-15), particularly preferably (I-1) and (I-3).

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing crude drug having a water-soluble group used in the present invention is
At least 1.3X 10 per 112 ordinary color developer
-" mole is preferable, but from the viewpoint of rapid processing, 1.5X 10-' to 2X per 112 color developer solution
A range of 10-' moles is more preferred.

The color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
- May be used in combination with pyrazolidone, metol, etc.

Next, the polystyrene sulfonic acid derivatives used in the present invention refer to styrene polymers, styrene copolymers, or styrene block copolymers into which sulfonic acid groups are introduced. A polystyrene sulfonic acid derivative more preferably used from the viewpoint of effectiveness is a compound represented by the following general formula (A).
- Below 1, lower margin (... General formula (A) (wherein, B represents SO, M' or 1et-O3OJ'' group, n represents an integer from 5 to 4000, and a+liO,3
~4.5. However, m other than an integer means that acid groups are regularly or irregularly present in the molecule, and represents the arithmetic average number of sulfonic acid groups in all molecules.

M 1 and M 2 represent a hydrogen atom, an alkali metal atom such as sodium, potassium, lithium or ammonium ion, or an organic group. ) In the above general formula, n is preferably in the range of 10 to 3,000, more preferably in the range of 50 to 1,000.

Moreover, ■ is preferably in the range of 0.5 to 4, more preferably in the range of 0.8 to 3. Among those representing M, more specifically, examples of organic groups include monoethanolamine, jetanolamine, triethanolamine,
Examples include pyridinium, picolinium, and quinolinium.

Furthermore, the above polystyrene sulfonic acid derivative is used in color developer I.
It is preferably used in the range of 0.5 to 12 g per ff, more preferably in the range of 0.2 to 25 g, most preferably 0.
．． It is in the range of 2 to 7 g.

Commercially available products can be used as these polystyrene sulfonic acid derivatives, such as Gearon 1 manufactured by Lion Corporation.
00O, Chemistat 6120 and Chemistat SA-9 manufactured by Sanyo Chemical Industries, Ltd., and others can be easily obtained from Toyo Soda Co., Ltd. and the like.

In addition to the above, specific examples of polystyrene sulfonic acid derivatives include the following: The color development time of the processing method according to the present invention varies depending on the type of light-sensitive material, processing conditions, etc., but is 35 seconds or less. The present invention can be achieved by the following processing, preferably in the range of 3 seconds to 30 seconds, particularly preferably in the color development processing of 5 seconds to 25 seconds. The development temperature at this time is in the range of 20 to 50°C, preferably 25 to 40°C.

Processing solutions other than the color developing solution according to the present invention, such as bleach-fix solutions and stabilizing solutions, may be used at temperatures in the range of 20 to 50°C, usually 33 to 50°C.
45°C is standard.

However, if necessary, it is possible to set the temperature and time within a range that does not cause any problems, such as by increasing the temperature to shorten the processing time, or conversely by decreasing the temperature to improve the stability of the processing liquid and the image quality.

In addition, during continuous running processing, a replenisher is used for each processing solution including the color developer to prevent fluctuations in the liquid structure and obtain a stable finish.

When the color developing solution of the present invention contains a compound represented by the following general formula CII), not only the desired effects of the present invention are better achieved, but also the fog density in the unexposed areas of the photographic material is kept low. Therefore, it is preferable to use it in combination with the color developing solution of the present invention.

Specific compounds of general formula (II) are described in U.S. Patent No. 3.287,12.
No. 5, No. 3,293.034, No. 3,287.1
No. 24, etc., and particularly preferred specific exemplified compounds are shown below.

In the formula, R1 and R3 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

In general formula (U), R3 and R3 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom,
The alkyl groups represented by R1 and R2 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of R1 and R2 include those having substituents, and examples of the ring formed by bonding R1 and R1 include heterocycles such as piperidine and morpholine.

Hydroxylamine system ll- represented by general formula (II)
1. These hydroxylamine compounds are usually hydrochloride,
It is used in the form of sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, and non-salt forms.

The concentration of the compound represented by the general formula (I) of the present invention in the color developer is usually 0.2 to 509/Q, preferably 0.
It is 5 to 30 y/β, more preferably 1 to 15 g/ff.

Further, the compounds represented by the general formula (n) may be used alone or in combination of two or more.

