JPS62283336A - Silver halide color photographic sensitive material capable of rapid processing and having excellent shelf life - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of the rapid processing and having the good shelf life and processing stability by incorporating a specific compd. and a nitrogen contg. heterocyclic compd. having mercapto group to a photographic constituting layer. CONSTITUTION:At least one kind of the compd. selected from the compds. shown by formulas I and II, is incorporated to at least one layer of the photographic constituting layers. At least one layer of the photographic constituting layers contains at least one of the nitrogen contg. heterocyclic compd. having at least one of the mercapto group. In the formulas, R<1> and R<2> are each hydrogen atom or alkyl group, R<3> is halogen atom, alkyl or aryl group, R<4> is hydrogen atom or aryl group, (n) is an integer of 0-5, X and Y are each a group capable of releasing by hydrolysis. Said groups may be substd. The compd. shown by formula I or II is exemplified by a precursor of 3-pyrazolidone compd. The representative example of the heterocyclic ring mercapto compd. is concretely shown by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and in particular to a precursor of a 3-pyrazolidone compound.
This invention relates to a silver halide color photographic material containing.

Specifically, the present invention relates to a halogenated color photographic material that can be rapidly processed, has good processing stability, good storage stability, and provides high sensitivity.

[Prior art]

In recent years, there has been a desire in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have good storage stability, have excellent processing stability, and are low cost. In particular, silver halide color photographic materials that can be rapidly processed are desired.

In other words, \Rogenized color photographic light-sensitive materials are subjected to running processing in the automatic developing machines installed at each Laboratory IJ. It is now required that the product be processed and returned to the user within a few hours, and in recent years, it has even been requested that the product be returned within a few hours of receiving the product.
There is an urgent need to develop silver halide color photographic materials that can be processed more rapidly. In addition, in running processing, photographic properties vary greatly between laboratories or even within the same laboratory due to changes in the composition of the processing solution and fluctuations in conditions, making it difficult to obtain stable photographic performance and resulting in poor processing stability. There's a problem. Processing stability here refers to the degree of variation in sensitometry with respect to fluctuations in processing solution composition, pit, temperature, and contamination of other compounds other than the processing solution composition. Such changes in the composition of the processing solution and fluctuations in conditions are considered to be due to contamination of other processing solution components during development processing (running), elution and accumulation of photographically active substances from the light-sensitive material, and other causes.

The accumulation of purchases of other processing liquid components becomes noticeable when the amount of processing liquid replenishment decreases and the rate at which the tank liquid is replaced with replenishment liquid becomes low, and becomes even more noticeable when the monthly use of the liquid becomes longer. Become. The above-mentioned "contamination with other processing solutions" is the so-called "contamination of other processing solutions" in which components of the processing solution after development are brought into the color developing solution by spranoches of neighboring processing solutions, conveyance leaders, belts, hangers for hanging the film, etc. in the processing machine. Caused by back contamination. Among these accumulated contaminants, periosulfate ion, which is a fixing agent, accelerates development. That is, this problem occurs particularly when bleach-fixing is performed directly after color development. In particular, by promoting the shield part of the photographic characteristic curve, remarkable high contrast is produced. In addition, increased contamination of metal salts as bleaching agents, especially ferric salts, promotes the decomposition of hydroxylamine as a preservative, producing 7-monomer ions. The generation of ammonia ions promotes physical development in the same way as periosulfate ions, resulting in high contrast.

Such fluctuations in photographic performance due to changes in the composition of the processing solution and slow changes in conditions are a problem even with current processing times, but they become a bigger problem in rapid processing.

Therefore, if we look at the conventional techniques for silver halide color photographic materials that can be processed rapidly, for example,
Silver halide micrograining technology as described in No. 1-77223, ■ JP-A-58-184142, JP-A-56-1
1-aryl-3-birapritone having a specific structure as described in JP-A-56-64339 in a silver halide color photographic light-sensitive material. Addition technology, and JP-A-57
-144547, 58.50534, 58-5
0535 and No. 5B-50536 are known, in which l-arylpyrazolidones are added to silver halide color photographic materials, and in addition, A technique of using a color development accelerator when developing a material using an aromatic primary amine color developing agent is also known. For example, such color development accelerators are described in U.S. Pat.
, No. 970, No. 2,515゜147, No. 2,496,
No. 903, No. 4,038,075, No. 4゜119.4
No. 62, British Patent No. 1,430.998, British Patent No. 1,455
, No. 413, JP-A No. 53-15831-1, No. 55-6
No. 2450, No. 55-62451, No. 55-6245
No. 2, No. 55-62453, No. 51-12422,
There are compounds described in Japanese Patent Publication No. 55-62453, Japanese Patent Publication No. 51-12422, Japanese Patent Publication No. 55-49728, and the like.

However, when using ■ or ■ of these conventional techniques,
Although the processing time was shortened, the processing stability was poor, and there were also problems with fogging and storage stability in same-day performance.

When the low silver bromide emulsion (2) is used, less bromide ions are eluted into the processing solution from the silver halide color photographic light-sensitive material containing the low silver bromide emulsion, and the concentration of bromide ions in the processing solution is low. Although it is possible to achieve rapid processing because the bromine ion concentration can be set low, processing stability is poor when a silver halide color photographic light-sensitive material containing a low silver bromide emulsion is processed using a processing solution with a low bromine ion concentration.

Furthermore, when the fine-grained silver halide of (1) was used, there was a drawback (B) of poor processing stability, and another drawback was that the finer the grain, the lower the sensitivity.

