JPH0619528B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having an improved inter-image effect and improved sharpness without increasing fog.

(Prior Art) By color-developing a silver halide color photographic material, an oxidized aromatic primary amine color developing agent and a coupler react to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is known that similar dyes are formed and color images are formed. In this method, a subtractive color method is usually used for color reproduction, and a yellow, magenta, and cyan color image forming agents that have a complementary color relationship with a silver halide emulsion that is selectively exposed to blue, green, and red, respectively. Is used. To form a yellow color image, for example, an acylacetanilide or a dibenzoylmethane-based coupler is used, and for forming a magenta color image, mainly pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano are used. Acetophenone or indazolone type couplers are used, and mainly phenol type or naphthol type is used for forming a cyan image.

By the way, the dyes produced from these couplers are not ideal spectral absorption spectra, and in particular, magenta and cyan dyes have broad absorption spectra and have sub-absorption in the short wavelength region, which makes them suitable for color photography. Not desirable for color reproduction of material.

In particular, the secondary absorption in the short wavelength region tends to cause a decrease in saturation. As a means for improving this, it can be improved to some extent by expressing an inter-image effect.

As one of means for improving the inter-image effect, US Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
No. 78, Japanese Patent Laid-Open No. 49-129,536, etc., and DIR hydroquinone.

These DIR hydroquinones are substances that release a development inhibitor by being oxidized during the development process. However, until now, the DIR hydroquinone was oxidized during the development process so that the interimage effect was improved. If the speed of increasing the speed is increased, the fog increases during the aging of the raw film and the fog increases during development, which is a very serious problem in photographic performance. On the other hand, if the reducing property of DIR hydroquinone is reduced to the extent that these fog increases do not occur, the reducing power during development processing is insufficient, the release of the development inhibitor is small, and the interimage effect can be improved almost. I couldn't do it.

Also, there are known US Pat. No. 2,131,038.
No. 2694716, No. 2444605, No. 22
When a fog inhibitor as disclosed in No. 32707 is used in combination with this DIR hydroquinone, fog can be suppressed to some extent, but the development activity of DIR hydroquinone decreases, so that the interimage effect also decreases.

As described above, it has been very difficult to develop a large interimage effect without increasing the fog caused by DIR hydroquinone. There has been a strong demand for a technique of exhibiting an inter-image effect while suppressing the increase of fog caused by DIR hydroquinone.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a multilayer color photographic light-sensitive material having a large inter-image effect without increasing fog.

The second object of the present invention is to provide a multilayer color photographic light-sensitive material having a high intersharpness and a high sharpness without deteriorating the graininess.

The third of the objects of the present invention is, without increasing fog,
A black-and-white silver halide light-sensitive material having high sharpness and good graininess.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and represented by the following general formula [I]. At least one compound represented by the following general formulas [II] and [III] is contained in the photosensitive silver halide layer and / or the adjacent hydrophilic colloid layer. This has been achieved with a silver halide photographic light-sensitive material characterized by containing in a silver halide layer.

General formula [I] A- (Time) _t -X General formula [II] General formula (III) According to the studies of the present inventors, the compounds represented by the general formulas [II] and [III] of the present invention improve the interimage effect themselves.

By using these compounds in combination with the compound represented by the general formula [I], the increase in fog due to the compound represented by the general formula [I] was suppressed, and surprisingly the interimage effect was dramatically improved.

Instead of the compounds represented by the general formulas [II] and [III], U.S. Pat. Nos. 21,310,38, 2,694,716 and 24,446 known to have a fog-inhibiting effect.
Fog was suppressed by the combination of the compounds disclosed in Nos. 05 and 2232707 and the compound represented by the general formula [I], but the interimage effect by the general formula [I] was also reduced.

On the other hand, US Pat. Nos. 3,536,486 and 3,53
6,487 discloses that diffusible 4-thiazoline-2-thione improves the interimage effect. Even if the diffusible 4-thiazoline-2-thione and the compound represented by the general formula [I] are used in combination,
Although the fog increase due to the compound represented by the general formula [I] was suppressed, the inter-image effect was not improved but was rather decreased.

In the general formula [I], A means a redox mother nucleus, which is firstly oxidized by being oxidized during photographic development processing. Represents the atomic group that makes it possible for the
Represents a sulfur element, a timing group linked to A by a nitrogen atom or an oxygen atom, t is an integer of 0 or 1, and
X means a development inhibitor.

The compound of the general formula [I] used in the present invention will be described below.

First, A of the general formula [I] will be described in more detail. A
Examples of the redox mother nucleus represented by the formula:
-Aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol and the like can be mentioned. At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 carbon atoms.
Examples of the sulfonyl group include a substituted or unsubstituted aliphatic sulfonyl group and an aromatic sulfonyl group. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of the protecting group are those having 1 to 25 carbon atoms, such as an acyl group,
Alkoxycarbonyl group, carbamoyl group, further JP-A-59-197,037, JP-A-59-201,057
And the protecting groups described in. Further, this protecting group may be bonded to a substituent of A described below, if possible, to form a 5, 6, or 7-membered ring.

The redox mother nucleus represented by A may be substituted at a suitable position with a suitable substituent. Examples of these substituents are those having 25 or less carbon atoms, such as an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amino group, an amide group, a sulfonamide group, and an alkoxycarbonylamino group. , Ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom,
Acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, or And so on. These substituents may be further substituted with the above-mentioned substituents. If possible, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol,
1,4-naphthalenediol, 1,4-aminonaphthol and the like can be mentioned. More preferable examples of A include hydroquinone, catechol, p-aminophenol and o-aminophenol. Most preferably, A is hydroquinone.

Preferred specific examples of A in the general formula [I] are shown below. In addition, (*) in each structural formula Indicates the position where is bound.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) Is the first time when the redox mother nucleus represented by A in the general formula [I] undergoes a cross oxidation reaction during development and becomes an oxidant. Is a group released as.

Time is a timing group that contacts A with a sulfur atom, a nitrogen atom, or an oxygen atom, and is released during development. To a group capable of releasing X through a reaction in one or more steps. The time is, for example, US Pat. Nos. 4,248,962 and 4,409,323.
No., British Patent No. 2,096,783, US Patent No. 4,
No. 146, 396, Kokai Sho 51-146, 828,
Examples include those described in JP-A-57-56,837. Time may be a combination of two or more selected from those described in these.

The timing group represented by Time in the general formula [I] is particularly preferably represented by the following general formula. Where * represents the site where the redox nucleus is bound,
** represents a site to which PUG binds. As Time,
The following two or more combinations may be used.

General formula (T-1) Where Z ₁ is Or Represents Here, R ₃₁ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

X ₁ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, Cyano group, halogen atom (eg fluorine, chlorine, bromine,
Iodine) or nitro group. R ₃₂ and R ₃₃ may be the same or different and each represents the group described for R ₃₁ .
X ₂ represents the group described for R ₃₁ .

q represents an integer of 1 to 4. When q is 2 or more, X ₁
The substituents represented by may be the same or different. q
When is 2 or more, X _1's may be connected to each other to form a ring.

p represents 0, 1 or 2. r represents 0 or 1.

The group represented by formula (T-1) is described in, for example, US Pat. No. 4,248,962.

General formula (T-2) In the formula, Z ₁ , X ₁ , X ₂ , q and r are represented by the general formula (T
It has the same meaning as defined in -1).

General formula (T-3) Z ₂ Or Represents m is an integer of 1 to 4, preferably 1, 2, or 3. Regarding R _31, X ₂ , and r, the general formula (T
It has the same meaning as defined in -1).

General formula (T-4) In the formula, Z ₃ is —O—, —S— or Represents Here, R ₃₆ represents an aliphatic group, an aromatic group, an acyl group, a sulfonyl group or a heterocyclic group. R ₃₄ and R ₃₅ have the same meaning as R ₃₁ defined in formula (T-1).
X ₁ and q have the same meaning as defined in formula (T-1).

The group represented by formula (T-4) is a timing group described in, for example, US Pat. No. 4,409,323.

General formula (T-5) In the formula, Z ₃ , X ₁ , R ₃₄ , R ₃₅ , and q are represented by the general formula (T-
It has the same meaning as defined in 4).

General formula (T-6) In the formula, X ₃ is composed of at least one atom selected from carbon, nitrogen, oxygen or sulfur and has 5 to 7 members.
Is an atomic group necessary for forming a heterocyclic ring of a member. This heterocycle may be further condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepine, oxepin, indole, benzofuran and quinoline. R ₃₄ , R ₃₅ , Z ₃ , X ₁ and q have the same meanings as defined in formula (T-4). The group represented by formula (T-6) is, for example, British Patent No. 2,0.
A timing group described in No. 96,783.

