JPS6156347A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To improve a photosensitivity and a contrast and to prevent a color stain apt to generate in developing by using an anti-foggant or a compd. releasing its precursor in an amount proportional to that of a developing silver in developing. CONSTITUTION:The material provides at least one of silver halide emulsion layers on a base material and contains a color stain inhibitor represented by the formula and the anti-foggant or the compd. releasing its precursor in the amount proportional to that of the developing silver in developing. In the formula, R<1> and R<2> are each a hydrogen atom, a halogen atom and a carboxyl group or a sulfone group capable of a forming a salt; R<1> together with R<2> may be composed of a carbon right. One of X<1>-X<4> groups is a hydroxyl group, remainder two groups are each hydroxyl group or a sulfonamide group. further remainder one group is an atom or a group of R<1> or R<2>. Total carbon numbers of R<1>, R<2>, and X<1>-X<4> amount to >=10. Therefore, the effects of improving the photosensitivity, the contrast and preventing the color stain are obtd.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic material which is sensitized and has high contrast, and which prevents color staining during development. Regarding photosensitive materials.

Prior Art In a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion and developed using a color-forming developing agent such as paraphenylenediamine, the oxidized color-forming developing agent produced during development is It is well known that so-called "color-mixing" development occurs in which undesired dyes migrate into the imaging layer.

Furthermore, it is known that during one-color development, undesirable "color fog" development occurs due to air resistance of the color developing agent, fog of the emulsion, and the like.

In the following, this "color turbidity" and "color fog" will be collectively referred to as one-color contamination.

In order to prevent color staining, various methods using hydroquinone have been proposed. For example, the use of seven-chain linear alkylhydroquinone is described in U.S. Pat. No. 453, West German Patent Publication No. 2,149,789, Japanese Unexamined Patent Publication No. 15643/1984
No. 8 and No. 49-106329.

On the other hand, regarding dilinear alkylhydroquinone, U.S. Pat.
British Patent No. 752.146, L, 086.208 and Chemical Abstracts, Vol. 58, 6367h, and for di-branched alkylhydroquinone, US Pat. No. 3,700.453, No. 2, 732.

No. 300, British Patent No. 1.086.208, cited above in "Chemical Abstracts" magazine, JP 50-156438.
No., Special Publication No. 50-21219, No. 56-40,818
There is a description in the issue etc.

In addition, regarding the use of alkylhydroquinone as a color stain inhibitor, British Patent No. 558.258, British Patent No. 557,750 (corresponding U.S. Patent No. 2,360,290), British Patent No. 557, 802, British Patent No. 731, 301 issue(
Corresponding U.S. Patent No. 2.701,197), U.S. Patent No. 2,3
36.327, 2,403,721, 3.58
No. 2,333, West German Patent Publication No. 2,505.016 (corresponding to JP-A-50-110337), Japanese Patent Publication No. 56-408
It is also mentioned in issue 16.

It is known that "color turbidity" develops in color diffusion transfer photographic rolls as well as in ordinary color photographic sensitizers.
In order to prevent this, the above-mentioned hydroquinones are used.

Hydroquinone used as an agent for preventing color turbidity in diffusion transfer sensitive materials is described in JP-A-58-21249. Regarding the use of sulfonamide phenols as color clouding preventive agents for diffusion transfer sensitive materials, "Research Disclosure 3, 15162 (1973), p. 83, JP-A-55-72158, JP-A-57-24941 (
Corresponding U.S. Pat. No. 4,366,226).

On the other hand, recently, compounds (FRA compounds) that release caprase agents (FA) or their precursors upon reaction with oxidized products of the developing agent (FRA compounds) have been used in color photographic materials in accordance with the amount of developed silver during development. Attempts are being made.

・1 For example, JP-A No. 57-150845 describes a coupler that releases acylhydrazines, and due to the action of FA released when one silver halide grain is developed, multiple surrounding silver halide grains are Development of the silver halide grains is started, and the number of developing areas increases, resulting in the effects of sensitization and contrast enhancement.

However, in color photographic materials that use FR compounds in combination, the number of development initiation points increases due to the action of FA that is released imagewise during silver development, and therefore a larger amount of oxidized developing agent is generated than usual.

Therefore, in a color photographic material containing an FR compound, the above-mentioned color staining is more likely to occur than in a normal light-sensitive material.

Color staining due to the use of this type of FR compound cannot be prevented by the color stain preventing materials that are effective for conventional sensitive materials not using FR compounds as described above.

The main object of the present invention is to achieve sensitization and high contrast by using a compound that releases caprase agents or their precursors in response to the amount of developed silver during development, and to make it easier to remove dirt. An object of the present invention is to provide a photographic material that prevents color staining. Such objects are achieved by the invention described below.

That is, the present invention provides a silver halide photographic photosensitive material having at least one silver halide emulsion layer on a support and containing at least one coupler that reacts with an oxidized product of a color developing agent to form a dye. A silver halide material, characterized in that the material contains a compound that releases a caplase agent or its precursor in response to the amount of developed silver during development, and a color stain preventive agent represented by the following general formula (I). It is a photographic material.

General formula CI) (wherein R1 and R2 are each a hydrogen atom, a halogen atom, a carboxyl group or a sulfo group that may form a salt, or a substituted or unsubstituted alkyl group, an aryl group, an acylamide group, Represents an alkoxy group, aryloxy group, alkylthio group, arylthio group, carbamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, carbamoyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group or sulfonyl group. , R1 and R2 may be taken together to form a carbocycle.

X1, X2, Represents any of the atoms or groups listed above.