When the color developing solution of the present invention contains a compound represented by the following general formula CB), not only the objective effects of the present invention can be better achieved, but also the general formula [B) (B-7 ) (B-8) General formula (B
), X represents 〉N or 〉CR, and Rl-R*
each represents a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, or a lower alkyl group which may have a substituent.

Specific examples of the compounds represented by the general formula CB) include the following.

(B-1) (B-2) (B -3') (B -4) (B
-5) (B-6) (B-9) (B-10) Most of these compounds represented by the general formula (B) can be obtained as commercial products.

The compound represented by the above general formula CB) is preferably used in an amount of 0.1"100 g per 1Q of color developing solution, more preferably in a range of 0.2 to 30 g.

Among the above-mentioned exemplified compounds, from the viewpoint of the desired effects of the present invention,
(B-1) and (B-2) are most preferably used.

Normally, an IS salt is used as a preservative in a color developer, but the concentration of sulfite in the color developer according to the present invention is
When used at 1.6 x 10 moles or less per 112 color developing solutions, it is possible to suppress the decrease in color density that is thought to be caused by dissolution physical development of photosensitive materials containing high silver chloride, and also to prevent a decrease in storage ability. Since the amount of chloride is extremely slight, it is possible to provide a color developing solution that enables rapid processing using photosensitive materials containing high silver chloride, and a method for processing silver halide color photographs using this solution. A sulfite concentration of 1.6X 10-' mol/l or less is preferably used.Furthermore, this effect is better exhibited at a sulfite concentration of 1X10-' mol/l or less, more preferably 4 X 10-' mol/l. -3 mol/Q or less. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

When the color developer according to the present invention contains a compound represented by the following general formula [C], it not only exhibits the effects of the present invention better, but also prevents air oxidation of the color developer. It is more preferably used because it shows an improvement effect.

General formula [C] (In the formula, R2□ is a hydroxyalkyl group having 2 to 6 carbon atoms, R1ff1 and R13 are each a hydrogen atom, and 1 carbon number
~6 alkyl group, hydrokyl integer X having 2 to 6 carbon atoms
' and Z' each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [C] are as follows.

(C-1) Ethanolamine, (C-2) Jetanolamine, (C-3) Triethanolamine, (C-4) Di-
Isopropanolamine, (C-5) 2-methylamine ethanol, (C-6) 2-ethylaminoethanol,
(C-7) 2-dimethylaminoethanol, (C-8)
2-diethylaminoethanol, (C-9) 1-diethylamino-2-propanol, (C-10) 3-diethylamino-1-propanol, (C-11) 3-dimethylamino-1-propanol (C- 12) Isopropylaminoethanol, (C-1
3) 3-Amino-1-propatol, (C-14)2-
Amino-2-methyl-1,3 propanediol, (C-15) ethylenediaminetetraisopropanol, (C-16) benzyljetanolamine, (C-17)
)2-amino-2-(hydroxymethyl)1.3-7'
Lovandiol.

These compounds represented by the general formula [C] have the objective effect of the present invention of Ig'' 10 per color developer IQ.
It is preferably used in the range of 0g, more preferably 3g~
It is used in a range of 50g.

In the present invention, when a triazylstilbene fluorescent brightener represented by the following general formula [W] is used in the color developing solution according to the present invention, capri is generated as shown in the general formula [W]Y.

In the general formula [W], X r, X 2. Y + and Y2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (e.g. methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g. phenoxy, p-sulfophenoxy, etc.), an alkyl group (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (e.g. methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydrokine ethylamino, di(β -hydroxyethyl)amine, β-sulfoethylamino, N-(β-sulfoethyl)N/-methylamine, N-(β-hydroxyethyl-N'-methylamino, etc.), arylamino groups (e.g. anilino, o- m-p-sulfoanilino, o-m
-p-chloroanilino, o-m-p-1-riidino, o
-m-p-carboxyanilino, o-m-p-hydroxyanilino, sulfonaphthylamino, o-m-p-aminoanilino, o-m-p-anidino, etc.). M
represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds can be mentioned: mulberry
- The triadylstilbene-based brightener represented by the general formula [W] is, for example, "Fluorescent Brightener" by Kasei Kogyo Kinsen (1933).
It can be synthesized by the usual method described on page 8 (Published August 1, 2013).

These triacylaminostilbene brighteners are preferably used in an amount of 0.2 to 10 g, particularly preferably 0.4 to 5 g, per 1Q of the color developer of the present invention.