Among these conventional techniques, a method of incorporating 3-pyrazolidones into a photographic light-sensitive material is one that has a particularly large effect of accelerating development. Pyrazolidones may act on silver halide to generate fog nuclei, or themselves may become oxidized and lose their effectiveness, or the oxidation products may bleach and desensitize the photosensitive nuclei of silver halide. , sufficient photographic performance could not be obtained.

In order to solve this problem, a method has been proposed in which, instead of using 3-pyrazolidones themselves, they are incorporated as a precursor that is decomposed by an alkali and releases 3-pyrazolidones. The advantage of these compounds is that they do not act on silver halide prior to development and do not undergo air oxidation, and by optimizing the compound, the timing of release during development can be controlled. The following are known examples of these precursors: That is, JP-A-55-53
330, 55-73048, 57-135949
, 57-179842, 58-1139, 5
8-1140, 58-117544, 57-1
9732, 57-40245, 59-93442,
59-104641, 59-116649, 5
9-121328, 59-137945, 59-
140445, 59-197037, 59-1
98453, 59-201057, 59-202
459, 59-218439, 59-21974
1, 60-41034, 60-53950, 6
0-53951, 61-32839, GB-2073
734, EP 45129, BE 863052, U
Compounds described in SP 4.358,525, RD (Research Disclosure)-181042, etc. are known.

However, using only these compounds does not provide all the characteristics such as rapid development and sufficient photographic performance, that is, high sensitivity, low fog, good processing stability, and good storage stability. It was impossible to obtain a satisfactory color photographic material.

[Problem that the invention seeks to solve]

The present invention has been made in view of the above, and an object of the present invention is to provide a silver halide color photographic material that can be rapidly processed, has good storage stability, and has improved processing stability. shall be.

[Means for solving problems]

The above technical object is achieved by the following silver halide color photographic light-sensitive material of the present invention.

That is, the silver halide color photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant aqueous coupler on a support. contains at least one compound selected from the group of compounds represented by the following general formulas (1) and (II), and at least one of the photographic constituent layers contains at least one This is a silver halide color photographic light-sensitive material characterized by containing a nitrogen-containing heterocyclic compound having two mercapto groups.

[In the formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group, R3 represents a halogen atom, an alkyl group, or an aryl group, R4 represents a hydrogen atom or an aryl group, and n represents an integer of 0 to 5. , X and Y represent groups that can be separated by hydrolysis.

Each of the above groups also includes those containing π-converted water. ]Also the above-
The present invention also includes light-sensitive materials containing compounds represented by formulas (+) and (■) in combination.

As a result of continuing intensive research to solve the above-mentioned technical problem, the present inventors have discovered the precursor of the 3-pyrazolidone compound of the present invention represented by the formula (■) and (II) and the present invention. The inventors have discovered that the objective can be achieved by selecting a heterocyclic mercapto compound, and have completed the present invention.

The present invention will be explained in more detail below.

The compound represented by the general formula (1) or ([1) used in the silver halide color photographic material of the present invention is a precursor of a 3-pyrazolidone compound.

The compound represented by the general formula (1) or (II) of the present invention will be explained in detail below.

The compound represented by the general formula (1) or (II) of the present invention can be used, for example, in JP-A-55-53330 and JP-A-55-73048.
, 57-135949, 57-179842,
58-1139, 58-1140, 58-11
7544, 57-19732, 57-40245
, 59-93442, 59-104641, 5
9-116649, 5-121328, 59-
137945, 59-140445, 59-1
97037-59-198453, 59-201
057, 59-202.459, 59-218
439, 59-219741, 60-4103
4, 60-53950, 60-53951, 61
-32839, GB-2073734, EP 4512
9, BE-863052, USP 4,358,525
．． 1? D (Research Disclosure)-1810
42 etc.

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

Margin 7th1) - These precursors of the 3-pyrazolidone compound of the present invention can be easily synthesized by the method described in the above-mentioned exemplary patent or in accordance therewith.

The precursor of the 3-pyrazolidone compound of the present invention is:
It can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer.

The precursor of the 3-pyrazolidone compound of the present invention is 2
It may contain more than one species, or may be contained in two or more different layers.

The amount of the precursor of the 3-pyrazolidone compound of the present invention is generally 0.1 n+g per 1 photosensitive material.
-100m, more preferably 5mg - 50mg.

In order to incorporate the precursor of the 3-pyrazolidone compound of the present invention into a photographic light-sensitive material, if the compound is water-soluble, it may be added as an aqueous solution, or if it is alkali-soluble, it may be added as an alkaline solution. It's okay,
In addition, if it is oil-soluble, it may be added after being dissolved in a suitable aqueous solvent.
No. 27, No. 2,801.170, No. 2,801,
No. 171, No. 2.272.191 and No. 2, 3
According to the method described in each specification of No. 04.940, the compound of the present invention may be dissolved in a high-boiling point solvent, optionally in combination with a low-boiling point solvent, and dispersed and added onto fine particles.

Next, the heterocyclic mercapto compound of the present invention will be further explained.

The nitrogen-containing heterocyclic compound having at least one memercapto group used in the present invention includes an imidaline ring, an imidazole ring, an imidacilone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxacilone ring, Thiazoline ring, thiazole ring, thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benzoxazole ring, benzthiazole ring , benzoxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring (e.g. triazaindene ring, tetrazaindene ring, pentazaindene ring) It is preferable to choose from the following. Among these, particularly preferred heterocyclic turcapto compounds include:
These are mercaptooxadiazole, mercaptothiadiazole, mercaptotriazole, mercaptotetrazole, mercaptobenzimidazole, mercaptobenzoxazole, and mercaptobenzthiazoles represented by the general formulas (I[I), (IVY, and (V)).