However, when XI, X2 and x3 simultaneously represent a hydroxyl group, R1 and X2. When X3 and x4 both represent a hydroxyl group, R2 is an atom or group other than a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group among the atoms or groups shown as R1 and R2 above.

Mata, R1, R2, Xi, X2, X3 t-3
The total number of carbon atoms in cl: and x4 is 10 or more. )■
Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below.

The silver halide photographic material of the present invention has at least one silver halide emulsion layer on a support, and contains at least one coupler that reacts with an oxidized form of a color developing agent to produce a dye. .

This silver halide photographic material also contains a compound (FR compound) that releases a capacitive agent (FA) or a precursor thereof in response to the amount of developed silver during development.

The FR compound is used not only in the silver halide emulsion layer but also in other photographic layers (intermediate layer, filter layer, protective layer, etc.) that constitute the silver halide photographic light-sensitive material and are laminated on the silver halide emulsion layer.
It may be added to any layer.

The FR compound is preferably used in an amount of tio-a to 0.5 mol, preferably 5 x 10-7 to 0.01 mol, per mol of silver halide in the silver halide emulsion layer to be added. When the compound is added to a layer adjacent to the silver halide emulsion layer, the amount of
It is preferable to increase the amount by 100%.

When the photosensitive silver halide emulsion layer is composed of two or more layers having the same color sensitivity but different sensitivities, it is preferable to add the FR compound to layers other than the lowest sensitivity layer.

FR compounds that can be used in the present invention include the following.

(1) A coupler that releases FA or its precursor upon coupling with the oxidation product of an aromatic primary amine developing agent.

(it) A coupler that couples with the oxidation product of an aromatic primary amine developing agent to yield a diffusible coupling product, which coupling product functions as an FA or a precursor thereof.

A redox compound that releases FA or its precursor by a redox reaction with the oxidation product of a developing agent or by a subsequent reaction of this reaction.

The above compounds +4+, (ri) and (mark) are represented by the following general formulas [1], [2] and [3], respectively.

(1) CP −(TIM E ) n −F
A(2)BALL-Cp-(TIME)n-FA(3
)RED -(TIME)n-FA In the above formula, , cp
represents a coupler residue capable of a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and BALL can be separated from Cp by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Represents a diffusion-resistant group, RED
represents a compound residue capable of redox reaction with the oxidation product of the developing agent.

TIME is Cp or R depending on the coupling reaction.
Represents a timing group that releases further FA after leaving the ED.

n represents 0 or 1, and when n is O, FA is
It is a group that can be separated from Cp or RED by a coupling reaction, and when n is 1, it is a group that can be released from TIME.

However, in the case of the compound represented by the general formula [2] in the above formula, FA does not have to be separated from Cp or TIME after the coupling reaction.

In general formula [1], -(T I ME) n -F
A binds to the coupling position of Cp, and the bond is cleaved during the coupling reaction.

In general formula [2], BALL is bonded to the coupling position of Cp, and the bond is cleaved during the coupling reaction. Moreover, since -(TIME)n-FA is bonded to a non-coupling position of Cp, the bond is not immediately cleaved upon coupling.

According to the general formula [3], -(TIME)n-FA is R
The ED is coupled to a device comprised of the RED by a redox reaction or subsequent reaction with the oxidation products of the developing agent.

Here, FA represents a so-called capulase agent that acts on silver halide grains during development to generate fog nuclei capable of initiating development.

FA acts reductively on silver halide grains during development to produce capri nuclei, or acts on silver halide grains to produce silver sulfide nuclei, which are fog nuclei that can initiate image formation, to brighten the grains. Examples include groups such as

A preferable group as FA is a group containing a group having adsorption properties to silver halide grains, and its general formula can be expressed as follows.

AD-(L)m-X In the formula, AD represents a group having adsorption property to silver halide, L represents a divalent group, m represents O or l, and X represents a reducing group. group or a group capable of acting on silver halide to produce silver sulfide.

However, if X is the latter, it may also have an AD machine spear, so AD-(L)m- is not necessarily necessary in this case.

When FA is a group represented by AD-(L)m-X,
The position that binds TIME, Cp or RED is AD-(
L) Any position of m-X may be used.

On the other hand, the group represented by TIME may be a trivalent group in the case of general formula [1].

That is, one of the trivalent bonds binds to FA, one of the remaining two bonds binds to the coupling position of Cp, and the other one binds to the non-coupling position of Cp. be.

The characteristic of compounds and products having such a structure is that during the coupling reaction with an aromatic primary amine developing agent, the bond with TIME bonded to the coupling site is broken, but the bond to the non-coupling position is broken. The bond with TIME that is cleaved is not cleaved, and the bond part (anion) of the cleaved TIME is
The bond between TIME and FA can be cleaved by intramolecular electron transfer and/or intramolecular nucleophilic substitution reaction to release FA.

Therefore, in the case of such a compound, it is necessary not only to be a trivalent group but also to have a structure capable of releasing FA by intramolecular electron transfer and/or intramolecular nucleophilic substitution reaction.

Below, regarding general formulas [1], [2], and [3],
This will be explained in more detail.

In the general formula (1), the coupler residue represented by Cp has a partial structure of the following yellow, magenta, and cyan couplers, as well as a colorless coupler and a black coloring coupler.

Here, typical examples of yellow couplers among couplers are U.S. Pat.
No. 10, 3, 265.

No. 506, No. 2.298.443, No. 3,048.1
No. 94, No. 3,447,928, etc.

Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas [■] and ([[I)] are suitable.

[■]

(m) R1 Note that the tree represents the bonding position of the FA group or TIME group (the same holds true up to general formula (XVI) below).