In addition, a commonly used chelating agent can be added to the color developer according to the present invention, but when a chelating agent represented by the following general formula [[] is used, the preservability becomes even better, and Since it also produces a development accelerating effect, it is particularly preferably used in combination with the present invention.

General formula [■] In the general formula (I[[), AI to A are each -C
OOM or -P03M2M3. M, , M, and M each represent a hydrogen atom, an alkali metal atom, or an ammonium group, and n represents 1 or 2.

Specific compounds represented by the general formula (I[I) are known as diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentamethylenephosphonic acid, and triethylenetetraminehexamethylenephosphonic acid, and their salts (potassium, Alkali metal salts such as sodium and lithium, and ammonium salts are also known and can be obtained as commercial products.

The amount of the compound represented by the general formula (I [ used.

Among the compounds represented by the general formula (II), diethylenetriaminepentaacetic acid and its salts are particularly preferably used from the viewpoint of the desired effects of the present invention.

Next, the replenishment amount of the color developer according to the present invention is the photographic material l m
It is preferable to treat at a rate of 250 IIIa or less per liter, and more preferably at a rate of 5 m12 to 200 mQ. Particularly preferably l Om(l
to 150t12, most preferably 201
It ranges from 112 to 120 Q.

The color developing solution of the present invention preferably does not substantially contain benzyl alcohol. Here, "substantially free" refers to 2 rtr (1/(l) or less of benzyl alcohol, and in the present invention, it is most preferable to contain no benzyl alcohol at all. This is because benzyl alcohol has extremely low solubility and the amount of replenishment is extremely small. This is because in the process of the invention, the color developing solution tends to be concentrated, resulting in extremely troublesome problems such as failure of adhesion to photographic materials due to oil precipitation and generation of tar due to oxidation of the color developing agent.

After the color development treatment according to the present invention, treatment is performed with a processing solution having bleaching ability.

A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching solution or bleach-fixing solution used as the processing solution having bleaching ability, and the metal rust salt oxidizes the metallic silver produced by development to halogenate it. It has the effect of converting it into silver, and its composition is aminopolycarboxylic acid or oxalic acid,
It is a complex formed with an organic acid such as citric acid and a metal ion such as iron, cobalt, or copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these organic acids include the following.

(1) Ethylenediaminetetraacetic acid (2) Diethylenetriaminepentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N, N', N
″-triacetic acid (4) 1,3-propylenediaminetetraacetic acid (5) nitrilotriacetic acid (6) cyclohexanediaminetetraacetic acid (7) iminodiacetic acid (8) dihydroxyethylglycincitric acid (9) ethyl ether diamine tetraacetic acid ( lO) Glycol ether diamine tetraacetic acid (11) Ethylene diamine tetrapropionic acid (12) Phenyl diamine tetraacetic acid The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and also contains various additives. Additives include, in particular, alkali or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, nitrates and the commonly known bleaching agents. It is desirable to include an accelerator.Additionally, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, and polyethylene oxides are known to be added to ordinary bleaching solutions. It is possible to add as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffering agent consisting of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium dihydroxide, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination.

In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the bleach bath or bleach-fix bath and the bleach replenisher solution or bleach-fix replenisher storage tank, if desired. Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

In the processing after color development according to the method of the present invention, a bleach-fix solution is preferably used from the viewpoint of rapid processing, and when a high silver chloride photographic material is used as in the present invention and the bleach-fix treatment is carried out immediately after color development, A stain called bleaching blade yellowing is likely to occur. For this reason, as a result of various studies, we found that the pH of the bleach-fix solution was
It has been found that by using H in the range of 4.5 to 6.8, this drawback can not only be solved, but also the silver bleaching rate can be increased.

Particularly, this effect is good when the pH of the bleach-fixing solution is 5 to 6.3, and particularly good when the pH is 5.2 to 5.9.

In the processing method of the present invention, silver may be recovered by known methods from processing solutions containing soluble silver complexes such as washing or washing substitute stabilizing solutions, fixing solutions, bleach-fixing solutions, and the like. For example, the electrolysis method (French Patent No. 2.299.667), the precipitation method (Japanese Unexamined Patent Publication No. 52-73037, Narrow-Scale Patent No. 2,331)
．． 220), the ion exchange method (Japanese Unexamined Patent Publication No. 5117114, German Patent No. 2.548.237), and the metal substitution method (British Patent No. 1,353.805) can be effectively used.