General formula (T-7) In the formula, X ₅ is an atomic group necessary for forming a 5-membered to 7-membered heterocycle, which is composed of at least one atom selected from carbon, nitrogen, oxygen and sulfur. X ₆
And X ₇ is Alternatively, -N =. Here, R ₃₇ represents a hydrogen atom, an aliphatic group, or an aromatic group. This heterocycle may be further condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrole, imidazole, triazole, furan, oxazole, oxadiazole, thiophene, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepine, oxepin and isoquinoline. R ₃₄ , R ₃₅ , Z ₃ , X ₁ and q have the same meanings as defined in formula (T-4).

General formula (T-8) In the formula, X ₁₀ is composed of at least one atom selected from carbon, nitrogen, oxygen or sulfur and has 5 to 7 members.
Is an atomic group necessary for forming a heterocyclic ring of a member. X ₈ and X ₉ are Or Is. This heterocycle is further a benzene ring or 5 to 7 members.
Membered heterocycles may be condensed. Preferred heterocycles include, in addition to those described in formula (T-6), pyrrolidine, piperidine, benzotriazole and the like.

Z ₁ , X ₁ , X ₂ , n and qr have the same meanings as defined in formula (T-1).

General formula (T-9) In the formula, X ₁₁ has the same meaning as X ₁₀ defined in formula (T-8). Z ₃ has the same meaning as defined in formula (T-4), and l represents 0 or 1. Examples of the preferable heterocycle for X ₁₁ include the following.

Here, X ₁ and q have the same meanings as defined in formula (T-1), and X ₁₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a sulfamoyl group. Represents a heterocycle or a carbamoyl group.

General formula (T-10) In the formula, X ₁ and X ₂ have the same meanings as defined in the general formula (T-1), and Z ₃ has the same meaning as defined in the general formula (T-4). m has the same meaning as defined in formula (T-3), and is preferably 1 or 2.

In the above general formulas (T-1) to (T-10),
When X ₁ , X ₂ , R ₃₁ , or R ₃₇ includes an aliphatic group moiety, it preferably has 1 to 20 carbon atoms, and is saturated or unsaturated, substituted or unsubstituted, chain or cyclic, straight chain or It may be branched. When X ₁ , X ₂ , R ₃₁ to R ₃₇ each include an aromatic group moiety, the number of carbon atoms is 6 to 20,
It is preferably 6 to 10, more preferably a substituted or unsubstituted phenyl group. Further, the above X ₁ , X ₂ , R ₃₁
When R ₃₇ to R ₃₇ contains a heterocyclic group, it is a 5- or 6-membered heterocycle containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. As the heterocyclic group preferably pyridyl group, furyl group, thienyl group, triazolyl group, imidazolyl group, pyrazolyl group,
A thiadiazolyl group, an oxadiazolyl group or a pyrrolidinyl group.

Preferred timing groups are, for example, those shown below.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) _{(32) * -S-CH 2} - ** (33) (34) (35) (36) (37) (38) (39) (40) (41) X means a development inhibitor. Examples of development inhibitors include:
Examples thereof include a compound having a mercapto group bonded to a heterocycle or a heterocyclic compound capable of producing imino silver. X
Since it acts as a development inhibitor only after it is released during development, it is preferable that it be bonded to Time at the position of the sulfur atom of the mercapto group or the nitrogen atom forming imino silver. Examples of compounds having a mercapto group bonded to the heterocycle include, for example, substituted or unsubstituted mercaptoazoles (e.g., 1-phenyl-5-mercaptotetrazole, 1-propyl-5-mercaptotetrazole, 1-
Butyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 3-
Methyl-4-phenyl-5-mercapto-1,2,4-
Triazole, 1- (4-ethylcarbamoylphenyl) -2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-
1,3,4-oxadiazole, 1- {3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1- (4-nitrophenyl) -5-mercaptotetrazole, 5- (2-ethylhexanoyl) Amino) -2
-Mercaptobenzimidazole, etc.) and substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaindene, 4,6-dimethyl-2-mercapto-1) , 3, 3
a, 7-Tetrazaindene etc.) and substituted or unsubstituted mercaptopyrimidines (eg 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine etc.) and the like.

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (for example, 1,
2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole, etc.), substituted or unsubstituted Indazoles (eg, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, etc.), and substituted or unsubstituted benzimidazoles (eg, 5-nitrobenzimidazole, 5,6-dichlorobenzimidazole) Etc.) and so on.

In addition, X is released from Time of the general formula [I] to become a compound having development inhibitory properties, and then it undergoes a certain chemical reaction with the developer component to substantially suppress development inhibitory properties. It may have no compound or may be converted to a compound having a significantly reduced amount. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group. Examples of such a deactivating development inhibitor include, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole and 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole.
(4-Phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (3-maleimidophenyl)
-5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5 -Nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4-benzoyloxyphenyl) -5-mercaptotetrazole, 5-
(2-Methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4 Examples include -succinimidophenyl} -5-mercapto-1,3,4-oxadiazole and 6-phenoxycarbonyl-2-mercaptobenzoxazole.

In order to describe the content of the present invention more specifically, specific examples of the compound represented by the general formula [I] are shown below, but the compounds usable in the present invention are not limited thereto.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) (I-16) (I-17) (I-18) (I-19) (I-20) (I-21) (I-22) (I-23) (I-24) (I-25) (I-26) (I-27) (I-28) (I-29) (I-30) (I-31) (I-32) (I-33) (I-34) (I-35) (I-36) (I-37) (I-38) (I-39) (I-40) (I-41) (I-42) (I-43) (I-44) (I-45) (I-46) (I-47) (I-48) (I-49) (I-50) (I-51) (I-52) (I-53) (I-54) (I-55) (I-56) The compound represented by the general formula [I] can be generally synthesized by the following two methods. First, Time is just a bond (t =
In the case of 0), the first is in chloroform, 1,2-dichloroethane, carbon tetrachloride, tetrahydrofuran, without catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid. In addition, benzoquinone, orthoquinone, quinone monoimine and quinone diimine derivatives are reacted with a development inhibitor at a temperature between room temperature and 100 ° C. Second
Is a benzoquinone substituted with chlorine, bromine or iodine in the presence of a base such as potassium carbonate, sodium hydrogen carbonate, sodium hydride or triethylamine in an aprotic polar solvent such as acetone, tetrahydrofuran or dimethylformamide, orthoquinone or quinone mono. Imine,
Add quinone diimine derivative and development inhibitor from -20 ° C to 10
In this method, the quinone compound obtained by reacting at 0 ° C. is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfite.

[Reference: Research Disclosure 18227 (197)
9); Liebigs Ann. Chem. 764.131 (197)
2)] Then, also in the case of the type (t = 1) in which X is released via Time, it can be synthesized by a method substantially similar to the above. That is, use Time-X instead of the above development inhibitor (X),
Alternatively, it is a method in which Time having a substitutable group for X (for example, a halogen atom, a hydroxy group, or a precursor thereof) is first introduced into the redox nucleus, and then X is linked by a substitution reaction.

The compound represented by the general formula [I] may be added as an emulsion obtained by dissolving in a high boiling point oil and stirring at high speed, or may be dissolved in a water-soluble organic solvent such as alcohol or cellosolve in a gelatin solution to obtain fine particles by stirring. It may be dispersed and added to.

In the general formula [II], R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group, and Z
Represents a polar substituent. Y is And R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ ,
R ₉ and R ₁₀ each represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. However, when Y is -S-, Z is not an amino group. X'is -O-, Alternatively, -S- is represented, and R'represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively. R ″ represents a hydrogen atom or a group capable of substituting it. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions.
Or 1, and m represents 0, 1 or 2. However, when X'is -S-, m = 0 is not included. l is 4-
represents m.

More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group,
Etc.), a linear or branched alkenylene group (eg, vinylene group, 1-methylvinylene group, etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), an arylene group (eg, phenylene, naphthylene, etc.) Etc.).