In the formula, R3 is a hydrogen atom, an amino group, a hydroxyl group, a hydrazino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryol group, -NHCORh group, -NH3O,R
' group, -3R'' group.

In the formula, R2 represents an alkyl group, an aryl group, an alkenyl group, or a cycloalkyl group.

In the formula, Rff, R4, and R' are each a hydrogen atom, mercapto group, amino group, hydroxyl group, hydrazino group, alkyl group, alkenyl group, cycloalkyl group, aryl group, -NHCOR'' group, -NH3O□R1° group ,-S
Rl l group, nitro group, cyano group, halogen atom, Q
RI Z group, -COR'3 group, -3O□R, 5OtR
14 groups, -CONHR" group, -5Ox N HR" group,
NHCONHRI7 group, -COORI I+ group, -NH
cooR" group, -0CONHR" group, etc., and R'ff
l R:, At least one of R' represents a mercapto group.

In the formula, Y' is a hydrogen atom, an amine group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -CONHR''
group, -COR" group, -NHCOR2" group, N HS
02R" group. In the formula, Z represents a nitrogen atom, a sulfur atom or an oxygen atom. n represents 1 when Z is a nitrogen atom, and represents O when Z is an oxygen atom or a sulfur atom.

R''' to R24 are each an alkyl group, an alkenyl group,
Represents a cycloalkyl group or an aryl group.

To explain the general formulas (m), (■), and (v) in detail, the alkyl groups represented by R:, R',, R;, R2, R5, and Y' are carbon atoms. Numbers 1-18
, later are preferred, such as methyl group, ethyl group, propyl group, butyl group, octyl group, isopropyl group, benzyl group, etc. Examples of cycloalkyl group include cyclohexyl group, cyclopentyl group, etc. (Alkenyl group includes cyclohexyl group, cyclopentyl group, etc.) Those having 2 to 18 carbon atoms are preferable, such as allyl group, octenyl group, etc., and examples of aryl group include phenyl group, naphthyl group, etc. 6 Further, as the alkyl group represented by Rh''R24, carbon atom A straight chain or branched one having numbers 1 to 18, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.The alkenyl group preferably has 2 to 18 carbon atoms, such as an allyl group, an octenyl group, an octadecenyl group, and an aryl group. Examples of the group include phenyl group and naphthyl group.

In addition, an alkyl group represented by R, RR4 and Y',
Each of the cycloalkyl group, alkenyl group, and aryl group may have a substituent, and examples of such substituents include alkyl group, cycloalkyl group, aryl group, alkenyl group, halogen atom, nitro group, and cyano group. , mercapto group, 7mino group, carboxyl group, hydroxyl group,
Examples include sulfo group, alkoxy group, alkylthio group, alkoxycambonyl group, alkylamino group, and aryloxycarbonyl group.

Furthermore, the compounds represented by the general formulas (I[I), [IV], and (V) of the present invention exhibit sewage-like tautomerism.

N-N　　　　　　　　　　N-NHH The present invention also includes these tautomers.

Typical specific examples of the heterocyclic mercapto compound of the present invention are described below, but the present invention is not limited thereto.

I -11-2 1-3f -4 1-5I-6 ! -7 CH Cz Hs CHz CH= CHz ~ IN ■ -15 ■ -18 ~ He ■ -19 r-24CH3 I-26 ■ -27 l ■ -28 ■ -30 ! -31 ■ -33 ■ -36 1,zH8 ■ -37 C8゜■ -38 ■ -39 ■ -40 ■ -44 ■ -46 ■ -47 ■ -48 -N ■ -50 ■ -51 ■ -52 ■ - 53 ■ -54 ■ -55 ~ N I -56 ■ -57 ■ -59 ■ -62 n ■ -63 ■ -64 i ■ -66 CzH,Cf ■ -67 ■ -69 C41b (n) ■ -70 ■ - 71 ■-72 ■-73 H ■ -78 CH u■ -79 zHs ■ -80 ■ -81 ■ -82 ■ -86 ■ -89 n 1-91 H ■-97 ■ -98 S Oz H! -99H,■! -100H p~■ cto, Q The above compounds are generally known, and are disclosed in, for example, JP-A-51
-107.129, 4B-102,621, 55-59.463, 59-124.3
It is described in the following publications: No. 33, No. 61-48.832, and British Patent No. 1.204,623.

The heterocyclic mercapto compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer, but it is preferably added to a light-sensitive silver halide emulsion layer.

The heteromeric mercapto compound of the present invention may be contained in two or more types, and may be contained in two or more different layers.

These heteromeric mercapto compounds of the invention generally contain 10-s mol-10-4 mol per 1%, preferably 10-s mol-10-4 mol/%.
-1 mole - 10''s mole is used.

Further, the hetero-sensitive mercapto compound of the present invention may be added as an alkali metal salt, for example, a sodium salt, a potassium salt, a lithium salt, or the like.

Further, the precursor of the 3-viratritone compound of the present invention and the hetero-sensitive mercapto compound may be contained in the same layer or in different layers.

Preferably, they are contained in the same layer or adjacent layers.