In the processing method of the present invention, after color development processing, bleaching, fixing, and IT (or bleach-fixing) processing, stabilization processing may be performed without washing with water, or washing processing with water may be performed, followed by stabilization processing. In addition to the above steps, dura mater, neutralization, black and white development,
Known auxiliary steps may be added as necessary, such as inversion and washing with a small amount of water.

A typical example of a preferred treatment method includes the following steps.

(1) Color development - bleach fixing, one water wash (2) color development - bleach fixing → small amount of water washing - water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable (5) color development Development - Bleach-fixing - 1st stability - 2nd stability (6)
Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) Color development → stop → bleach-fixing → washing with water (or stable) (8) Color development - bleaching → washing with water → fixing → washing with water → stable (9) )
Color development → Bleaching → Fixing → Washing → Stable (10) Color development →
Bleaching → Washing with a small amount of water → Fixing → First stability - Second stabilization (11) Color development → Bleaching → Washing with a small amount of water → Fixing → Washing with a small amount of water →
Washing with water → Stable (12) Color development → Washing with a small amount of water - Bleaching - Washing with a small amount of water and fixation →
A small amount of water washing→Water washing→Stabilization (13) Color development→Stop→Bleaching→Small amount of water washing→Fixing→Small amount of water washing→Water washing→Stabilization Among these steps, steps (4) and (5) are particularly preferably used.

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention is allowed to flow into the subsequent bleaching solution or bleach-fixing solution. This shows that when a certain amount of the color developer according to the present invention is introduced into a bleach or bleach-fix solution, the generation of sludge in the bleach or bleach-fix solution can be suppressed, and surprisingly, silver from the bleach-fix solution can be suppressed. This is because the recovery efficiency is also improved.

Furthermore, in addition to the above-mentioned method, when part or all of the overflow liquid of the stabilizing liquid in the subsequent process is poured into the bleach-fixing liquid or the fixing liquid, the above-mentioned effects are particularly well achieved.

The silver halide grains used in the silver halide emulsion layer of the photographic material used in the processing method of the present invention have a silver chloride content of 70%.
It is necessary that the silver chloride content is 90 mol% or more, and preferably close to 100 mol%, but the effects of the present invention are better achieved when the silver chloride content is 90 mol% or more, and especially when the silver chloride content is 95 mol%
In the above case, the intended effects of the present invention are particularly well achieved.

The silver chloride used in the present invention is at least 70 mol%
The silver halide emulsion layer containing silver halide grains consisting of a color coupler has a color coupler. These color couplers react with color developer oxidation products to form non-diffusible dyes. Color couplers are advantageously incorporated in non-diffusive form in or closely adjacent to the photosensitive layer.

Thus, the red-sensitive layer may contain, for example, a non-diffusive color coupler that produces a cyan image, generally a phenol or alpha-naphthol coupler. The green-sensitive layer may contain, for example, at least one non-diffusive color coupler that produces a magenta image, typically a 5-pyrazolone color coupler and a pyrazolotriazole.

The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler that produces a yellow image - generally a color coupler having open-chain ketomethylene groups.

Color couplers can be, for example, 6-14- or 2-equivalent couplers.

In the present invention, 2-equivalent couplers are particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Agfa research report (formerly tteilungln aus
den Forschungslaboratory
n der Agfa), Lehr x Aykusen/
Munich (Leverkusen/Munchen)
, Vol., m, p. 111 (1961), in ``Color coupler J (Farbkupler)'' by W. Pe1z; K. Venkataraman, [The Chemistry of Synthetic Soybean J (The
Chemistry of 5ynthetic D
yes), Vat.

4.341-387, Academic Press (Acad
emic Press), rThe Theory of the
Photographic Process J (The The
ory of the Photographic P
rocess), 4th edition, pp. 353-362; and Research Disclosure.
osure) No. 17643, Section 2 is preferred.

In the present invention, in particular, JP-A-63-106655
General formula CM-1 as described in the specification, page 26]
A magenta coupler represented by General formula (C-I) or [
C-II) (Specific examples of cyan couplers include (C'-1) to (C'-82), (C"l) to (C'-1) to (C'-82), (C"l) to ( C"
-36)), high-speed yellow couplers described on page 20 of the same specification (specific examples of yellow couplers include (Y'-1) - described on pages 21 to 26 of the same specification)
(y'-39)) is preferably used in combination with the photographic material according to the present invention from the viewpoint of the desired effects of the present invention.