The polar substituent represented by Z includes, for example, a substituted or unsubstituted amino group (including a salt form, for example, amino group, hydrochloride of amino group, methylamino group, dimethylamino group, hydrochloric acid of dimethylamino group). Salt, dibutylamino group,
Dipropylamino group, N-dimethylaminoethyl-N-
Methylamino group, etc.), quaternary ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, etc.) , An aryloxy group (eg, phenoxy group, etc.), an alkylthio group (eg, methylthio group,
Butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic oxy group (eg, 2-pyridyloxy group, 2-imidazolyloxy group, etc.), heterocyclic thio group (eg, 2-benzthia) Zolylthio group, 4
-Pyrazolylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group ( For example, an unsubstituted sulfamoyl group, a methylsulfamoyl group, etc.), a carbonamide group (for example,
Acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), ureido group (eg, no Substituted ureido group, methylureido group, ethylureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), thioureido group (eg, , An unsubstituted thioureido group, a methylthioureido group, etc.), a sulfonyloxy group (eg, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, etc.), a heterocyclic group (eg, a 1-morpholino group, 1
-Piperidino group, 2-pyridyl group, 4-pyridyl group, 2
-Thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group,
2-tetrahydrothienyl group, etc.) and a hydroxy group.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R
₁₀ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl) Group, etc.),
It represents a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

R'is a hydrogen atom or a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, 2-hydroxyethyl group, 2-imidazolylethyl group, 2-dimethylaminopropyl group). ,
Etc.) and a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.).

R represents a hydrogen atom or a group substitutable for it, and examples of the substitutable group include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), substituted or unsubstituted with 1 to 6 carbon atoms. Alkyl group (eg, methyl group, trifluoromethyl group, ethyl group, n-butyl group, etc.), substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, 4-methylphenyl group, etc.), carbon number A substituted or unsubstituted alkoxy group having 1 to 6 (eg, methoxy group, ethoxy group, etc.), a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms (eg, phenoxy group, 4-methylphenyl group, etc.), carbon number 1 To 12 sulfonyl groups (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.), C1-12 sulfonamide groups (eg, methanesulfone group) Bromide group, p- toluenesulfonamide group, ethanesulfonamide group), 1 carbon atoms
12 sulfamoyl groups (eg, diethylsulfamoyl group, phenylsulfamoyl group, etc.), 1 to 12 carbon atoms
Carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), C2-C12 amide group (eg, acetamide group, benzamide group, etc.), C1-C12 ureido group (eg, Substituted ureido group, 3-methylureido group, 3-phenylureido group, etc.), C2-C12 aryl or alkoxycarbonyl group (for example, methoxycarbonyl group, phenoxycarbonyl group, etc.), C2-C12 aryl or Examples thereof include an alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.) and a cyano group.

M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), or X under alkaline conditions. = H or a group that can be an alkali metal (eg, acetyl group, cyanoethyl group, methanesulfonylethyl group, etc.).

In the general formula [II], preferably R is a substituted or unsubstituted alkylene group and Y is Or This is the case where R ₂ , R ₃ , R ₆ , and R ₇ are hydrogen atoms, X ′ is —NH— or —O—, and Z is a substituted or unsubstituted amino group or salt thereof, or a heterocyclic group.

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

(II-1) (II-2) (II-3) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) (II-15) (II-16) (II-17) (II-18) (II-19) (II-20) (II-21) (II-22) (II-23) (II-24) (II-25) (II-26) (II-27) (II-28) (II-29) (II-30) (II-31) (II-32) (II-33) (II-34) (II-35) (II-36) (II-37) (II-38) (II-39) (II-40) The compound represented by the general formula [II] used in the present invention is (Organic Synthesis) Organic Synthesis, IV,
569 (1963); (Journal of the American Chemical Society) Journal of the Ameri
can Chemical Society, 45 , 2390 (1923);
(Chemissier Berichte) Chemische Berichte, 9 , 46
5 (1876) or the like or a typical synthesis example shown below.

Synthesis Example 1 Synthesis Method of Exemplified Compound (II-1) 5-Amino-2-mercaptobenzimidazole 36.
To 6 g of pyridine and 17.1 ml of pyridine, 250 ml of N, N-dimethylacetamide was added, and 34.4 g of phenyl chloroformate was added dropwise at room temperature. The mixture was stirred at room temperature for 1.5 hours, and then added to ice water 1.5 to precipitate crystals. The crystals obtained were taken and recrystallized from acetonitrile to give 2
47.7 g of -mercapto-5-phenoxycarbonylaminobenzimidazole was obtained.

Acetonitrile was added to 8.6 g of the obtained 2-mercapto-5-phenoxycarbonylaminobenzimidazole.
0 ml was added and the mixture was heated with stirring at 45 ° C., and 14.5 g of N, N-dimethylaminoethylenediamine was added dropwise. After stirring at 45 ° C. for 1.5 hours and collecting the precipitated crystals, N, N
-Recrystallization from a mixed solvent of dimethylformamide and methyl alcohol gave 6.2 g of the desired product (yield 74%).

Melting point 240 ° C. (decomposition) Synthesis example 2 Synthesis method of exemplified compound (II-11) 100 ml of ethyl alcohol was added to 14.3 g of 2-mercapto-5-phenoxycarbonylaminobenzimidazole obtained in Synthesis example 1, and room temperature was added. Lower 3-N, N-dimethylaminopropylamine was added dropwise. 2 at 40 ℃ after dropping
After stirring for 100 hours, 100 ml of acetonitrile was added to precipitate crystals. The precipitated crystals were collected and recrystallized twice with a mixed solvent of N, N-dimethylformamide and acetonitrile to obtain 7.2 g of the desired product (yield 49%).

Melting point 280 ° C. or higher (decomposition) Synthesis Example 3 Synthesis method of Exemplified compound (II-6) 100 ml of ethyl alcohol was added to 14.3 g of 2-mercapto-5-phenoxycarbonylaminobenzimidazole obtained in Synthesis Example 1 at room temperature. Below, 8.7 g of 3-morpholinopropylamine was added dropwise. After dropping, the mixture was stirred at 50 ° C. for 30 minutes and then cooled to room temperature to precipitate crystals. The precipitated crystals were collected and recrystallized from a mixed solvent of N, N-dimethylformamide and acetonitrile to obtain 6.7 g of the desired product.
(Yield 42%) was obtained. Melting point 280 ° C. or higher (decomposition) Synthesis Example 4 Synthesis method of Exemplified compound (II-27) 6-carboxy-2-mercaptobenzothiazole 1
To 2.6 g, 80 ml of N, N-dimethylformamide was added, 12.6 ml of triethylamine was added dropwise under ice cooling, and 8.6 ml of ethyl chloroformate was further added. After stirring for 30 minutes under ice cooling, 9.7 g of 2-methanesulfonamidoethylamine was added dropwise, and the mixture was stirred for 4 hours. The reaction solution was added to ice water 1 and the precipitated crystals were collected and recrystallized from ethyl alcohol to obtain 12.1 g of the desired product (yield 61%). Melting point 242 to 244 ° C. Synthesis Example 5 Method for synthesizing exemplified compound (II-28) p- (2-N, N-dimethylaminoethoxy) -o-phenylenediamine 7.8 g potassium hydroxide 2.4 g ethyl alcohol In addition to 120 ml of the solution, 12 ml of carbon disulfide was added dropwise at 40 ° C. After the dropwise addition, the mixture was heated under reflux for 5 hours, 6 ml of concentrated hydrochloric acid was added, and the solvent was distilled off under reduced pressure. The obtained oily residue was purified by a silica gel column and then recrystallized from acetonitrile to obtain 3.8 g of the desired product (yield 40%).

Melting point 233 to 235 ° C. (decomposition) Synthesis example 6 Method for synthesizing exemplified compound (II-13) 2-mercapto-6-phenoxycarbonylaminobenzoxazole 17.2 synthesized in the same manner as in Synthesis example 1.
Ethyl alcohol was added to g, and 6.2 g of N, N-dimethylethylenediamine was added dropwise at room temperature. 3 at 50 ℃ after dropping
After stirring for 0 minutes and cooling to room temperature, crystals were precipitated.
Precipitated crystals were collected and recrystallized from a mixed solvent of N, N-dimethylformamide and acetonitrile to obtain Target 1
3.3 g (yield 79%) was obtained.

Melting point 280 ° C. or higher (decomposition) In formula [III], R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z ′ represents a hydrogen atom or a polar substituent. Y'is -S- And R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇
Alternatively, R ₁₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or an aralkyl group. M represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a group that cleaves under alkaline conditions. n represents 0 or 1. However, when Y'is -S-, Z'is not an amino group.

More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group,
Etc.), a linear or branched alkenylene group (eg, vinylene group, 1-methylvinylene group, etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), an arylene group (eg, phenylene, naphthylene, etc.) Etc.).