The amount of silver in the silver halide emulsion layer (Bank M) of the silver halide color photographic material of the present invention in the optical material is preferably 0.3 to 1 g/r+ (i.e. , in order to obtain excellent image quality, the amount of silver must be Ig/
On the other hand, in order to obtain a high maximum concentration and high sensitivity, the amount of cough silver is preferably 0.3 g/m or more. In the present invention, the silver ffi is particularly preferably 0.4-0.8 g/rrl.

Silver halide compositions preferably used in the present invention include silver chlorobromide and silver chloroiodobromide. Furthermore, a combination mixture may be used in which silver chloride and silver bromide are mixed separately, that is, when the silver halide emulsion according to the present invention is used in a color photographic paper. In particular, since fast developability is required, the silver halide preferably contains a chlorine atom as a halogen composition, and is particularly preferably silver chlorobromide or silver chloroiodobromide containing at least 1% silver chloride. preferable.

The monodisperse silver halide grains preferably used in the present invention may be obtained by any conventionally known preparation method such as an acidic method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, PHLrAg etc. in the reaction vessel are controlled, and the amount of silver ions and halides commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A No. 54-48521. It is preferable to implant and mix the ions sequentially and simultaneously.

1tJ WJJ of silver halide grains used in the present invention is carried out, for example, as described above. A composition containing silver halide grains as described above is hereinafter referred to as silver halide emulsion 11.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium enhancers; reduction enhancers such as stannous salts, sulfur dioxide, Polyamines, etc.; Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-
Exacerbating agents such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chlorovaladate (these Depending on the amount, they act as y-enhancing agents or fog suppressants. It may also be chemically exacerbated (e.g. in combination with selenium aggravating agents).

The silver halide emulsion used in the present invention is prepared by adding a sulfur-containing compound to form a chemical compound, and before, during, or after chemical ripening, a nitrogen-containing emulsion containing at least one hydroxytetrazaindene and mercapto group is prepared. At least one type of hete L'J ring compound may be contained.

The silver halide used in the present invention is optically prepared by adding a suitable aggravating dye in an amount of 5X10-" to 3X10-" mole per mole of silver halide in order to impart photosensitivity to a desired wavelength range. It may be sensitized.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat.
, No. 503.776, No. 2,519.001, No. 2,
No. 912,329, No. 3.656,959, No. 3,6
No. 72,897, No. 3,694,217, No. 4,02
No. 5,349, No. 4,046,572, British Patent No. 1,
No. 242.588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
, No. 072,908, No. 2,739.149, No. 2,
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945,763, British Patent No. 505,979, and the like. Furthermore, as the enhancing dye used in the red-sensitive silver halide emulsion, for example, U.S. Pat.
No. 2,270゜378, No. 2,442,710, No. 2,454.629, No. 2゜776.280, etc. This can be cited as a representative example. Additionally, U.S. Patent 2,213,995
Green-sensitive silver halide emulsions or red-sensitive cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,493,748, No. 2519.001, West German Patent No. 929,080, etc. It can be advantageously used in silver halide emulsions.

These aggravating pigments may be used alone or in combination. Combinations of enhancing dyes are often used, especially for the purpose of supersensitization.

Typical examples are U.S. Patent Nos. 2.688545 and 2.97.
7. No. 229, No. 3, No. 397, No. 060, No. 3, 5
No. 22,052, No. 3,527゜641, No. 3,61
No. 7,293, No. 3.628.964, No. 3.666
, No. 480, No. 3,672,898, No. 3.679.
No. 428, No. 3,703,377, No. 3,769,3
No. 01, No. 3,841,609, No. 3,837,86
No. 2, British Patent No. 4,026,707 1゜344.2
No. 81, No. 1,507,803, JP-A-43-493
No. 64, No. 53-12375, JP-A-52-1106
No. 18, No. 52-109925.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hekioxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioxenol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584.609 and British Patent No. 1,27.
7.429, JP-A-48-85130, JP-A No. 49-9
No. 9620, No. 49-114420, No. 49-129
No. 537, No. 52-108115, No. 59-2584
No. 5, U.S. Patent No. 2,274,782, U.S. Patent No. 2,533,
No. 472, No. 2,956,879, No. 3,125,4
No. 48, No. 3.148゜187, No. 3.177, 07
No. 8, No. 3,247,127, No. 3゜540, 887
No. 3,575,704, No. 3,653.905, No. 3,718.472, No. 4,071,312,
It is described in No. 4,070,352.

Each of the silver halide emulsion layers in the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers.

These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow couplers include conventionally used closed ketomethylene compounds, active point -0-aryl substituted couplers called so-called two-equivalent type couplers, active point -0-acyl substituted couplers, active point hydantoin compound substituted couplers, and active point -0-aryl substituted couplers. Couplers substituted with urazole compounds, couplers substituted with succinimide compounds at the active site, couplers substituted with fluorine at the active site, couplers substituted with chlorine or bromine at the active site, couplers substituted with -0-sulfonyl at the active site, etc. can be used as effective yellow couplers.

Specific examples of yellow couplers that can be used include US Pat.
, No. 875.057, No. 3.265.506, No. 3,
No. 408,194, No. 3,551,155, No. 3,5
No. 82,322 No. 3,725゜072, No. 3,891
, No. 445, West German Patent No. 1547.868, West German Application No. 2,219,917, No. 2,261,361, No. 2.414,006, British Patent No. 1,425.020, Japanese Patent Application Publication No. 1973 No.-10783, JP-A-47-26133
No. 48-73147, No. 51-102636,
No. 50-6341, No. 50-123342, No. 50
-130442, 51-21827, 50-87
No. 650, No. 52-82424, No. 52-11521
No. 9, No. 58-95346, etc. 8 It is possible to list things that have been forgiven.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds.