Here, R1 represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, R2 is a hydrogen atom, 1 or more halogen atoms,
Lower alkyl group, lower alkoxy group or total carbon number 8~
When there are two or more R2's representing the diffusion-resistant groups of 32, they may be the same or different.

A typical example of a magenta coupler is U.S. Patent No. 2.600.
, No. 788, I'i'i 12, 369, 489, 2
, No. 343,703, No. 2,311゜082, No. 3,
No. 152,896, No. 3,519.429, No. 3.0
No. 62.653, No. 2.908,573, Special Publication No. 1973
-27411, Japanese Patent Application No. 58-45512, 5.8
No. -23434, No. 58-142801, No. 58-1
It is described in No. 51354, No. 59-27745, etc. Among these magenta couplers, pyrazolones or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferred.

Therefore, the magenta coupler residue (Cp) is
Those represented by the following general formulas (IV), (V) and (Vl) are preferred.

(IV) r (V) (Vl) 1H Here, R1 represents a diffusion-resistant group having a total number of carbon atoms of 8 to 32, and R2 represents one or more halogen atoms, lower alkyl groups, lower alkoxy groups. , phenyl group, or substituted phenyl group.

Z represents a nonmetallic atomic group necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and this azole ring may have a substituent (including a fused ring).

A typical example of a cyan coupler is disclosed in U.S. Pat. No. 2,772.
No. 162, No. 2.895.826, No. 3.002, 8
No. 36, No. 3,034,892, No. 2,474,29
No. 3, No. 2,423,730, No. 2.367.531
No. 3,041.236, Special ■ 1984-9934
No. 1, No. 57-155538, No. 57-204545
No. 58-189154 and No. 59-31953
No. 58-118643, No. 58-187928, No. 58-18798, U.S. Patent No. 4,333,999
Among those cyan couplers described in No. 1, etc., phenols or naphthols are preferred.

Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas [■], [■), (IX) and (X,) are preferable.

[■]

[■] ([X) (X) Here, R1 represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, and R2 represents one or more halogen atoms, lower alkyl groups, or lower alkoxy groups. However, when R2 is 2 or more, they may be the same or different.

Further, cp may be a so-called colorless coupler.

A typical example of a colorless coupler is U.S. Patent No. 391,251.
No. 3, No. 4204867, JP-A-52-152721
It is stated in the number etc.

Representative examples of these colorless coupler residues have skeletons represented by the following general formulas [Kari], [■] and [R].

(XI) Here, R1 represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, and R2 represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group.

Here, R1 represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, and (2) represents an oxygen atom, a sulfur atom, or a nitrogen source atom.

1: R1 and R2 may be combined to form a 5- to 6-membered ring, which represents a nitrogen-containing heterocycle.

In addition to the above, the CP may also be a coupler residue that develops a black color by reacting with the oxidized form of a developing agent. Examples of such couplers include U.S. Pat. No. 1,939,231.
No. 2,181.944, No. 2,333,106, No. 4.126,461, West German Patent (Publication) 2゜64
It is described in No. 4.194 and No. 2,650,764. Specifically, those coupler residues are represented by the following general formulas (W), [bi] and (xvr).

〔fan〕

[Store] (xv'i) 82 Here, R is an alkyl group having 3 to 20 carbon atoms, or a phenyl group (hydroxyl group, halogen atom, amine group, 1 carbon number)
R2 is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkenyl group having 6 to 20 carbon atoms. R3 represents a halogen atom, an alkyl group or alkoxy group having 1 to 20 carbon atoms, or another monovalent organic group,
When there are two or more R3s, they may be different from each other.

Cp represented by the above general formulas (II) to (XVI)
may form a dimer or higher multimer at a portion other than the coupling site, or may be bonded to the polymer at that portion.

In general formula [2], the coupler residue represented by Cp has a partial structure represented by the above-mentioned general formulas (I) to (xvi), and BALL is bound to the wooden seal, and one of the other parts is -(TIME)n-FA is bound to.

- In the general formula [2], the diffusion-resistant group represented by BALL has a size and shape that imparts non-diffusivity to the coupler, and even if it is a polymeric group with multiple leaving groups linked together. It may also contain an alkyl group and/or an aryl group that provides non-diffusibility.
In the latter case, the total number of carbon atoms in the alkyl group and/or aryl group is preferably about 8 to 32. BAL
L has a group for bonding to the coupling position of Cp, typical examples of which are l -0-1-S-1-N=N +, -o-c +.

vinegar It is.

In the general formula [3], the group represented by RED has a skeleton of hydroquinone, catechol, 0-aminophenol or P-aminephenol, undergoes an oxidative quinary reaction with the oxidation product of the developing agent, and is subsequently subjected to alkaline hydrolysis. -(TIME)n-FA group C following general formula (xvrr)
~(XXII) represents a group releasing a compound (hereinafter abbreviated as FR).

Specific examples thereof are shown in general formulas (in) to (xxn).

[Two ■]

[Xvm) Ll Ba(XIX) [Xx] (XXI) (XX11) In the above formula, R1 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an alkylthio group, Represents a cyan group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxy group, sulfo group, sulfonyl group, acyl group, carbonamide group, sulfonamide group, or heterocyclic group, and when there are two or more R] , may be different from each other, or the two mic-positions may be bonded to form a benzene ring or a 5- to 7-membered heterocycle, R2 is an alkyl group, an aryl group, an acyl group, T1 represents a hydrogen atom or a group capable of being hydrolyzed and separated under alkaline conditions.

If there are two 1's in the molecule, they may be different from each other. Typical examples of TI include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, an oxalyl group, etc. It will be done.