The polar substituent represented by Z ′ is, for example, a substituted or unsubstituted amino group (including a salt form, for example, an amino group, a hydrochloride of an amino group, a methylamino group, a dimethylamino group or a dimethylamino group). Hydrochloride, dibutylamino group, dipropylamino group, N-dimethylaminoethyl-
N-methylamino group, etc.), quaternary ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, Etc.), an aryloxy group (eg a phenoxy group, etc.), an alkylthio group (eg a methylthio group,
Butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic oxy group (eg, 2-pyridyloxy group, 2-imidazolyloxy group, etc.), heterocyclic thio group (eg, 2-benzthia) Zolylthio group, 4
-Pyrazolylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group ( For example, an unsubstituted sulfamoyl group, a methylsulfamoyl group, etc.), a carbonamide group (for example,
Acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), ureido group (eg, none Substituted ureido group, methylureido group, ethylureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), thioureido group (eg, Unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (for example, methanesulfonyloxy group, p-toluenesulfonyloxy group,
Etc.), heterocyclic groups (for example, 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 2-imidazolyl group, 2
-Tetrahydrofuryl group, 2-tetrahydrothienyl group, etc.) and cyano group. Here, Z ′ is not a sulfonic acid group, a carboxylic acid group, a hydroxy group, or an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.).

, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ ,
R ₁₇ or R ₁₈ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group,
2-dimethylaminoethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, Etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

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

(III-1) (III-2) (III-3) (III-4) (III-5) (III-6) (III-7) (III-8) (III-9) (III-10) (III-11) (III-12) (III-13) (III-15) (III-16) (III-17) (III-18) (III-19) (III-20) (III-21) (III-22) (III-23) (III-24) (III-25) (III-26) (III-27) (III-28) (III-29) (III-30) (III-31) (III-32) (III-33) (III-34) (III-35) (III-36) (III-37) (III-38) (III-39) (III-40) (III-41) (III-42) (III-43) (III-44) (III-45) (III-46) (III-47) (III-48) (III-49) (III-50) (III-51) (III-52) (III-53) (III-54) (III-55) (III-56) (III-57) (III-58) (III-59) (III-60) (III-61) (III-62) (III-63) (III-64) (III-65) The compound represented by the general formula [III] used in the present invention is described in "Advances in Heterocyclic Chemistry", Volume 9, 165 to 209 (1968), " Journal of Pharmacy Social Society
Japan (Journal of Pharmaceutical Society Japa
n) ", Vol. 71, pp. 1481 to 1484 (1951
, U.S. Pat. No. 2,823,208, and can be synthesized. Further, as Y ′, those which represent a ureido group or a thioureido group include 2-amino-5-mercapto-1,3,4-thiadiazole, isocyanates,
It can be easily synthesized by reacting isothiocyanates or by reacting 2-mercapto-5-phenoxycarbonylamino-1,3,4-thiadiazole with amines.

A typical synthesis example is shown below.

Synthesis Example 1 Synthesis method of compound (III-1) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-aminoethyl chloride hydrochloride 5.8
g and 4 g of pyridine were added to 60 ml of n-butanol and heated under reflux for 2 hours. The reaction solution was ice-cooled and the precipitated crystals were collected by filtration and recrystallized from methanol / water. Yield 7.1g Melting point 2
28 to 229 ° C. (dec) Synthesis Example 2 Synthesis method of compound (III-14) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-dimethylaminoethyl chloride hydrochloride 7.3 g, pyridine 4 g Was added to 60 ml of n-butanol and heated under reflux for 2 hours. The reaction solution was cooled with water and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 7.9 g Melting point 161-163 ° C. Synthesis example 3 Synthesis method of compound (III-13) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-diethylaminoethyl chloride hydrochloride 8.6 g, pyridine 4 g was added to 60 ml of n-butanol and heated under reflux for 2 hours. The reaction solution was ice-cooled and the precipitated crystals were collected by filtration and recrystallized from ethanol / water. Yield 10.1
g Melting point 184-186 ° C. Synthesis example 4 Synthesis method of compound (III-3) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 3-dimethylaminopropyl chloride hydrochloride 7.9 g, pyridine 4 g The mixture was added to 60 ml of n-butanol and heated under reflux for 2 hours. The reaction solution was ice-cooled and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 11 g Melting point 149 to 152 ° C. Synthesis example 5 Synthesis method of compounds (III-42) and (III-43) Synthesis method of 2- [N, N-bis (2-methoxycarbonylethyl) amino] ethyl chloride hydrochloride 2 -Aminoethanol (6.1 g) was added to methanol (75 ml), and methyl acrylate (20 ml) was added dropwise under ice cooling. After the dropping, the mixture was stirred under ice cooling for 2 hours and further at room temperature for 20 hours. 100 ml of chloroform was added to the oil (23 g) obtained by distilling off the reaction solution under reduced pressure, and 8.7 ml of thionyl chloride was added dropwise under cooling with water, followed by heating under reflux for 1 hour. The reaction solution was evaporated under reduced pressure and the obtained residue was recrystallized from isopropanol / n-hexane. Yield 21 g, melting point 103-104 ° C. Method for synthesizing compound (III-42) 2,5-dimercaptothiadiazole 7.5 g, 2-
[N, N-bis (2-methoxycarbonylethyl) amino] ethyl chloride 14.4 g, pyrimidine 8.1 g
Was added to 80 ml of dioxane and heated under reflux for 2 hours. The compound (III-42) was obtained as a syrup by purifying the residue obtained by distilling the reaction solution under reduced pressure by column chromatography (stationary phase alumina, developing solvent methanol / ethyl acetate). Yield 8.4 g Method for synthesizing compound (III-43) 7.3 g of compound (III-42) was added to 20 ml of 20% aqueous sodium hydroxide solution, and the mixture was stirred at 50 ° C. for 2 hours. The reaction solution was ice-cooled and neutralized with 35% hydrochloric acid, and the resulting precipitate was collected by filtration and recrystallized from DMF / ethanol to obtain compound (III-43). Yield 3.2g mp 188
Synthetic Example 6 Synthesis method of compound (III-4) 2,5-dimercapto-1,3,4-thiadiazole 1
5.0 g, 20 ml of 28% sodium methoxide solution,
To 100 ml of ethyl alcohol was added and dissolved by heating, and 13.5 g of 2-chloroethylurea was added dropwise. After the dropping, the mixture was heated under reflux for 4 hours. After the reaction, the reaction solution was poured into 700 ml of ice water, and the precipitated crystals were taken and recrystallized from methanol. Yield 1
6.4 g Melting point 174-176 ° C. Synthesis Example 7 Method for synthesizing compound (III-2) 15 g 2,5-dimercapto-1,3,4-thiadiazole was added to 300 ml acetone, and then 22 ml sodium methoxide 28%. 12 g of solution β-chloropropionamide was added.

Furthermore, 15 g of sodium iodide was added to this reaction solution, and 2
The mixture was heated under reflux for 0 hours. After cooling, the obtained crystals were taken and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide-methanol to obtain the compound (III-2). Yield 12.0 g Melting point 175-177 ° C. Synthesis example 8 Method for synthesizing compound (III-44) 2,5-dimercapto-1,3,4-thiadiazole 1
5.0 g, 1- (2-chloroethyl) imidazole hydrochloride 20.0 g, pyridine 9.5 g and acetonitrile 10
It was added to 0 ml and heated under reflux for 4 hours. After the reaction, the reaction solution is cooled, and the precipitated crystals are collected and recrystallized from a mixed solvent of dimethylformamide and methanol to give the compound (III-4
9) was obtained. Yield 11.2 g Melting point 226-228 ° C Synthesis example 9 Method for synthesizing compound (III-45) 2-mercapto-5-phenoxycarbonylamino-
200 ml of acetonitrile was added to 12.7 g of 1,3,4-thiadiazole, and 6.2 g of 3-N, N-dimethylaminepropylamine was added dropwise at room temperature. After dropping, at 50 ° C 1.
The mixture was heated and stirred for 5 hours, and the precipitated crystals were collected and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to give the compound (III-4
5) was obtained. Yield 10.7 g Melting point 228-230 ° C. Synthesis example 10 Synthesis method of compound (III-46) 2-amino-5-mercapto-1,3,4-thiadiazole 13.3 g was dissolved in acetonitrile 100 ml, dimethylacetamide 40 ml, Under room temperature, 15.9 g of 3- (N, N-dimethylamino) propyl isothiocyanate was added dropwise. After the dropping, the mixture was heated with stirring at 50 ° C. for 2 hours, the precipitated crystals were taken and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain a compound (III-46). Yield 12.6 g Melting point 146-148 ° C. Synthesis example 11 Synthesis method of compound (50) 2-mercapto-5-phenoxycarbonylamino-
100 ml of ethyl alcohol was added to 12.7 g of 1,3,4-thiadiazole, and 8.7 g of 3-morpholinopropylamine was added dropwise at room temperature. After the dropping, the mixture was stirred at room temperature for 5 hours, the precipitated crystals were taken, and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain a compound (50). Yield 10.9 g Melting point 255-257 ° C. When the compounds represented by the general formulas [I], [II] and [III] of the present invention are used in a multilayer color photographic light-sensitive material,
A silver halide emulsion layer, or a yellow filter layer, an antihalation layer, an intermediate layer adjacent to the emulsion layer,
Alternatively, it is contained in at least one layer such as a protective layer, but it is preferably contained in the silver halide emulsion layer or an intermediate layer adjacent to the emulsion layer. Most preferably, the compounds represented by the general formulas [II] and [III] are contained in the silver halide emulsion layer, and the compound represented by the general formula [I] is contained in the emulsion layer and / or the adjacent layer (halogenated layer). It may be a silver emulsion layer or a gelatin intermediate layer).