These magenta couplers are similar to the yellow couplers 4
It may be a two-equivalent type coupler as well as an ordinary coupler. A specific example of a magenta coupler is US Patent 2.
, No. 600.788, No. 2,983.608, No. 3.
No. 062.653, No. 3,127.269, No. 3゜3
No. 11.476, No. 3,419,391, No. 3,51
No. 9,429, No. 3,558,319, No. 3.582
, No. 322, No. 3,615,506, No. 3,834.
No. 908, No. 3,891,445, West German patent 1.81
No. 0,464, West German Patent Application (OLS) 2,40
No. 8.665, No. 2,417,945, No. 2,418
, No. 959, No. 2,424, No. 467, Special Publication No. 1973-
No. 6031, JP-A-51-20826, JP-A No. 52-58
No. 922, No. 49429538, No. 49-74027
No. 50-159336, No. 52-42121,
No. 49-74028, No. 50-60233, No. 51
-26541, 53-55122, patent application 1982-
Examples include those described in No. 110943 and the like.

Further, examples of the cyan coupler used in the present invention include phenol couplers, naphthol couplers, and the like. And these cyan couplers are not 4-pin @ type couplers like the yellow couplers,
It may also be a two-way type coupler. Specific examples of cyan couplers include U.S. Patent Nos. 2.369.929 and 2,4
No. 34,272, No. 2,474゜293, No. 2,52
No. 1,908, No. 2,895.826, No. 3.034
．． No. 892, No. 3,311,476, No. 3.458,
No. 315, No. 3,476.563, No. 3.583.9
No. 71, No. 3,591゜383, No. 3,767.41
No. 1, No. 4,004,929, West German patent application (OL
S) 2,414.830, 2,454.329, JP-A-48-59838, JP-A-51-26034,
No. 48-5055, No. 51-146827, No. 52
-69624, 52-90932, 58-95
Examples include those described in No. 346 and the like.

In order to incorporate these couplers into the silver halide emulsion in the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution; if they are oil-soluble, they may be added as an alkaline solution, for example, as described in US Pat. 2,322,0
No. 27, No. 2,801,170, No. 2,801,
No. 171, No. 2,272,191 and No. 2.3
It is preferable to dissolve the coupler in a high-boiling point solvent and, if necessary, in a low-boiling point solvent in accordance with the method described in each specification of No. 04,940, and to disperse the coupler in the form of fine particles and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones,
Urea derivatives, ethers, hydrocarbons, etc., especially di-n-
Butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate,
Di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl,
N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-di-5ec-amylphenyl butyl ether, monophenyl-zilow chlorophenyl phosphate Alternatively, a high boiling point solvent such as fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycoacetate, nitromethane, carbon tetrachloride,
Dissolved in a low boiling point solvent such as chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate and sorbitan. It is mixed with an aqueous solution containing a nonionic surfactant such as monolauric acid ester and/or a hydrophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion device to form a silver halide emulsion. added.

In addition, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Specification Publication and Research Disclosure, August 1976, No. 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like.

The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. , a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, fluorescent substances such as albumin and casein, Any of cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761,791;
．． 94L, No. 898, a simultaneous coating method of two or more layers can be used.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, a blue-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer,
It is preferable to arrange a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

In these constituent layers, hydrophilic colloids that can be used in the silver halide emulsion layer as described above can be similarly used as a binder, and they may be contained in the emulsion layer as described above. Various photographic additives can be included.

There are no particular limitations on the method of processing the silver halide color photographic light-sensitive material according to the present invention, and any processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary; bleaching and fixing are performed separately after color development; A method in which water washing and/or stabilization treatment is performed; or a method in which prehardening, neutralization, color development, stop fixing, water washing, bleaching, fixing, water washing, post hardening, water washing, color development, water washing, and supplementary processing are performed. A method in which color development, stopping, bleaching, fixing, washing, and stabilization is performed in this order, and a development method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of produced dye, etc. It may be processed using the following method.

The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably a pH of 9 to 12.

The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethylene-N-β
-Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3
-acetamide, 4-amino-N.

N-dimethylaniline, N-ethyl-N-β-[β-(
β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates, hydrochloride, sulfite,
p-toluenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set; however, in order to increase the activity, it is preferable to increase the amount used. The amount used ranges from 0.0002 mol/β to 0.7 mol/l. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Any combination of ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline may be used depending on the purpose.

The color developing solution used in the present invention further contains various commonly added components, such as alkali agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkaline earth halides, benzyl alcohol,
A water softener, a thickening agent, a development accelerator, etc. can also be optionally included.

However, it is preferable that benzyl alcohol is not added to the color developing solution.

In other words, benzyl alcohol has a pollution load value of BO
D-? ) Since benzyl alcohol has a high COD and low hydrophilicity, diethyl glycol or triethylene glycol is required as a solvent, but glycols also have high BOD and COD, so they are discarded due to overflow. The processing liquid used in this process has the problem of environmental pollution. Furthermore, benzyl alcohol has low solubility in a developer and requires a long time to prepare a developer or a replenisher, which poses operational problems. Furthermore, if the amount of replenishment is large, the number of times the replenisher must be prepared increases, which also becomes a burden on the work.

Therefore, it is very preferable that the color developing solution does not substantially contain benzyl alcohol, since environmental pollution and operational problems can be eliminated.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Compounds for rapid processing solutions such as alkali iodide, nitrobenzimidazole, metcaptobenzimidazole, 5-methyl-benzotriazole, ■-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. It may also contain an agent. Further, when a bleach-fix solution is used in the bleaching step, a solution containing a halogenation-limiting binder in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As with the bleach solution mentioned above, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added. It may be added or contained.