The timing group represented by TIME includes U.S. Pat.
As described in No. 7, etc., after separation from Cp or RED by a coupling reaction or redox reaction, FA is removed by an intramolecular substitution reaction.

British Patent No. 2,072,363A, Japanese Unexamined Patent Publication No. 154-1987
No. 234, No. 57-188035, No. 56-1149
No. 46, No. 57-56837, No. 58-209736
No. 58-209737, No. 58-209738, No. 58-209740, No. 58-98728, etc., which separate from FA by electron transfer via a conjugated system.

Examples include those which are coupling components capable of removing FA through a coupling reaction with an oxidized product of an aromatic primary amine developer, as disclosed in JP-A-57-111536.

These reactions may occur in one step or in multiple steps.

As previously mentioned, a trivalent TIME that binds to the coupling and non-coupling sites and FA is also preferred, and an example of its incorporation into a yellow coupler is described in JP-A-58-209740.

When FA is a group containing AD-(L)m-X, AD may be directly bonded to the carbon atom at the coupling position, or if L or X can be detached by the coupling reaction. These may be bonded to the coupling carbon, or what is known as a so-called two-button leaving group may be present between the coupling carbon and AD.

These groups include alkoxy groups (e.g. methoxy, !l!;), aryloxy groups (e.g. phenoxy, !!:), alkylthio groups (e.g. ethylthionoph), arylthio groups (e.g. phenylthio), heterocycles. Examples include oxy groups (eg, tetrazolyloxy groups), heterocyclic thio groups (eg, pyridylthio groups), and heterocyclic groups (eg, hydantoinyl groups, birazolyl groups, triazole groups, benzotriazolyl groups, etc.).

In addition, those described in British Patent Publication No. 2,011,391 can be used as the FA.

Groups adsorbable to silver halide represented by AD include nitrogen heterocycles with dissociable hydrogen atoms (pyrrole, imidazole, triazole, tetrazole, benzimidazole, benzimidazole, benzotriazole, uracil, tetraaza). indene, imidazo 1
heterocycles with at least one nitrogen atom and another heteroatom (oxygen, sulfur, selenium, etc.) in the ring (oxazole, thiazole, thiazoline, etc.); Thiazolidine, thiadiazole, benzothiazole,
benzoxazole, benzselenazole, etc.), heterocycles with mercapto groups (2-mercaptobenzthiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 1-phenyl-5-mercaptotetrazole, etc.), quaternary IM (tertiary amines, pyridine, quinoline, benzthiazole, benzimidazole, benzoxazole, etc. quaternary salts), thiophenols, alkylthiols (cysteine, etc.), thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbyl acids, etc.).

The divalent linking group represented by L in FA is alkylene, alkenylene, phenylene, naphthylene, -0-1
-S-1-SO-1-so2-1-N=N-, carbonyl, amide, thioamide, sulfonamide, ureido,
It is composed of a ring selected from thioureiol, heterocycle, etc.

If one of the divalent linking groups constituting L is appropriately selected to be a group that can be cleaved by the action of components in the developer (for example, aqueous ions, hydroxylamine, sulfite ions, etc.),
It is also possible to inhibit or deactivate the caprase action.

Examples of the group represented by , tetrazolium salts, quaternary salts such as ethylene bispyridinium salts, carbazic acid, etc.) or compounds that can form silver sulfate during development (e.g., thiourea, ioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidine compounds, etc.) ) residues, etc.

Among the groups represented by I can do it.

Note that the bonds of these compound residues may be in normal positions.

Furthermore, particularly preferred among FAs are the following general formulas (xx
m) and (xxrv).

General Formula (XXI[I) General Formula (XXIV) In the formula, R2 is an acyl carbamoyl group, an alkylsulfokol group, or an arylsulfonyl group.

7 represents a alkoxycarbonylbonyl group or a sulfamoyl group, R2 represents a hydrogen atom, an acyl group, an alkoxycarbomyl group, or an aryloxycarbonyl group, and R3 represents a halogen atom, an alkoxy group, an alkenyl group, an aryl group, an aryloxy group , an alkylthio group, an arythio group, a carbonamide group or a sulfonamide group.

In addition, m represents an integer from O to 4, and when m is 2 or more,
R3 may be the same or different, or two or more may be bonded together to form a condensed ring. L has the same meaning as before, ie, represents a divalent linking group, and n is O
Or represents 1. Zl represents a single ring, a fused heterocycle, or a fused heterocycle.

Examples of substituents are discussed in more detail below.

R1 is an acyl group (formyl group, acetyl group, propionyl group, trifluoroacetyl group, pyruvoyl group, etc.), a carbamoyl group (dimethylcarbamoyl group, etc.),
Alkylsulfonyl group (methanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), or sulfamoyl group (methylsulfamoyl 31)
R2 is a hydrogen atom, an acyl group (such as a trifluoroacetyl group), an alkoxycarbonyl group (such as a methoxycarbonyl group), or an aryloxycarbonyl group (such as a phenoxycarbonyl group), and R3 is a halogen atom (such as a fluorine atom, chlorine atoms, etc.)
, alkoxy group (methoxy group, methoxyethoxy group, etc.)
, alkyl group (methyl group, hydroxymethyl group, etc.), alkenyl group (allyl group, etc.), aryl2t; (phenyl group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, etc.), arylthio group ( phenylthio group, etc.), carbonamide group (acetamide group, etc.), or sulfonamide group (methanesulfone 7mide group, etc.).

′) as well as An example of this is shown in the AD example given below.

Examples of FR compounds used in the present invention include JP-A-57-
No. 150845, No. 59-50439, Special WI11i
No. 1158-31610, No. 58-31611, No. 5
No. 8-146097, No. 58-214808, No. 58
-237101 etc.