When the silver halide emulsion layers having the same color sensitivity are composed of two or more layers, the compounds represented by the general formulas [II] and [III] are most preferred among the silver halide emulsion layers having the same color sensitivity. It is preferably contained in the low-sensitivity emulsion layer.

Further, when the present invention is applied to a black-and-white photographic light-sensitive material,
The compounds represented by the general formulas [I], [II] and [III] are contained in the silver halide emulsion layer and / or the protective layer.

The compounds of the present invention represented by the general formulas [I], [II] and [III] are generally formed in the same layer or adjacent layers, although they vary depending on the properties, purpose or development processing method of the silver halide photographic light-sensitive material to be applied. The amount is 1 to 10 ^-5 mol, preferably 3 × 10 ^-1 to 1 mol of silver halide present.
It is 3 × 10 ⁻⁴ mol.

To introduce the compounds represented by the general formulas [II] and [III] of the present invention into a light-sensitive material, water, methanol, ethanol, propanol, or a solvent commonly used in photographic light-sensitive materials such as fluorinated alcohols is used. After dissolution, add to hydrophilic colloid. When it is contained in the silver halide emulsion layer, during grain formation of the silver halide emulsion,
During physical ripening, just before chemical sensitization, during chemical sensitization, after chemical sensitization,
Alternatively, it may be selected at the time of preparing the coating liquid, and it is selected according to the purpose.

The compound represented by the general formula [I] and the compounds represented by the general formulas [II] and [III] may be added in the same layer or different layers. Alternatively, it is preferably added in the adjacent layer.

Photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer types), color papers, color positive films, color reversal papers,
Color photographic light-sensitive materials such as color diffusion transfer process, die transfer process, black and white negative film,
Any black-and-white photographic light-sensitive material such as black-and-white photographic paper, roentgen film and lith film can be used.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse grain having a wide distribution. It may be an emulsion.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure,
176, NO.17643 (December 1978), 22
Pp. 23, "I. Emulsion Preparation and
Types) ”and ibid., 187, No. 18716 (19)
(November 1979), p.648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chi.
mie et Physique Photographique Paul Montel, 196
7), "Photoemulsion Chemistry" by Duffin, published by Forcal Press (GF Duffin, Photographic Emulsion Chemis
try (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Forcal Press (VL.
Zelikman et al, Making and Coating Photo-graphic E
mulsion, Focal Press, 1964) and the like. That is, the acidic method,
A neutral method, an ammonia method, or the like may be used, and a method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.
As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Known silver halide solvents (for example, ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, SHO 54-100717
Physical aging in the presence of thioethers and thione compounds described in JP-A No. 54-155828. By this method also, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation.
For details, see, for example, Photographic Science and Eng.
ineering) Vol. 6, 159-165 (1962); Journal of Photographic Science (Jour)
nal of Photo-graphic Science), Volume 12, 242-2
51 (1964), U.S. Pat. No. 3,655,394 and British Pat. No. 1,413,748.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as within 0% can be used in the present invention.
A method for producing such an emulsion is described in US Pat. No. 3,574,6.
28, 3,655,394 and British Patent 1,413,748. In addition, JP-A-4
8-8600, 51-39027, 51-83
097, 53-137133, and 54-4852.
1, No. 54-99419, No. 58-37635,
Monodisperse emulsions such as those described in JP-A-58-39938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering,
Volume 14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. It can be easily prepared by the method described in No. 2,112,157. When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitizing efficiency by the sensitizing dye, which are described in detail in the above-cited US Pat. No. 4,434,226. .

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent 1,027,1
46, U.S. Pat. Nos. 3,505,068 and 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. Nos. 4,094,684, 4,142,900,
No. 4,459,353, British Patent No. 2,038,79.
No. 2, U.S. Pat. Nos. 4,349,622 and 4,39.
5,478, 4,433,501, 4,46
No. 3,087, No. 3,656,962, No. 3,85
2,067, JP-A-59-162540 and the like.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, the Nudel washing, the flocculation precipitation method or the ultrafiltration method is used.

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643 (December 1978) and No. 1 mentioned above.
8716 (November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure mentioned above.
No. 17643, VIII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors (that is, yellow magenta and cyan) of the subtractive method by color development is important, and specific examples of the diffusion-resistant hydrophobic 4-equivalent or 2-equivalent coupler are described above. Research Disclosure No.17643, VII-C
In addition to the couplers described in the patents described in paragraphs D and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Pat. No. 2,
No. 407,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a representative example thereof is US Pat.
311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and No. 3,936,015.
As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. European Patent No. 7
The 5-pyrazolone-based coupler having a ballast group described in JP-A No. 3,636 provides high color density. As a pyrazoloazole coupler, US Pat. No. 3,061,43
2 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure NO. 24220 (June 1984)
And the research discloser described in JP-A-60-33552.
No. 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable in view of low yellow sub-absorption of a color forming dye and light fastness, and are described in European Patent 119,860A. Pyrazolo [1,5-b]
[1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenol couplers. The naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. 052
No. 212, No. 4,146, 396, No. 4,22
Typical examples are the oxygen atom desorption type two-equivalent naphthol couplers described in JP-A-8,233 and JP-A-4,296,200. Further, specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2,8.
01,171, 2,772,162, 2,
No. 895,826.

A cyan coupler which is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or more at the meta-position of the phenol nucleus described in US Pat. No. 3,772,002. A phenolic cyan coupler having a group, US Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent No. 121,365, and the like, and 2,5-diacylamino-substituted phenol-based couplers and US Pat. Nos. 3,446,622 and 4 , 333, 999, 4,451, 559 and 4,427, 767.
And the like, which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

The cyan coupler described in European Patent No. 161,626A in which the 5-position of naphthol is substituted with a sulfonamide group or an amide group is also excellent in the fastness of a color image.
It can be preferably used in the present invention.

In order to correct the unnecessary absorption of the chromophores, it is preferable to mask the color negative photosensitive material for photographing with a colored coupler. Yellow colored magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413 or U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258 and British Patent No. 1,
Typical examples are magenta colored cyan couplers described in JP-A-146368. Other colored couplers are the above-mentioned Research Disclosure, NO.1
7643, VII-G.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
U.S. Pat. No. 4,366,237 and British Patent No. 2,
Specific examples of magenta couplers are disclosed in 125,570, European Patent No. 96,570 and West German Patent Application Publication No. 3,2.
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above Research Disclosure, No. 17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-
No. 151944, a developer inactivating type; U.S. Pat. No. 4,248,962 and JP-A-57-154234.
Timing type represented by the Japanese Patent No. 59-39653
No. 57-151944, JP-A No. 58-217932 and JP-A Nos.
Developer inactivating DIR couplers described in Japanese Patent Application Nos. 59-75474, 59-82214, 59-82214 and 59-90438, and Japanese Patent Application No. 59-75438.
It is a reactive DIR coupler described in JP-A-39653 and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water or ultrafiltration, and then used for coating.

The process of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The light-sensitive material produced by using the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds As a representative example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. These layer arrangements can be arbitrarily selected as needed. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or blue-sensitive, red-sensitive and green-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support usually used for photographic light-sensitive materials such as plastic film, paper, cloth or a rigid support such as glass, pottery and metal. To be done. Useful as flexible supports are cellulose derivatives (cellulose nitrate,
Films composed of cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymer), etc. It is a paper or the like coated or laminated with. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally
It is subjected to a subbing treatment to improve the adhesion with the photographic emulsion layer and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, a day coating method, a roller coating method, a curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Pat. No. 2,681,29 as required
No. 4, No. 2,761, 791, No. 3,526, 5
No. 28, No. 3,508,947 and the like may be used to simultaneously coat multiple layers.