In the present invention, when a nitrogen-containing heterocyclic mercapto compound is used in combination with the high silver chloride photographic material according to the present invention,
This invention not only satisfactorily achieves the desired effects of the present invention, but also has the additional effect of minimizing the effect on photographic performance that occurs when a bleach-fixing solution is mixed into a color developing solution. In the invention, this can be mentioned as a more preferred embodiment.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (■'-1) to (1'-87) described in JP-A-63-106655, pages 42 to 45.

Known photographic additive materials can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Ro-17643 and RD18 from Research Disclosure shown in the table below.
Examples include compounds described in No. 716.

Additive RD-17643RD-18716 page
Classification Page Classification 23 I [I 648 upper right 23 1V 64g right - 649 left 29 XX
I 648-Top right 24 Vl 649-Bottom right 24 Vl 649-Bottom right 25 ■ 650 Left-Right 25 ■ 25-26 ■ 649 Right-650 Left Chemical sensitizer Sensitizing dye development accelerator Antifoggant Stabilizer Color staining Inhibitor Image stabilizer Ultraviolet absorber Filter dye 25-26■ 649 Right-65
0 Left whitening agent 24 V Hardening agent 26 X 651 Right coating aid 26-27
7 ff 650 right slip agent 27
III Anti-static agent 27 Xll
650 right matte agent 28XV1
650 Right Binder 26 [651 Right As the support for the light-sensitive material, ordinary supports can be used, such as cellulose acetate supports and polyester supports. Paper supports are also suitable and these can be coated, for example, with polyolefins, especially polyethylene or polypropylene. Regarding this, see Research Disclosure No. 1 above.
7643, Saekungyong X■ can be referred to.

For the present invention, if the photosensitive material contains a coupler and is processed by the so-called internal development method,
Color paper It can be applied to any color photosensitive material such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper.

[Specific embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A photographic material was prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer l: 1.0 g/m'' gelatin, 0.30 g/m
1,OX 10-' mole g/m dissolved in the blue-sensitive silver halide emulsion spectrally sensitized in (S-1) and 0.50 g/m of dioctyl phthalate (- conversion, same hereinafter) 2. A layer containing the yellow coupler described below.

Layer 2: Intermediate layer consisting of 0.61 g/3 gelatin.

Layer 3...1. Gelatin of 0.2g/m2, 0.22g/m
A spectrally sensitized green-sensitive silver halide emulsion (S-2') and a magenta coupler of 1, OX 10 - 'mol g/s' dissolved in 0.28 g/ll' dioctyl phthalate were added. Containing layer.

Layer 4: Intermediate layer consisting of 0.60 g/m'' gelatin.

Layer 5 - 1.10 g/m'' gelatin, 0.22 g/l spectrally sensitized red-sensitive silver halide emulsion (S-3) and dissolved in 0.25 g/m'' dibutyl phthalate. A layer containing 1,75 x 10-'mol g/la'' of the cyan coupler described below.

Layer 6...1.0 g/m'' gelatin and 0.25 g
0,30 g/m2 dissolved in dioctyl phthalate/
A layer containing m2 of Tinuvin 328 (ultraviolet absorber manufactured by Ciba Geigy).

Layer 7: Layer containing 0.40 g/+z gelatin.

In addition, 2,4-dichloro-6-human' was used as a hardening agent.

Sodium xy-S-triazine was added into layers 2.4 and 7 at 0.016 g/ta gelatin, respectively.

Note that the average silver halide composition in all silver halide emulsions has a AgBr/kgcQ (mole ratio) of 0.4/9.
9.6 mm was used.

Furthermore, Al-1 and Al-2 described later were used as anti-irradiation dyes.

Yellow coupler: a-r4-(1-benzyl-2
-7enyl-3,5-dioxo-1,2,4-driazolidinyl)]-]αvivalyl-2-chloro-5-γ-(
2,4-di-tert-amylphenoxy)butyramido]acetanilide magenta coupler: 1-(2,4
,6-dolichlorophenyl)-3-(2-chloro-5-
octadecylsuccinimide anilino)-5-pyrazolone cyan coupler = 2,4-dichloro-3-methyl-6-
[α-(2,4-di-tert-amylphenoxy)butyramide]phenol I-1 I-2 The color paper sample thus prepared was processed in an automatic processor according to the following processing steps.