An example of AD is shown below. The free bond is -(L)m-
Bonds to X and -(TIME)n-.

An example of L is shown below.

-CH2-, -CH2CH2-, -0CH2-.

-0CH2CH2+, -3CH2-, -Coo- Examples of X are shown below.

-NHNHCHO, -NHNHCOCH3.

-NHNH3O2CH3, -NHNHCOCF3.

-N-NHCHO COOC2H5.

-CONHNHCH3, -CONHNH2 further [1]
Preferred specific examples of FA in ~[3] are shown below.

l 11 CH2CH2NHCCH3 F represented by general formulas [1] to [3] used in the present invention
Specific examples of R compounds are as follows.

Example 1-+9 expressed by general formula [1]
- The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention includes:
Any of silver bromide, silver iodobromide, silver iodo-11 dibromide and silver chloride may be used as the silver halide. Preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. be. Particularly preferred is silver iodobromide containing from 2 mol % to 20 mol % silver iodide.

In addition, the amount of silver is assumed to be a normal debt.

The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the ridge length in the case of cubic grains, expressed as an average based on the projected area) is particularly important. However, it is preferably 3 pm or less.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like. It may have a crystal form or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is described in "Chimie et al." by P. Glafkides.
Physique Photo-graphique
” (Paul Mante 1, 1967), G.
, F. Duffin” Phatographic
Eo+ulsionChemistry” (Th
e Focal Press, 1966), V, L
, “Making” by Zelikman et al.
and Coating Photography
c Emulsion” (The Focal Pres.
s, 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondreau double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium Jl, iridium salt or its 7111, rhodium salt or its complex salt,
Iron salts or iron complex salts may also be present.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which is performed by gelatinizing gelatin, may be used. Polymers (e.g. polystyrene sulfonic acid) or gelatin derivatives (e.g. acylated gelatin, carbamoylated gelatin, etc.)
A sedimentation method (flocculation) may also be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see, for example, “Die Grundlagen,” edited by H. Frleser.
derPhotographischen Praz
ess witSilberhalogeniden
”(Akademische Verlagsgese
llschft, 1i388), pages 675-734, can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds);
Noble metal compounds (e.g., gold complexes, pt, Ir, P
A noble metal sensitization method using complex salts of metals of group Ⅰ of the periodic table such as d, etc. can be used alone or in combination.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include:
cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

The silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention contains at least one coupler that reacts with an oxidized product of a color developing agent to produce a dye.

These color-forming couplers may be used in conjunction with a polymeric coupler latex or alone in layers that do not use a polymeric coupler latex.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolone benzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides). Cyan couplers include naphthol couplers and phenol couplers.

These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either 4-equivalent or 2-equivalent to silver ions.

The amount of these color-forming couplers used is from 10@-4 to 10 moles of I.sub.X per mole of silver halide, preferably 2.times.
IO-3 to 1 mole.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DI couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain an R coupling compound.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

Two or more types of the above-mentioned couplers and the like can be used together in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers.

The photographic color couplers used are conveniently selected in combination to give a mid-tone gray color.The maximum absorption band of the cyan dye formed from the cyan color former is between about 600 and 720 nm, Preferably, the maximum absorption band of the magenta dye formed from the yellow color former is between about 500 and 580 nm, and the maximum absorption band of the yellow dye formed from the yellow color former is between about 400 and 480 nm.

The present invention can be used in general silver halide color photographic materials such as color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies, and color reversal film for TV. In particular, when used in color negative films and various color reversal films that require high sensitivity and high image quality, remarkable effects can be obtained in improving sensitivity, improving graininess, and speeding up processing.

The present invention can be applied to light-sensitive materials that use a single black coupler system or a mixed three-color coupler system. A detailed description of the one-way black coupler is provided in U.S. Pat. No. 3,622,629.
No. 3.73, No. 4,735, No. 4,12
No. 6,461, JP-A No. 52-42725, No. 55-1
No. 05247 and No. 55-105248, and the three-color coupler mixing system is described in Re53arc.
A detailed explanation can be found in H. Disclosure No. 1712. When these methods are used for X-ray films, for example, they have remarkable effects such as reducing the amount of coated silver, speeding up processing, and reducing exposure dose due to improved sensitivity.

The present invention can also be applied to light-sensitive materials for color diffusion transfer. Either direct reversal type or negative type silver halide can be used.

The present invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on a support. Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. The red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler (usually each of these is included, but different combinations may be used depending on the case). can.

The present invention is particularly advantageous in improving sensitivity when used in light-sensitive materials having at least two emulsion layers having the same color sensitivity but different sensitivities (see British Patent No. 923.045). Adding it to emulsion layers other than the sensitive layer is particularly advantageous for improving sensitivity.

Furthermore, in a light-sensitive material having at least three emulsion layers with the same color sensitivity but different sensitivities, adding an FR-emitting compound to the emulsion layers other than the lowest sensitivity layer not only improves the sensitivity but also improves graininess. It is also advantageous (see Japanese Patent Publication No. 49-15495).

In the present invention, a known method such as the method described in U.S. Pat. No. 2,322,027 can be used to introduce the FR compound or coupler used in the photosensitive material into the photographic photosensitive layer. .

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate) ), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelaate), trimesic acid esters (e.g. tributyl trimesate). ) etc., or organic solvents with a dissolution point of about 30 to 150 degrees, such as lower alcohol acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate. After dissolving in etc.
Dispersed in hydrophilic colloids. The above-mentioned high temperature point organic melt and low δ point organic solvent may be mixed and used. Also,
Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it can be introduced into the wood-philic colloid as an alkaline aqueous solution.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of other synthetic hydrophilic polymer substances include, for example, OLS No. 2,312°708, USA! +
') Permit No. 3.620.751, No. 3.879.20
No. 5, Japanese Patent Publication No. 43-7561.