Examples of silver halide fixing agents include sodium thiosulfate, ammonium periosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, thioether, and other silver halide fixing agents that react with silver halide and are used in ordinary fixing processes. Mention may be made of compounds that form water-soluble silver salts.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 5B-1
No. 34634 and No. 5B-18631 and patent application No. 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

[Example 1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Silver halide color photographic material No. 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side.

Layer 1-...1.2 glrdO) Gelatin, 0.32
g/m (silver equivalent, the same applies hereinafter) of front window silver chlorobromide emulsion (
A layer containing yellow coupler (Y-1) of 0.80 g/n dissolved in dioctyl phthalate with a particle size of 0.8 mol m) and 0.508/m.

Layer 2...0.70 g/m gelatin, 8 mg/m irradiation dye <Al-1) and 4 mg/- (AI
-2) the middle layer consisting of;

Layer 3...1.25g/m no gelatin, 0.20g/m
m-green chlorobromide emulsion (silver bromide content 70 mol%),
Layer N4 containing 0.62 g/- of magenta coupler (M-1) dissolved in 0.30 g/rr of dioctyl phthalate...intermediate layer consisting of 1.20 g/m of gelatin.

Layer 5...1.20 g/m gelatin, 0.30 g/m red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0
．． 0 dissolved in 20g/rd dioctyl phthalate
, 45 g/n (containing cyan coupler (C-1)).

Layer 6...1.00gzm? of gelatin and 0.20
0,30 dissolved in g/rd dioctyl phthalate
A layer containing ultraviolet absorption (UV-1) of g/rd.

Layer 7: Layer containing 0.50 g/rd of gelatin.

(Y-1) I UV-1> H As a hardening agent, 2.4-dichloro-6-hydroxy-3-) riazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

Further, in layer 1, the heterocyclic mercapto compound Th of the present invention (the amount added is shown in Table 1) was added, and in layer 2, the precursor of the 3-pyrazolidone compound of the present invention 5X10-'mol #+ (or the comparative compound 5X Table 1: 10-'mol/td
Samples t'h2 to t'h2 to t'h9 were prepared in the same manner as the above sample 1Vh1 except that they were added as follows.

The above photosensitive material sample! After each of lkl~9 was exposed through an optical wedge, it was processed in the next step.

Processing steps (35°C) Color development 1 minute and 1 minute 30 seconds Bleach fixing 1 minute water washing 1 minute drying 60-80°C 2 minutes The composition of each processing solution is as follows.

Color developer A> Pure water 800ml Hydroxyamine sulfate 2.0g Potassium bromide
1.5g sodium chloride
1.0g potassium sulfite 2.
0 g triethanolamine 2.0 g N-ethyl-N-β methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 8.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution)
1.5ml potassium carbonate 32g
Whitex BB (50% aqueous solution) 2
ml (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 12% potassium hydroxide or 10%
Adjust pH to 11.2 with dilute sulfuric acid.

<Bleach-fix solution> Pure water 550ml Iron ethylenediaminetetraacetate (1) Ammonium 65g Ammonium thiosulfate 85g Sodium bisulfite
Log sodium metabisulfite 2g
20g of sodium ethylenediaminetetraacetic acid-2-sodium 10g of sodium bromide Add pure water to bring the mixture to 1N, and adjust to pi (=7.0) with aqueous ammonia or dilute sulfuric acid.

Sensitometry was performed on each sample after the above treatment,
The sensitivity and capri of the pre-malignant emulsion layer were determined.

In addition, for the above samples 1 to 9, 50°C, 70%
The raw samples were forced to deteriorate by being left under RH conditions for 6 days, and the storage stability of the raw samples was evaluated by performing the same treatment as above (however, the color development time was only 1 minute and 30 seconds).

The results are shown in Table 1.

Phenidone, a comparative compound, has the following structure.

As is clear from Table 1, although sample 2 with phenidone added is rapid, the same-day sensitivity is low, and -1
Poor storage stability. Sample No. 3 to which the precursor of the 3-pyrazolidone compound of the present invention was added was able to achieve rapidity and improved storage stability, but it cannot be said to be sufficient yet. On the other hand, sample 11h4 using only the heterocyclic mercapto compound of the present invention has satisfactory storage stability, but cannot be stored quickly. Furthermore, even when the heterocyclic mercapto compound of the present invention is used in combination with phenidone (test $4Nn 5 ), the storage stability is not satisfactory, and the photographic performance (sensitivity) in 1 minute rapid processing is not sufficient. I can not say. On the other hand, samples lI & 1 in which the precursor of the 3-bizolidone compound of the present invention and the heterocyclic mercapto compound of the present invention were simultaneously used.
It can be seen that all of the samples with grades 1.6 to 9 have excellent photographic performance in rapid processing and have good storage stability.

Example 2 After exposing each of the holes 9 from the sample 11kLL of the present invention to light through an optical wedge, color development/F1. B was used in the next step.

Processing process (35℃) Color development 45 seconds and bleach fixing for 1 minute 15 seconds
Washing with water for 1 minute, drying for 1 minute, drying at 60-80 DEG C. for 2 minutes. Sensitometry was performed on each sample after the treatments described in section 2 to determine the sensitivity and fog of the growing emulsion layer.

The results are shown in Table 2.