The composition of the treatment liquid used is as follows.

[Color development tank liquid] Potassium bromide 20g Polyvinylpyrrolidone (RAS Rubiscoll) 0.
2g potassium sulfite (50% solution) 0.5
m12 color developing agent Listed in Table 1 Diethylhydroxylamine (85%) 5.0g Triethanolamine 12.5g Potassium carbonate 30g Ubitex CK
(manufactured by Cibaga Iggy) 3g Sodium polystyrene sulfonate Listed in Table 1 (Chemistat 6120...0 manufactured by Yokasei Co., Ltd.) Finished to 1Q with water and adjusted to pH 10.10 with potassium hydroxide or 50% sulfuric acid.

[Color development replenisher] Polyvinylpyrrolidone (BASF Rubisrubiscol 0.2g Potassium sulfite (50% solution) 1
．． Color developing agent listed in OmQ Table 1, 1.2 times the color developing tank solution Diethylhydroxylamine (85%) 7.0 g Triethanolamine 15.0 g Potassium carbonate 30 g Uvitex C
K (manufactured by Ciba Geigy) 3g Sodium polystyrene sulfonate (Chemistat 6120...0 manufactured by Yokasei [Co., Ltd.]) Table 1
The pH was adjusted to 10.60 with potassium hydroxide or 50% sulfuric acid.

[Bleach-fix tank solution] Diethylenetriaminepentaacetic acid ferric ammonium salt 65g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml 12 Ammonium thiocyanate 30g Ammonium sulfite (40% solution) 40mff Adjust to pH 5.7 with aqueous ammonia or glacial acetic acid At the same time, add water to make the total volume IQ.

[Bleach-fix replenisher] Diethylenetriaminepentaacetic acid ferric ammonium salt 75g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 120mff ammonium thiocyanate 40g ammonium sulfite (
40% solution) 501112 Adjust pI (5.0 to 1Q with ammonia water or glacial acetic acid).

[Water wash alternative stable tank liquid and replenisher] 5-chloro-2-methyl-4-isothiazolin 3-one 0.02g2-
Methyl-4-inchazolin-3-one 0.02g
Ethylene glycol 1.0 g 0-phenylpheno-4 sodium 0.5 g 2-octyl-4-thiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1 diphosphone (60% aqueous solution) 8. Og
BiC et al. (45% aqueous solution) 1.0
gMg5O,・7HxOO,2g Zn5Oa @7HzO003g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5g Nitrilotriacetic acid trisodium salt 1.5g N2 with water
Then adjust the pH to 7.0 with aqueous ammonia and sulfuric acid.

The above processing solution was put into an automatic developing machine, and a running test was conducted under the above conditions.

The running test was continued intermittently for 20 days until the amount of replenisher added to the color development tank became twice the amount of the color development tank. As a method for evaluating the residual color stain in the unexposed area of the wedge-exposed piece processed after the running test, the reflection density at 420n+1 and the reflection density after being left in direct sunlight for 1 hour were determined, and the difference of 7 points was taken as the residual color stain. Furthermore, the densities of the lowest magenta density part and the highest yellow density part of the same piece were determined.

Comparative color developing agent (D-1) (D-2) According to Table 1 above, a specific color developing agent was used in the color developing solution at 1.3 x 10-'' mole or more, and a polystyrenephonic acid conductor was used. It can be seen that when used in combination, a sufficient color density can be obtained, there is little residual color stain, and the magenta stain is also good.

Example 2 The magenta coupler in the color paper sample used in the experiment of Example 1 was converted into
Pyrazolotriazole type magenta couplers CM'-1), (M'-2), (M'-4), (
M'-21), (M'-37), (M'-61),
(M'-63) and conducted a similar experiment, both residual color stain and magenta stain were reduced by about 15 to 25%, which was extremely good.

Example 3 Examples of heterocyclic mercapto compounds (I'-24), (I'=
41), (I'-60), (I'-66), (I'
-79) and (I'-84) respectively at 0.16-g/
An experiment was conducted in the same manner as in Example 1 except that -2 was added, and both the residual color stain density and magenta stain were further improved by about 15 to 20%.

Example 4 Sodium polystyrene sulfonate used in the color developer of Example 1 (Oyo Kasei Kogyo Co., Ltd., Chemistats) 61
20), (Chemistat 5A- manufactured by Oyo Kasei Kogyo Co., Ltd.)
9) and (Caron 1000 manufactured by Lion Corporation), similar experiments were conducted, and almost the same results as in Example 1 were obtained.