The silver halide photographic light-sensitive material of the present invention has the following general formula CI
) Contains a color stain preservative represented by:

General formula [Engine] In the formula, R1 and R2 are each a hydrogen atom, a halogen atom [for example, chlorine, bromine, fluorine, etc.], a carboxyl group (which may form a salt with Na, etc.), a sulfo group (May form a salt with Na, etc.) Alkyl group [May be substituted with a halogen atom, hydroxyl group, alkoxy group, etc., preferably with a total number of carbon atoms of 1
-15, such as methyl group, ethyl group, t-butyl group, n-pentadecyl group], aryl group [aryl group is a halogen atom, an alkyl group,
The total number of carbon atoms is preferably 6 to 30, which may be substituted with an alkoxy group or the like. For example, 4-(n-
dodecyloxy]phenyl group, p-tolyl, group, 3,4-
dichlorophenyl group, 4-dodecylphenyl group], acylamino group [the acyl group may be substituted with an alkyl group, an aryl group, etc., and preferably has a total number of carbon atoms of 2 to 30, such as acetylamino 7 group, benzoylamino group, α-(2,4-di-t-amylphenoxy)butyramide group, etc.), alkoxy group [which may be substituted with a halogen atom, hydrogen group, aryl group, etc., preferably a general carbon number is 1
~10, for example, methoxy group, ethoxy group, butoxy group], aryloxy group [Aryl group may be substituted with / 3o is preferable, and may be substituted with, for example, phenoxy group, 4-n-dodecylphenoxy group], alkylthio group [)\rogen atom, hydroxyl group, alkoxy group, etc., and preferably has a total number of carbon atoms of 1 to 20. methylthio group, hexadecylthio group, etc.], arylthio group [The aryl group may be substituted with /\rogen atom, alkyl group, alkoxy X, etc., and the total number of carbon atoms is preferably 6 to 30, for example , phenylthio group, P-tolylthio group, 4-(n-totisyloxy)phenylqztru, etc.], carbamoyl amine 7 group [cal/hemoyl group may be substituted with alkylno&, aryl group, etc., preferably with a carbon number of Those with a total of 2 to 20, such as NH
2C0NH- group, N-7enylcarbamoylamino group, etc.], alkoxycarbonylamino group [the alkoxy group may be substituted with a halogen atom, a hydroxyl group, an aryl group, etc., and preferably has a total number of carbon atoms of 2 to 20. ,
For example, a methoxycarbonylamino group, an ethoxycarbonylamino group, etc.], the aryloxycarbonylamino group may be substituted with an alkyl group, chlorine, an alkoxy group, etc., and preferably has a total number of carbon atoms of 7 to 30; For example, phenoxycarbonylamide 7 groups], carbamoyl group [preferably those having an alkyl group or aryl group having 1 to 20 carbon atoms, such as N,N-di(n-
octyl) carbamoyl group], acyl group [preferably those having an alkyl group or aryl group having 1 to 20 carbon atoms, such as an acetyl group or an ethyl carbonyl group], an alkoxycarbonyl group [alkoxy group is a halogen atom, It may be substituted with a hydroxyl group, an aryl group, etc., and preferably has a total number of carbon atoms of 2 to 2.
0, for example, methoxycarbonyl group, ethoxycarbonyl group], aryloxycarbonyl group [aryl group is an alkyl group,
Chlorine, alkoxy group, (may be substituted with etc., preferably one with a total number of carbon atoms of 7 to 30, such as phenoxycarbonyl group), sulfamoyl group (sulfamoyl group is substituted with alkyl group, aryl group, etc.) For example, NH2s after the total number of carbon atoms is O~20.
o2-group, N,N-jib0pic 7. )b7・Ino' group, etc.]・1 Sulfonyl group [preferably one having an alkyl group or aryl group having 1 to 20 carbon atoms, for example.

p-toluenesulfonyl group], represents.

However, R1 and X2 when Xi, X2 and x3 described below simultaneously represent a hydroxyl group.

When x3 and x4 both represent a hydroxyl group, R2 is:
It is selected from groups and atoms other than the carbamoyl group, alkoxycarbonyl group, and aryloxycarbonyl group listed above.

Note that R1 and R2 may be taken together to form a fused benzene ring, especially on carbon.

In the general formula CI), Xi , X2 , X3 and x
4, one of them represents a hydroxyl group, the other two represent a hydroxyl group or a sulfonamide group, and the last one is R1
, represents an atom or group selected from the same range as R2.

In the above, the sulfonamide group is represented by the following formula: %formula% is a group represented by In the formula, R5 is.

Each substituted or unsubstituted 7-aryl group [The aryl group may be further substituted with a halogen atom, an alkyl group, an alkoxy group, etc. The total number of carbon atoms is preferably 6 to 30. For example, 4-(n-totisyloxy)phenyl group, p-tolyl group, 3,4-di-chlorophenyl group,
4-dodecylphenyl group, etc.].

Alkyl group [The alkyl group may be further substituted with a halogen atom, hydroxyl group, aryloxy group, alkoxy group, etc. Those having a total carbon number of 1 to 30 are preferable. For example, a methyl group, a trifluoromethyl group, an n-hexadecyl group, a 1-(m-bentadecyl quinoxylapropyl group, etc.), or an amino group [the amine group is further substituted with an alkyl group, an aryl group, etc.]. The total number of carbon atoms is preferably 0 to 30.