゛) Table-2 *3 Margin less than the relative value with the haze of 1 minute 15 seconds development of sample floor 1 as 100 ・4 From Table 2, the same tendency as the above example was observed in this example. It can be seen that the inventive samples exhibit excellent photographic performance.

Furthermore, as is clear from Table 2, sample m2 containing phenidone. N15 has no sensitivity after development.

On the other hand, the sample of the present invention can finally obtain sufficient sensitivity.

Example 3 For the above samples 11hl to 9, the bleach-fix solution was 0.6 mj for the color developer B11! was added and the same treatment was carried out to determine the variation in gamma value (.gamma.) compared to the case in which the bleach-fix solution of Example 2 was not added.

The results are shown in Table 3.

Processing step (35°C) Color development 1 minute 15 seconds Bleach fixing 1 minute water washing 1 minute drying 60-80°C Samples No. 3 and No. 4, in which the precursor of the 3-virapritone compound and the heterocyclic mercapto compound of the present invention were added alone, showed an improvement in gamma value fluctuations with respect to contamination with bleach-fix solution compared to sample No. 11hl. However, in Samples 6 to 9 of the present invention in which both were used in combination, even more remarkable improvement in process variation characteristics was observed.

Further, in samples 2 and 5, a decrease in gamma value was observed due to the addition of phenidone, but sufficiently high gamma values were obtained in samples 6 to 9 of the present invention.

〔Effect of the invention〕

As described above, according to the present invention, rapid processing is possible,
A silver halide color photographic material having good storage stability and improved processing stability can be obtained.

Patent applicant Konishiroku Photo Industry Co., Ltd. Agent Patent attorney Toru Takatsuki Procedural amendment (
July 28, 1985 Director General of the Patent Office Michibe Uga 1, Indication of the case 1985 Patent Application No. 083759 3, Relationship with the person making the amendment Patent applicant address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, subject of amendment by agent 66 Specification (12) ``Alikenyl group'' on page 28, lines 5-6 of the same specification as ``
"alkenyl group".

(13) "In the formula R*, R#+ R'" on page 28, line 7 of the same
``is'' is corrected to ``in the formula, R,', R4', R'is''.

(14) "Alkenyl group" on page 28, line 9 is corrected to "alkenyl group."

(15) rR3', R,', R' on page 28, line 16
"among" is corrected to "among rRx', Ra', R'".

(16) "Alkenyl group" on page 30, line 3 of the same page is corrected to "alkenyl group" (17) "Also, the above R7 to R24" on page 30, line 8 of the same page
.--and the above-mentioned R1' to R2'.

(18) "Alkoxycambonyl group" on page 30, lines 15-16 is corrected to "alkoxycarbonyl group."

(19) The three reaction formulas described on page 31 of the same are corrected as follows.

(Y'), l (Y'), 1j (Y'), (Y'), 1
i (20) "Hetero-sensitive mercapto compound" on page 55, lines 10, 13, 16, and 20 is corrected to "heterocyclic mercapto compound."

(21) "Silver amount (rooting amount) photosensitive silver halide emulsion layer" on page 56, lines 4 to 5 is corrected to "silver amount (rooting amount) is photosensitive silver halide emulsion layer."

(22) "Hemioxonol dye" on page 61, line 12 is corrected to "hemioxonol dye."

(23) "Hemioxonol dye" on page 61, line 14 is corrected to "hemioxonol dye."

(24) "Diethylene glycoacetate" on page 67, lines 10-11 is corrected to "diethylene glycol monoacetate."

(25) "Cyclohexanetetrahydrofuran" on page 67, lines 12-13 is corrected to "cyclohexane, tetrahydrofuran."

(26) "Blue-sensitive silver chlorobromide emulsion (grain size 0.8 mol m)," on page 79, lines 12-13 of the same book, was replaced with "blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol %)." ),” is corrected.

(27) The structural formula of r(Y-1)J on page 80 of the same is corrected as follows.

r(Y-1) (28) The structural formula of r(A I-2)J on page 81 of the same is corrected as follows.

r (AI-2) (29) "1" in the section of sample tooth 4 in Table-2 on page 89 of the same
Correct ro, 08J in the ``Capri'' column of ``Minute 15 Second Development'' to ro, 06J.

(30) "1" in the column of sample floor 9 in Table 2 on page 89 of the same
Correct "r102J" in the "Fog" column of "Minute 15 Seconds Development" to "ro, 08J".

Above (Amended "Claims" column) Claims A silver halide photographic light-sensitive material comprising a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support. , at least one of the photographic constituent layers contains at least one compound selected from the group of compounds represented by the following general formulas ([) and (II), and at least one of the photographic constituent layers contains: A silver halide color photographic light-sensitive material containing a nitrogen-containing heterocyclic compound having at least one mercapto group.

General formula (I) General formula (n) [In the formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group, R3 represents a halogen atom, an alkyl group, or an aryl group, and R4 represents a hydrogen atom or an aryl group. represents a group, n is O~5
, and X and Y represent groups that can be separated by hydrolysis. Indication of the case 1983 Patent application No. 083759 2, Name of the invention Silver halide color photographic light-sensitive material that can be processed quickly and has excellent storage stability 3, Person making the amendment Relationship to the case Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent Address: 506 Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo 102 FAX: 03 (221) 1924 5, Date of Amendment Order: Voluntary (1) The "Scope of Claims" on pages 1 and 2 of the specification (referring to the written specification attached to the written amendment submitted on July 28, 1985) is amended as shown in the attached sheet.

(2) "Halogen or silver color photograph" on page 10, line 2
Correct it to "silver halide color photograph".