Example 5 Similarly to Example 4, sodium polystyrene sulfonate was added to exemplified compounds (A-1), (A-3), (A-5), (
When similar experiments were carried out by replacing A-6) and (A-12), almost the same results as in Example 1 were obtained.

Example 6 The diethylhydroxylamine used in the experiment of Example 1 was changed to the same number of moles of the hydroxylamine derivative represented by the general formula (II) and hydroxylamine sulfate, and the other conditions were as in Experiment No. 1 of Example 1. An experiment similar to -2 was conducted. A running process was performed using the same processing steps, processing liquid, and color paper as in Example 1 except for the color developing solution.

The yellow reflection density of the highest density area and the magenta tin of the unexposed area of the processed color paper sample after the running process were measured using a Konica densitometer PDA65 (Konica Corporation).
(manufactured by).

The results are summarized in Table 2.

Table 2 From Table 2, it can be seen that the desired effects of the present invention are further promoted by using the hydroxylamine derivative represented by the general formula [I[] in combination with the color developer of the present invention.

Example 7 An endothermal emulsion (Eml) was prepared as follows.

While controlling the aqueous solution containing gelatin at 50°C, a silver nitrate aqueous solution and an aqueous solution containing potassium bromide and sulfur chloride (KBr: NaC4-55: 4 in molar ratio) were mixed.
5) A cubic emulsion with an average grain size of 0.35 μm was obtained by simultaneously adding the components using the tiger control double jet method. Sodium thiosulfate and potassium chloroaurate were added to the core emulsion thus obtained, and chemical ripening was performed at 55° C. for 120 minutes. This emulsion is called Emulsion A.

An aqueous solution containing emulsion A as a core and an aqueous silver nitrate solution, potassium bromide and sodium chloride (KBr in molar ratio)
: NaCQ=20:80) was added at the same time to obtain tetradecahedral particles with an average particle size of 0.46 μI. This emulsion is referred to as Emulsion F.

Sodium thiosulfate was added to this emulsion F to carry out chemical sensitization, and after completion of the chemical sensitization, 9 g of l-phenyl-5-mercaptotetrazole was added per mole of silver halide.

The photographic material shown below was prepared using the above-mentioned internal temperature emulsion (E m -1).

[Preparation of internal temperature type silver halide photosensitive material] On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side, and an internal latent image was prepared to prepare a photosensitive material sample.

Layer l Nidian-forming red-sensitive silver halide emulsion layer Cyan coupler, 2,4-dichloro-3-methyl-6-[α-(2
, 4-di-tert-amylphenoxy)butyramide] phenol 85 g, 2.5-di-tert-octylhydroquinone 2 g 1 tricresyl phosphate 5
Mix and dissolve 190 g of paraffin and 50 g of ethyl acetate, add a gelatin solution containing sodium dodecylbenzenesulfonate, and add the sensitizing dye (per mole of silver halide).
An internal latent image type silver halide emulsion (Em-1) sensitized with 3.3×10-' moles of I[I] was added to obtain a silver amount of 380
mg/m'', (A I dye-1) 19 mg/m'', and coupler amount 340 mg/m'.

Layer 2: Intermediate layer 5 g of gray colloidal silver and 2) 5-di-tert-octylhydroquinone dispersed in dibutyl 7 talate.
100 ml of 2.5% gelatin solution containing Og was applied to give a colloidal silver content of 350 mg/m''.

Layer 3: Magenta-forming green-sensitive silver halide emulsion layer Magenta coupler 1-(2,4,6-trichlorophenyl)-
3-(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone 100g 12.5-Z-ta
r[-octylhydroquinone 5g1 Sumilizer M
DP (manufactured by Sumima Kagaku Kogyo Co., Ltd.) 50g, paraffin 200g
.

Mix and dissolve 100 g of dibutyl phthalate and 50 g of ethyl acetate, add gelatin solution containing sodium dodecylbenzenesulfonate, and add 3.0 g of sensitizing dye (If) per mole of silver halide. A silver halide emulsion (Ern-1) was added to the internal latent image sensitized with 10-' mol of OX to reduce the amount of silver to 31
0mg/l", (AI dye-2) 20mg/m", and coupler amount 350mg/l2.