For example, dimethylamino group, dipropylamino group, etc.] represents.

R1, 112, X], X2, X3,
The total number of carbon atoms in X4 must be 10 or more for the purpose of suppressing the migration of the compound from the additive layer to other layers.

Among these, the most effective one is Xi.
, X2, X3 and x4 is a hydroxyl group, the remaining two are each a hydroxyl group or a sulfonamide group, and the last one is a hydrogen atom.

That is, there are 12 types shown below.

No, X”
X21 0HOH 20HOH 3-NH3O2R50H 4-NH5O2R50H 5-NH5O2R5H 60H-NHSO2Rs 7 0H-NHSO2Rs8 -N
H3O2Rs -NHSO2Rs9 -NH
SO2Rs -NH5O2Rsl 0 -N
H5O2Rs Hl 1 -NHS
O2R50H 12-NHSO2R5H X 3 X 40HH H0H OHH H0H OH0H OHH H0H OHH H0H -NHSO2Rs 0H-NH5O2
R5H OH-NH3O2R5 Among these, more preferable compounds are No. 1.2
, 4, 5, 7, 10.12.

Among these, especially No, 2°No, 4. N
o, 7. It is most preferred that one of R5 and R5 is a substituted or unsubstituted 7-mino group.

In addition, R1 and R2 are a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, an aryl group, an acylamino group, an alkoxy group, an alkylthio group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, respectively. , a sulfonyl group, or a fused ring.

Further, a hydrogen atom, a carboxyl group, a sulfo group, an alkyl group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, a sulfamoyl group, or a sulfonyl group are most preferred.

The compound of general formula CI) of the present invention can be used in the intermediate layer as a color turbidity preventing agent. In this case, -・
per layer, 1, O x 1 0-' to i. Preference is given to using oxios mol/m2.

In this case, it is particularly desirable to add the FR compound to an intermediate layer provided between the emulsion layer to which the FR compound is added and other color-sensitive emulsion layers.

It can also be used in emulsion layers as a color fog preventive agent. In this case, -1 per W, OXIO-'
It is preferable to use ~1, OXIO-6 mol/~2.

However, the amount added is not limited to these.

In addition, an intermediate layer that also prevents color dryness and color fogging is added.
It is also possible to add emulsion layers to both layers.

Specific examples of the compound of general formula (I) according to the present invention are shown below, but the present invention is not limited thereto.

Shir13 LnJ 'y4 1'19 Shin3 t, /n3 Sun3 Sun Shi2fi5 Lin Sh Sun (iot) The synthesis of the compound represented by the general formula (I) is described in JP-A-55
-72158, 58-17431, 58-15
No. 6933, No. 59-5247, Patent Application No. 58-688
No. 78, Publication No. 58-78606, West German patent f: JJ
It can be carried out using the synthesis method described in No. 2732971, etc., or a method analogous thereto.

These can be introduced into the emulsion layer and intermediate layer by a conventional method.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may contain coating aids, antistatic properties, sheer properties, emulsion dispersion, adhesion prevention, and improvements in photographic properties (e.g., development acceleration, high contrast, enhancement, etc.). A variety of surfactants may be included for various purposes, such as (sensitivity).

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene Glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty alcohol esters of polyhydric alcohols, alkyl esters of Nonionic surfactants; alkyl carboxylates, alkyl sulfone salt-resistant salts, alkylbensene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphorus butyesters, N-acyl-N-furkyltaurines, Acidic groups such as carboxy groups, sulfo groups, phosphoro groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amphoteric surfactants such as aminoxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide, sonoether, ester, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also include derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

For example, U.S. Patent No. 2,400,532;
No. 23.549, No. 2,716゜062, No. 3,
No. 617,280, No. 3.772,021, No. 3
, 808,003, British Patent No. 1,488,991, etc. can be used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhytantoin, etc.), dioxane derivatives (2,3 -dihydroxydioxane, etc.), active vinyl compound-(1,3,5=triacryloyl-hyxahydro-s-triazine, 1.3
-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-propanol, etc.),
- triazine, etc.), mucohalogenated vinegars (mucochlor, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

The photographic material of the present invention may contain an ultraviolet absorber in the wood-philic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophene compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used.

These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

The photographic material of the present invention may contain a water-soluble dye in the wood-philic colloid layer as a filter dye, to prevent irradiation, and for various other purposes.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, and shea.
Included are dinic dyes and azo dyes. Among these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be dyed with a cationic polymer or the like.

For example, British Patent No. 685.475, US Patent No. 2,6
No. 75,316, fJr No. 2,839°401, No. 2,882,156, No. 3.048.487,
3,184,309, 3,445,231, West German Patent Application (OLS) No. 1,914,362, JP-A-50-47624, JP-A-50-71332, etc. Any polymer can be used.

In the photographic light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain brighteners such as stilbene-based, triazine-based, oxazole-based, or coumarin-based brighteners.

These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion.

The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving one-dimensional stability.

For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, nutylene, etc. alone or in combination. , or a combination of these with acrylic acid, methacrylic butylene, α, β-unyielding dicarphonic acid, hydroxyalkyl allylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonate, etc. as a monomer component. Polymers can be used.

For photographic processing of the light-sensitive material of the present invention, for example, Research Dis-cl.
osure ) No. 176, pages 28-30 (RD-1
Any of the known methods and known treatment liquids, such as those described in 7643), can be used.

This photographic processing may be a photographic processing that forms a dye image (color photographic processing), and the processing temperature is usually selected between 18°C and 50°C, but temperatures lower than 18°C or 50°C are preferred. The temperature may exceed .