(3) Amend page 14 as shown in the attached sheet.

(4) Amend page 15 as shown in the attached sheet.

(5) Amend page 16 as shown in the attached sheet.

(6) Amend page 17 as shown in the attached sheet.

(7) Amend page 22 as shown in the attached sheet.

(8) Change “one mercapto conversion” to “one mercapto” on page 26, line 8 of the same page.
Corrected as "one mercapto group".

(9) "Turcapto compound J" on page 27, line 5 is corrected to "mercapto compound."

(lO) Correct "alkenyl group" in the second line of page 28 to "alkenyl group".

(11) On page 28, line 5, “R2 in the formula” is changed to “R2 in the formula
Correct it with "2 is".

(12) “Alikenyl group” on page 28, lines 5-6 of the same page is “
"alkenyl group".

(13) On page 28, line 7, "in the formula R,, R,, R'is" is corrected to "in the formula R, ゛, R,', R'is".

(14) "Alkenyl group" on page 28, line 9 is corrected to "alkenyl group."

(15) rR2', R,', R' on page 28, line 16
``Noura'' is corrected to ``rR,', R,'', R'.

(16) "Alikenyl group" in the third line of page 30 is corrected to "alkenyl group."

(17) [Also, the above R1 to R24] on page 30, line 8
is corrected as "Also, the above R0' to R24".

(1st) "Alkoxycambonyl group" on page 30, lines 15-16 is corrected to "alkoxycarbonyl group."

(19) The three reaction formulas described on page 31 of the same are corrected as follows.

I! R'z R'z (20) "Hetero-sensitive mercapto compound" on page 55, line 1O, line 13, line 16, and line 20 is corrected to "peterocyclic mercapto compound."

(21) "Silver amount (rooting amount) photosensitive silver halide emulsion layer" on page 56, lines 4 to 5 is corrected to "silver amount (1! attached) is photosensitive silver halide emulsion layer".

(22) "Hemioxonol dye" on page 61, line 12 is corrected to "hemioxonol dye."

(23) "Hemioxonol dye" on page 61, line 14 is corrected to "hemioxonol dye."

(24) "Diethylene glycoacetate" on page 67, lines 10-11 is corrected to "diethylene glycol monoacetate."

(25) "Cyclohexanetetrahydrofuran" on page 67, lines 12-13 is corrected to "cyclohexane, tetrahydrofuran."

(26) On page 79, lines 12 and 13, "Blue-sensitive silver chlorobromide emulsion (grain size 0.8 mol m)" was replaced with "Blue-sensitive chlorobromide emulsion (silver bromide content 80 mol m)". %),” is corrected.

(27) The structural formula of r(Y-1)J on page 80 of the same is corrected as follows.

r(Y-1) (28) The structural formula of r(AI-2)J on page 81 of the same is corrected as follows.

F' (AI-2) ) 100 C-C=C-CH=CH-C-C-C0
0HII l 11 II (2
9) “1 min 1
ro, 08J in the "Fog" column of "5 Second Development" is corrected to rO, 06J.

(30) 11 in the sample selection 9 section of Table 2 on page 89 of the same
Correct r102J in the "Fog" column of "Minute 15 Second Development" to rO,08J.

Above (Amended "Claims" column) (Claims) A silver halide photographic photosensitive material having a silver halide emulsion layer containing a diffusion-resistant hydrophobic coupler of at least IIw on a support. In the material, at least one of the photographic constituent layers contains at least one compound selected from the group of compounds represented by the following general formulas N) and (■), and at least one of the photographic constituent layers A silver halide color photographic light-sensitive material containing a nitrogen-containing heterocyclic compound having at least one mercapto group.

General formula (1) General formula (II) [wherein R1
and R1 each independently represent a hydrogen atom or an alkyl group, R3 represents a halogen atom, an alkyl group, or an aryl group, R4 represents a hydrogen atom or an aryl group, and n represents O-
represents an integer of 5, and X and Y represent groups that can be separated by hydrolysis.] Procedural amendment June 3, 1985 Commissioner of the Patent Office Kuro 1) Yu Akira Silver halide color photographic light material 3. Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. Dia Palace No. 506 FAX 03 (221) 19245, Date of amendment order June 9, 1988 Proceeding author's letter (self-motivated) May 8, 1988 Commissioner of the Patent Office Black 1 ) Yu Akira 1, Indication of the case 1983 Patent Application No. 083759 2, Name of the invention Silver halide color photographic light-sensitive material capable of rapid processing and excellent preservability, etc. 3, Relationship with the amended person case Patent Applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. Dia Palace No. 506 Name <8397) Patent attorney Toru Takatsuki Telephone: 03 (221) 1922 FAX: 03 (221) 1924 5, Subject of amendment "Scope of claims" in the specification column, “Detailed Description of the Invention” column.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support, in which at least one of the photographic constituent layers contains the following: Contains at least one compound selected from the group of compounds represented by general formulas (I) and (II), and contains at least one compound in at least one of the photographic constituent layers.
1. A silver halide color photographic light-sensitive material comprising a nitrogen-containing heterocyclized product having two mercapto groups. General formula (I)▲There are mathematical formulas, chemical formulas, tables, etc.▼General formula (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 each independently represent a hydrogen atom or an alkyl group. In the formula, R^3 represents a halogen atom, an alkyl group, or an aryl group, R^4 represents a hydrogen atom or an aryl group, n represents an integer from 0 to 5, and X and Y can be separated by hydrolysis. represents a group. ]