The color photographic light-sensitive material according to the present invention can be obtained by the usual method described in Research Disclosure, No. 17643, pages 28 to 29 and No. 18716, page 651, left column to right column. It can be developed.

When the silver halide photographic light-sensitive material of the present invention is a black-and-white light-sensitive material, the black-and-white development / fixing step is carried out; in the case of a color light-sensitive material, the color development / bleaching / fixing step is carried out;・ Reversal, color development, bleaching, and fixing steps are performed.

In the case of a color reversal light-sensitive material, a known developing agent can be used in the first developer (black and white development) used in the present invention. Examples of the developing agent include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolin , Ascorbic acid, and 1, as described in US Pat. No. 4,067,872.
A heterocyclic compound in which a 2,3,4-tetrahydroquinoline ring and an indole ring are condensed can be used alone or in combination.

In the black-and-white developer, if necessary, a preservative (for example, sulfite, bisulfite, etc.), a buffer (for example, carbonate,
Boric acid, borate, alkanolamine), alkaline agent (eg hydroxide, carbonate), solubilizing agent (eg polyethylene glycols, esters thereof), pH adjuster (eg organic acid such as acetic acid), Sensitizers (eg, quaternary ammonium salts), development accelerators, surfactants, toning agents,
An antifoaming agent, a hardener, a viscosity imparting agent, etc. may be contained.

The first developing solution used in the present invention needs to contain a compound which acts as a silver halide solvent, and the sulfite salt added as the preservative usually plays the role. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN, NaSCN, K ₂ SO ₃ , Na ₂ S
O ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O ₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O ₃
And so on.

Further, a development accelerator is used for imparting a development accelerating action. Particularly, a compound represented by the following formula (A) described in JP-A-57-63580 is used alone or in combination of two or more kinds, May be used in combination with the above silver halide solvent.

General formula [A] If the amount of these silver halide solvents used is too small, the progress of development is slowed, and if the amount is too large, fogging occurs in the silver halide emulsion, and therefore, there is a preferable amount used by itself. Can be easily done by those skilled in the art.

For example, SCN ^- is 0.005 to 0.0 per developer.
It is preferably 2 mol, particularly 0.01 to 0.015 mol, and SO ₃ ²⁻ is 0.05 to 1 mol, particularly 0.1 to 3.
It is preferably 0.5 mol.

When the compound of the general formula [A] is used by adding it to the black and white developer, the addition amount is preferably 5 × 10 5 per 1 developer.
^-6 mol to 5 × 10 ^-1 mol, more preferably 1 × 10 ^-4 mol to 2 × 10 ^-1 mol.

The pH value of the developer thus prepared is selected to be sufficient to give the desired density and contrast, but is preferably in the range of about 8.5 to about 11.5.

To perform a sensitization process using such a first developing solution,
The time may be extended up to about 3 times the standard processing.
At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The fogging bath used in the inversion step may contain a known fogging agent. That is, stannous ion-organic phosphate vinegar (US Pat. No. 3,617,282),
Stannous Ion Organic Phosphonocarboxylic Acid Acetate (Japanese Patent Publication Sho 5
6-32616), stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1,209,050), and other stannous ion complex salt borohydride compounds (US Pat. No. 2,984,567). Compounds), boron compounds such as heterocyclic amine borane compounds (British Patent No. 1,011,000), and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and the pH is 2 to 12, preferably 2.5 to 1.
The range is 0, particularly preferably 3 to 9.

The color developer used in the present invention has a composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are the following p-phenylenediamine derivatives. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-
N-laurylamino) toluene, 4- [N-ethyl-N
-(Β-Hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, N-ethyl-N- (β-methanesulfoamidoethyl) -3 -Methyl-4-aminoaniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-
Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline and 4-amino-3-methyl-N-ethyl-described in U.S. Pat. Nos. 3,656,950 and 3,698,525. N-β-ethoxyethylaniline and 4-amino-3-methyl-
N-ethyl-N-β-butoxyethylaniline and salts thereof (for example, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) are preferred representative examples.

The color developer may contain other known developer component compounds. For example, caustic soda, caustic potash, sodium carbonate, potash carbonate, and the like can be used as the alkaline agent and the buffer.
Tertiary sodium phosphate or potassium, potassium metaphoric acid, borax, etc. may be used alone or in combination.

A sulfite salt (for example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine which is usually used as a preservative can be added to the color developer.

If necessary, any development accelerator can be added to the color developing solution. For example, various pyridinium compounds represented by U.S. Pat. No. 2,648,604, JP-B-44-9503 and U.S. Pat. No. 3,671,247, other cationic compounds, cationic dyes such as phenosafranine, thallium nitrate and Neutral salts such as potassium nitrate,
JP-B-44-9504, US Pat. No. 253399.
No. 0, US Pat. No. 2,531,832, 2
Non-ionic compounds such as polyethylene glycol and its derivatives and polythioethers described in 950970 and 2577127, JP-B-44-9509.
No. 6,284,862, and organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, etc. F. A. Mason, "Photographic Processing Chemistry (Photographic Processing
Chemistry) ", pages 40-43 (Focal Press, 1966).

Further, the color developer may contain an aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid as a water softener. .

Competing couplers and compensating developers can also be added to the color developer.

Citrazinic acid, J acid, H acid and the like are useful as competitive couplers.

As the compensating developer, p-aminophenol, N-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc. can be used.

The pH of the color developing solution is preferably in the range of about 8-13. The temperature of the color developing solution is selected in the range of 20 ° C to 70 ° C, preferably 30 ° C to 60 ° C.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitrone compounds are used. For example, ferricyanide, dichromate, iron (II
Organic complex salts of I) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid Persulfate, permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) acetate and ammonium ethylenediaminetetraacetate (III) ammonium salt are particularly useful. Aminopolycarboxylic acid iron (III)
The complex salts are useful in either a stand-alone bleaching solution or a one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, US Pat.
No. 3,241,966, Japanese Patent Publication No. 45-8
Various additives can be added, including the bleaching accelerators described in JP 506, JP-B-45-8836 and the like.

In the fixing bath of the present invention, as a fixing agent, ammonium salts, sodium salts and potassium salts of thiosulfate are 30 g /
It is used in an amount of up to about 200 g / s. In addition, stabilizers such as sulfites and isomeric bisulfites, hardeners such as potassium alum, acetates, borates, phosphates, carbonates, etc.
A pH buffer or the like can be included. The pH of the fixer is 3-10
And more preferably 5 to 9.

After development, bleach-fixing or fixing treatment, washing treatment or stabilizing treatment is usually carried out.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. 2-9 in the case of this step
A countercurrent bath in the bath is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinones, irithiazolones, 4-thiazoline) as required. Various additives such as benzimidazoles, halogenated phenols, etc.), surfactants, fluorescent brighteners and hardening agents may be used, and two or more of the same or different target compounds may be used in combination. Good.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

In addition, stabilizers such as sulfite and isomeric bisulfite,
Hardening agents such as potassium alum, pH buffering agents such as acetates, borates, phosphates, carbonates and the like can be included. The pH of the fixing solution is 3 to 10, more preferably 5 to 9.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1. As a sample, a multi-layer color light-sensitive material 1 comprising each layer having the following composition on a cellulose triacetate film support
01 was produced.