Layer 4: Yellow Filter Layer Yellow 2.5% gelatin solution containing 5 g of colloidal silver and 5 g of 2) 5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was mixed with colloidal silver 150B.
/s”.

Layer 5: Yellow-forming blue-sensitive silver halide emulsion layer yellow coupler, α-(4-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-driazolidinyl)]
-] α-Vivalyl-2-chloro-5-γ-(2,4-di-tert-amylphenoxy)butyramide] acetanilide 120 g, 2,5-di-tert-octylhydroquinone 3.5 gs, paraffin 200 g, Tinuvin (manufactured by Ciba Geigy) 90 g , dibutyl phthalate 9
0g of ethyl acetate and 7QtaQ of ethyl acetate were mixed and dissolved, a gelatin solution containing sodium dodecylbenzenesulfonate was added, and 3.0g of sensitizing dye was added per mole of silver halide. OX 10-'
Internal latent image type silver halide emulsion (Em-
1), silver amount 350 mg/m'', coupler amount 38
It was applied so that it became 0.gem'.

Layer 6: Protective layer It was applied so that the amount of gelatin was 200 mg/m''.

All of the above layers contained saponin as a coating aid. In addition, as a hardening agent, 2,4-dichloro-6-hydroxyni-s-triazine sodium was added in layers 2.4 and 6 to a concentration of 0.02 g per Ig of gelatin, respectively, in the above-mentioned photosensitive material. After exposure through an optical wedge, the sensitizing dye was processed in the following steps.

Sensitizing dye■ The composition of each treatment liquid is as follows.

[Color developer]

In addition, the concentration of the main drug in the color replenisher is 1.2 of that in the tank liquid.
I doubled it and used it.

[Bleach-fix solution J (Common to tank solution and replenisher solution) Diethylenetriaminepentaacetic acid iron(II[) ammonium salt
65g ammonium thiosulfate
85g ammonium thiocyanate
40g Sodium bisulfite 15g
Sodium metabisulfite 2g Ethylenediaminetetraacetic acid-2-sodium 2g 2-amino-5
・Mercapto-1,3,4-thiadiazole
Add 2.0 g of pure water to make iff, and adjust the pH to 6.0 with aqueous ammonia or acetic acid.

However, the pH was adjusted using 50% potassium hydroxide and 50% sulfuric acid.

[Water washing alternative stabilizer j (common for tank solution and replenisher solution) Ortho-phenylphenol 0.2g Ethylenediaminetetraacetic acid 2g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 5.0g
Bismuth chloride 3g Ammonia water 0.5g Polyvinylpyrrolidone 0.5g Add water to make IQ,
Adjust DH to 7.0 with aqueous ammonia and acetic acid.

The above processing solution was put into an automatic developing machine, and a running test was conducted under the above conditions.

The internal temperature type silver halide photosensitive material prepared above was subjected to running processing at a rate of 15 days per day. After the running process was completed, the maximum density cyan reflection density and magenta tin of the processed paper were measured.

Table 3 From Table 3 above, it can be seen that when a polystyrene sulfonic acid derivative is used in the color developing solution and the treatment is performed with a specific coloring agent and concentration, magentastin and maximum density are good.

[Example 8] The same experiment as in Example 1 was conducted except that the fluorescent whitening agent in the color developing solution used in the experiment of Example 1 was changed as shown in Table 4 below. The remaining color stain and magenta stain of the color paper after processing were measured.

The results are summarized in Table 4. - Margin Table 4 below [Effects of the Invention] According to the present invention, the stability of the color developing solution is significantly improved, and as a result, the occurrence of residual color contamination is significantly reduced even when processing with a used solution that has been aged for a long time. An excellent color image was obtained, which was suppressed and free of magentastin, and had sufficient dye density.

Such effects of the present invention were clearly observed in color papers that are rapidly and continuously processed.

optical brightener (W’-1)

Claims (2)

[Claims] (1) Contains at least 1.3 x 10^-^2 mol/l of a color developing agent represented by the following general formula [1], and at least one selected from polystyrene sulfonic acid derivatives. A color developer for silver halide color photographic materials. (2) A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution according to claim (1). General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents a hydrogen atom, a halogen atom, or an alkyl group; At least one of R^2 and R^3 represents an alkyl group substituted with a water-soluble group or the formula ■CH_2■_mO■_nR^4. R^4
represents a hydrogen atom or an alkyl group, and m and n represent integers of 1 to 5. ]