1st layer: Anti-halation layer Black colloidal silver: Gelatin layer containing 0.18 g / m ² Second layer: Intermediate layer 2,5-di-t-pentadecylhydroquinone: 0.18 g / m ² coupler C-3: Gelatin layer containing 0.11 g / m ² Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.4 μ) Silver coating amount (same as below) 0.72 g / m ² Sensitizing dye A ………… 9.0 × 10 ⁻⁵ mol per mol silver sensitizing dye B ………… 3.0 per mol silver × 10 ^-5 mol Sensitizing dye C ………… 4.2 mol per mol of silver 4.2 × 10 ^-4 mol Sensitizing dye D ………… against 1 mol of silver 3.0 × 10 ^-5 mol Coupler C- 4 ...... 0.093g / m ² coupler C-5 ......... 0.31g / m ² coupler C-6 ......... gelatin layer 4 containing 0.01 g / m ² ; Second red-sensitive emulsion layer Silver iodobromide emulsion .................. 1.0g / m ² (silver iodide 10 mol%, average particle size 1.0 micron) to Sensitizing Dye A ......... 1 mol of silver On the other hand, 7.8 × 10 ⁻⁵ moles Sensitizing dye B ... …… 2.2 × 10 ⁻⁵ moles to 1 mole of silver Sensitizing dye C ………… 3.0 × 10 ⁻ to 1 mole of silver ⁴ moles Sensitizing dye D ………… 2.2 × 10 ^-5 moles per 1 mole silver Coupler C-4 ………… 0.1 g / m ² coupler C-5 …… 0.061 g / m ² coupler C-7 ...... 0.046g / m gelatin layer a fifth layer comprising a ^2: third red-sensitive emulsion layer silver iodobromide emulsion .................. 1.7g / m ² (silver iodide 10 mol%, Sensitizing dye A ..... 8.0 × 10 ^-5 mol per 1 mol of silver Sensitizing dye B ......... 2.4 × 10 ^-5 mol per 1 mol of silver Sensitizing dye C ………… 1 mol of silver 2.4 × 10 ^-5 mol Coupler C-7 ......... 0.32g / m ² Coupler C-17 ... 0 with respect to 3.3 × 10 ^-5 mol sensitizing dye D ......... 1 mol of silver for Gelatin layer containing 0.001 g / m ² 6th layer; intermediate layer Gelatin layer 7th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion 0.55 g / m ² (5 mol% silver iodide) , Average particle size 0.5 μ) Sensitizing dye G ………… 3.8 × 10 ^-4 mol with respect to 1 mol of silver Sensitizing dye E ………… 1.5 × 10 ^-4 mol with respect to 1 mol of silver include a coupler C-8 ......... 0.29g / m ² coupler C-3 ......... 0.04g / m ² coupler C-10 ... 0.055g / m ² coupler C-11 ... 0.058g / m ² gelatin layer 8th layer: second green-sensitive emulsion layer silver iodobromide emulsion .................. 1.0g / m ² (silver iodide 6 mol%, spherical average particle size 1.2μ Child) Sensitizing dye G ......... 1 mol of silver 1.1 × 10 ^-4 mol Coupler C-8 ...... against 2.7 × 10 ^-4 mol sensitizing dye E ......... 1 mol of silver relative to ... 0.25 g / m ² coupler C-3 ... 0.013 g / m ² coupler C-10 ... 0.009 g / m ² coupler C-11 ... gelatin layer containing 0.011 g / m ² 9th layer; 3 Green-sensitive emulsion layer Silver iodobromide emulsion: 2.0 g / m ² (8 mol% silver iodide, spherical particles having an average grain size of 1.8 μ) Sensitizing dye G: 1 mol of silver To 3.0 × 10 ^-4 mol Sensitizing dye E ... 1.2 mol / mol silver to 1.2 × 10 ^-4 mol Coupler C-3 ... 0.008 g / m ² coupler C-12. 0.05 g / m ² coupler C-18 ... Gelatin layer containing 0.001 g / m ² 10th layer; Yellow filter layer Yellow colloidal silver 0.04 g / m ² 2,5-di-t-pentadecylhydroquinone ・ ・ ・ Gelatin layer containing 0.03 g / m ² 11th layer; 1st blue sensitive emulsion layer Silver iodobromide emulsion ………… 0.32 g / m ² (silver iodide 5 mol%, average particle size 0.4 micron) coupler C-13 ...... 0.68g / m ² coupler C-14 ...... 0.03g / m ² coupler C-19 ... Gelatin layer containing 0.015 g / m ² 12th layer; second blue-sensitive emulsion layer Silver iodobromide emulsion 0.29 g / m ² (10 mol% silver iodide, average grain size 1.0 μm) ) sensitizing dye F ......... gelatin layer 13 layer containing 2.2 × 10 ^-4 mol coupler C-13 ...... 0.22g / m ² per mol of silver; fine emulsion layer silver iodobromide emulsion A gelatin layer containing 0.4 g / m ² (silver iodide 2 mol%, average grain size 0.15 μ) 14th layer; Third blue-sensitive emulsion layer Silver iodobromide emulsion 0.79 g / m ² (14 mol% silver iodide, average grain size 2.3 μ) Sensitizing dye F ………… for 1 mol of silver 2.3 × 10 ^-4 mol coupler C-13 ...... 0.19g / m ² coupler C-15 ... gelatin layer 15th layer comprising 0.001 g / m ^2; the first protective layer UV absorber C-1 ... ... 0.14 g / m ² UV absorber C-2 ...... Gelatin layer containing 0.22 g / m ² 16th layer; second protective layer Polymethylmethacrylate particles (diameter 1.5 µ) ...... 0.05 g / M ² containing gelatin layer Each layer contains, in addition to the above composition, a gelatin hardening agent, C-16.
And surfactants were added. The sample manufactured as described above was designated as Sample 101.

The compounds used to prepare the samples are shown below.

C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-10 C-11 C-12 C-13 C-14 C-15 C-16 C-17 C-18 C-19 Sensitizing dye A Sensitizing dye B Sensitizing dye C Sensitizing dye D Sensitizing dye E Sensitizing dye F Sensitizing dye G Preparation of Samples 102 to 118 Sample 102 was prepared in the same manner as Sample 101, except that the compounds shown in Table 1 were added to the third layer and the fourth layer of Sample 101 in the amounts shown in Table 1. ~ 118 were produced.

Part of each of these samples 101 to 118 is subjected to red wedge exposure, and the other part is exposed to white wedge (red +
Green + blue light). The amount of red exposure at the time of white exposure and the amount of exposure at the time of red exposure were equivalent.

Each of these exposed samples was color-developed with a color developer.

Development processing in this case was carried out at 38 ° C. as described below.

By comparing the cyan of red light exposure and the cyan of white light exposure, it can be said that the inter-image effect is greater as the exposure amount difference ΔlogE at the density of 0.6 is larger.

Granularity (RMS granularity) is 1000 of the standard deviation of the density fluctuation that occurs when scanning with a microdensitometer.
The value is doubled.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Settling 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2 0.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100 0.0 g Ethylenediaminetetraacetic acid dinatrium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 pH 6.0 Fixer ethylenediaminetetraacetic acid dinatrium salt 1.0 g Sodium sulfite 4.0 g Thio Ammonium sulfate aqueous solution (70%) 175.0 ml Sodium acid 4.6 g Water added 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water added 1.0 Compound A Compound B From these results, the present invention provides excellent inter-image effect and graininess as compared with the comparative example, and further, Dm
It can be said that in is low.

Example 2. Then, the first to twelfth layers were applied on the triacetate film base in the following order to prepare a sample 201.

First layer: anti-halation layer (gelatin layer containing black colloidal silver).

Second layer: gelatin intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
10% of 1% of 10% gelatin aqueous solution and 2 kg of emulsion obtained by high-speed stirring together with 1 kg of non-chemically sensitized fine grain emulsion (grain size 0.06μ, 1 mole silver iodobromide emulsion)
It was mixed with 1.5 kg of gelatin and coated so as to have a dry film thickness of 2 μ (silver amount 0.4 g / m ² ).

Third layer: low-sensitivity red-sensitive emulsion layer 100 g of 2- (heptafluorobutyramide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide) -phenol, which is a cyan coupler, 100cc of cresyl phosphate and 100cc of ethyl acetate
500 g of an emulsion obtained by dissolving in a 1% aqueous solution of 10% gelatin and stirring at high speed was added to 1 kg of a red-sensitive silver iodobromide emulsion.
(Containing 70 g of silver and 60 g of gelatin, the iodine content was 4 mol%), and coated so that the dry film thickness was 1 μm.
(Silver amount: 0.4 g / m ² ) 4th layer: High-sensitivity red-sensitive emulsion layer 2- (heptafluorobutyramide) -5- {2 '-(2 ", 4" -di-t-, which is a cyan coupler. Aminophenoxy) butyramide} -phenol (100 g) was added to tricresyl phosphate (100 cc) and ethyl acetate (100 cc).
1000 g of an emulsion obtained by dissolving in a 1% aqueous solution of 10% gelatin and stirring at high speed was added to 1 kg of a red-sensitive silver iodobromide emulsion.
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 2.
5 mol%) and coated so that the dry film thickness would be 2.5 μm. (Silver amount: 0.6 g / m ² ) Fifth layer; Intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
1 kg of an emulsion obtained by high-speed stirring with 1 kg of an aqueous solution in 10% gelatin was mixed with 1 kg of 10% gelatin to obtain a dry film thickness of 1
It was applied so as to have a thickness of μ.

Sixth layer: low-green emulsion layer C-2 which is a magenta coupler instead of the cyan coupler
0 g was used to obtain 300 g of an emulsion obtained in the same manner as the emulsion of the third layer, and 1 kg of a green-sensitive silver iodobromide emulsion (70 g of silver).
g, and 60 g of gelatin, the iodine content was 3 mol%), and the mixture was applied to give a dry film thickness of 1.3 μm. (Amount of silver 0.8 g / m ² ) 7th layer: Highly sensitive green emulsion layer C-2 which is a magenta coupler instead of the cyan coupler
0 g was used to prepare 1000 g of an emulsion obtained in the same manner as the emulsion for the third layer, and 1 kg of a green-sensitive silver iodobromide emulsion (silver 70
g and 60 g of gelatin, and the iodine content was 2.5 mol%), and the mixture was applied so that the dry film thickness would be 3.5 μm. (Amount of silver: 0.8 g / m ² ) Eighth layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated so as to have a dry film thickness of 1 μm.

Ninth layer: low-sensitivity blue-sensitive emulsion layer α-which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, and 1 kg of a blue-sensitive silver iodobromide emulsion (70 g of silver). , Containing 60 g of gelatin,
Iodine content is 2.5 mol%), dry film thickness 1.5
It was applied so as to have a thickness of μ. (Silver amount: 0.6 g / m ² ) 10th layer: high-sensitivity blue-sensitive emulsion layer α- which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, and 1 kg of the above spherical silver iodobromide emulsion B (70 g of silver). , 60 g of gelatin, and iodine content of 2.5 mol%), dry film thickness 3
It was applied so as to have a thickness of μ. (Amount of silver: 1.1 g / m ² ) Eleventh layer; Second protective layer 1 kg of the emulsion of the ultraviolet absorber C-1 used in Example 1
It was mixed with 1 kg of 10% gelatin and applied so as to have a dry film thickness of 2 μm.

Twelfth layer; First protective layer Surface-fogged fine grain emulsion (grain size 0.1 μ,
1 mol% silver iodobromide emulsion) An aqueous gelatin solution containing polymethylmethacrylate particles (diameter: 1.5 μm, 0.05 g / m ² ) was coated to a dry film thickness of 0.8 μm.

A gelatin hardening agent C-16 and a surfactant were added to each layer.

Preparation of Samples 202 to 220 Samples 201 to 220 were the same as Sample 201 except that the compound shown in Table 2 was added to the layer shown in Table 2 in the fifth layer or the sixth layer. Samples 202 to 2 in exactly the same manner
20 was produced.

C-20 Part of each of these samples 201 to 220 was exposed to green wedging at a different position, and white was exposed to other part (red + green + blue light). The exposure amount of green light during white exposure was the same as the exposure amount of green light exposure.

The exposed samples were subjected to the following development processing.

Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 38 ° C Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water washing 4 minutes 〃 Safety The composition of the 1-minute normal-temperature drying treatment liquid is as follows.

First developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 3 g sodium sulfite 20 g hydroquinone monosulfonate 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4-hydroxymethyl- 3 Pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water added 1000 ml Reversal solution water 700 ml Nitro NNN trimethylenephosphonic acid 5 Natriu Mu salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water added 1000 ml Color developer water 700 ml Nitrilo / N / N / N-trimethylenephosphonic acid / 5 Sodium salt 3g sodium sulfite 7g tertiary phosphoric acid Thorium (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazine acid 1.5 g N.ethyl-N- (β-methanesulphonamidoethyl) -3-methyl -4-Aminoaniline / sulfate 11g Ethylenediamine 3g Water is added 1000ml Adjusted water 700ml Sodium sulfite 12g Sodium ethylenediamine / tetraacetate (dihydrate) 8g Thioglycerine 0.4ml Glacial acetic acid 3ml Water is added 1000ml Bleached water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ethylenediaminetetraacetate Iron (III) ammonium (dihydrate) 120 g Potassium bromide 100 g Water is added 1000 ml Fixer water 800 ml Sodium thiosulfate 80.0 g Sodium sulfite 5.0 g Heavy Sodium sulfite 5.0 g Water added 1000 ml Stabilized water 800 ml Formalin (37% by weight) 5.0 ml Fuji Drywell (Fuji Film Co., Ltd. surfactant) 5.0 ml Water added 1000 ml With the above developer With respect to the developed sample, the magenta at the time of exposure to green light and the magenta at the time of exposure to white light were compared, and the exposure amount difference ΔlogE at a density of 1.0 was measured.

It can be said that the larger the value of ΔlogE, the greater the interimage effect.

Also, the MTF value of 10 cycles / mm was measured.

The results are shown in Table 2.

From these results, it is clear that the present invention brings about an excellent inter-image effect and also an improvement in sharpness without a decrease in Dmax due to an increase in fog, as compared with the comparative example.

Example 3. Potassium bromide and potassium iodide and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare a silver iodobromide emulsion (AgI = 3 mol%) having an average particle size of 0.7 μm, which was desalted and then chloroauric acid. Then, silver iodobromide emulsion A was prepared by optimally sensitizing gold and sulfur with sodium thiosulfate.

Similarly, Emulsion B (average particle size: 1.3 μAgI = 3 mol%) was prepared.

As a sample, a black-and-white photographic light-sensitive material having the following composition was prepared on a cellulose triacetate film support.

First layer; low-sensitivity silver halide emulsion layer Emulsion A (coating silver amount: 1 g / m ² ) Second layer: High-sensitivity silver halide emulsion layer Emulsion B (coating silver amount: 2.5 g / m ² ) Third layer; protective layer gelatin (1.3 g / m ²⁾ polymethyl methacrylate particles (diameter 1.5μ) 0.05g / m ² in addition to gelatin hardener C-16 of the composition in each layer, a surfactant and a thickener Polystyrene sodium sulphonate was added. The sample manufactured as described above was designated as sample 301.

These samples were exposed through a pattern for measuring graininess, and then subjected to the development processing described below.

Developer (E) Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax.5H ₂ O 1.53 g Water was added 1 Developer (F) Metol 2 g Sodium sulfite 100 g Hydroquinone 5 g Borax.5H ₂ O 1.53 g Potassium iodide (0) 1%) 5 ml Water is added 1 Fixer Ammonium thiosulfate 200.0 g Sodium sulfite (anhydrous) 20.0 g Boric acid 8.0 g Ethylenediaminetetraacetic acid disodium 0.1 g Aluminum sulfate 15.0 g Sulfuric acid 2.0 g Glacial acetic acid 22 1.0 g of water was added (pH is adjusted to 4.2), and black and white development was carried out with the above developing solution at 20 ° C. for 7 minutes.

Granularity (RMS granularity) is 1000 of the standard deviation of the density fluctuation that occurs when scanning with a microdensitometer.
The value is doubled.

The sharpness was measured by the MTF value.

The results are shown in Table 3.

From these results, it is clear that the sample using the present invention has less fog and is excellent in graininess and sharpness as compared with the comparative example.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 59-74557 (JP, A) JP 53-147529 (JP, A) JP 55-21067 (JP, A) JP 61- 48832 (JP, A) JP-A-49-129536 (JP, A) US Patent 3639417 (US, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one compound represented by the following general formula [I] is light-sensitively halogenated. It is contained in the silver layer and / or the adjacent hydrophilic colloid layer and has the following general formulas [II] and [II]
A silver halide photographic light-sensitive material comprising at least one compound represented by the formula [I] in a light-sensitive silver halide layer. General formula [I] A- (Time) t-X General formula [II] General formula (III) In the general formula [I], A means a redox mother nucleus, and is not oxidized by being oxidized during photographic processing. Represents a group of atoms capable of leaving, Tmie represents a timing group linked to A by a sulfur atom, a nitrogen atom, or an oxygen atom, t is an integer of 0 or 1, and X is a development inhibitor. Represent. In the general formula [II], R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group, and Z
Represents a polar substituent. Y is R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group,
It represents an alkenyl group or an aralkyl group. However, Y is -S
When-, Z is not an amino group. X'is -O
-, Alternatively, -S- is represented, and R'represents a hydrogen atom or a substituted or unsubstituted alkyl group or alkenyl group, respectively. R ″ represents a hydrogen atom or a group capable of substituting it, M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions. N represents 0 or 1, m represents 0, Represents 1 or 2.
When X'is -S-, m = 0 is not included. l represents 4-m. In the general formula [III], R represents a linear or branched alkylene group, an alkenylene group, an aralkylene group, or an arylene group, and Z'represents a hydrogen atom or a polar substituent. Y'is -S-, And R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇
Alternatively, R ₁₈ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, or an aralkyl group. However, when Y'is -S-, Z'is not an amino group. n represents 0 or 1.