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is contained in an emulsion layer and developed by processing the photosensitive material in an aqueous alkaline solution.

Among the developing agents, hydrophobic ones are described in Research Disclosure No. 169 (RD-16928) and U.S. Pat.
, 739,890, British Patent No. 813,253, or West German Patent No. 1.547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

The color developer may also contain a pH buffer, a development inhibitor, an antifoggant, and the like.

In addition, if necessary, water softeners, preservatives, 41 solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarbonate chelating agents, oxidizing agents, etc. It may also contain an inhibitor or the like. Specific examples of these additives can be found in Research Disclosure (
RD-17643), near Fus 4 +
No. 083.723, West German Publication No. 2,622,950, etc.

IV. Specific Effects of the Invention According to the present invention, since a compound that releases caplase agents or their precursors in response to the amount of developed silver during development is used in the silver halide photographic light-sensitive material, the number of developing areas increases. ,
Effects of sensitization and contrast enhancement can be obtained.

In addition, at this time, as the number of developing areas increases, a larger amount of oxidized developing agent is generated than usual, making single-color staining more likely to occur. 9 color contamination is significantly suppressed.

Therefore, the present invention provides a silver halide photographic material that has both the effects of sensitization and contrast enhancement and the effect of preventing color staining.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in more detail.

Example 1 A multilayer color negative photographic material was prepared by coating the following layers 1 to 15 on a cellulose triacetate film support.

1st layer: Antihalation layer Black colloidal silver...0.18g/12 Ultraviolet absorber C-1...0.12g/m24 〇-
Gelatin layer containing 2--.O, 17 g/m2 Second layer: Intermediate layer 2.5-di-t-pentadecylhydroquinone...0.18 g/+2 coupler C-
3-・-0, 11 g/m2 Gelatin layer containing silver iodobromide emulsifier (silver iodide 1 mol% average grain size 0.07 JLm) ...0.15 g/c2 Third layer: first red-sensitive emulsion Layered silver iodobromide emulsion (average grain size 1.8 lm)...0
．． 723/m2 Sensitizing dye processing... 7 O per mole of silver
X 10-S mole sensitized color; l II...2 per mole of silver
．． 0X10-5 mole sensitizing dye ■...2.8XI per mole of silver
O mol sensitizing dye JV...2 per 1 mol of silver,
OX I O-5 molar coupler C-4=0, 093 g/+2 coupler C
-5"...0, 31 8/m2 coupler C-6-...-
0, gelatin layer containing OI Ogem2 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2 m)...1
, 2 g/m2 Sensitizing dye processing...5.2X1 per mole of silver
0-S mole sensitizing dye II...1.5 per mole of silver
X10-5 mole sensitizing dye ■...2.1X1 per mole of silver
0-S mole sensitizing dye■...1.5X1 per mole of silver
0-5 mole coupler C-4...O, l Og/m2 coupler C
-5”0, 061 g/+2 coupler C-7”0
, 046 g/m2 Gelatin layer Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.8 JLm)...
1.5 g/m2 Sensitizing dye processing: 5.5Xl per mole of silver
O'mol sensitizing dye II... per mole of silver
1.6Xlo-5 mol sensitizing dye ■...2.2Xl per 1 mol of silver
O-5 mole sensitizing dye ■...1.6Xl per mole of silver
Gelatin layer containing O-5 molar coupler C-5...0, 044 g/m2 coupler C-7=0, 16 310+2 6th layer: Intermediate layer Silver iodobromide emulsifier (silver iodide 2 mol% average grain Gelatin layer containing O, l g/m2 (size 0.07 m) 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.5 pm)...0
．． 55g/m2 Sensitizing dye■...3.8X per mole of #i
10-4 mol sensitizing dye ■...3.0 per ftli mol
XIO'molar sensitizing dye ■...1.2X1 per mole of silver
0-4 mole coupler C-8-...0, 29 g/m2 coupler c-s...0.040 g/m2 coupler C-
10...0.055g/m2 coupler C-11...
8th layer of gelatin layer containing 0.058 g/m2: 2nd grain-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2 m)...1
,0 g/++2 Sensitizing dye ■...2.7X1 per mole of silver
0-'Mole sensitizing dye ■...2.1X1 per mole of silver
0'mol sensitizing dye■...8.5 per 1 mol of fFi
X10' mole coupler 〇-8...0, 25 g/m2 coupler CJ...O, OL 3 g/m2 coupler C-10...0, 009 g/a2 coupler C-11...・Gelatin layer containing O, OL 1g/a+2 9th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.8 lm)...2
, 0 g/m2 Sensitizing dye V...3, O per mol of silver
X 10-4 mol Sensitizing dye■...2.4X1 per 1 mol of silver
0-5 mol sensitizing dye ■...9.5XI per 1 mol of silver
O-5 mole coupler C-8”0, 013 g/m2 coupler C
Gelatin layer containing -12=0,070 g/m2 10th layer: yellow filter one layer yellow colloidal silver...0-08 g/m22.5-1 pentadecylhytroquinone...0,031 g7 Gelatin layer containing .2 Eleventh layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 pm)...0
．． 32 g/ff12 Coupler C-13..." 0, 68 g/m2 Gelatin layer containing coupler C-14=0, 030 g/m2 12th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.8pm) ----0
, 29g/a2 Sensitizing dye■...2.2X1 per mole of silver
Gelatin layer containing 0-4 molar coupler C-13...0,223/m2 Thirteenth layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 2, OIL+1)
...0.79g/m2 Sensitizing dye■ ...2.3X1 per mole of silver
Gelatin layer 14th layer containing 0-4 molar coupler C-13...0.19 g/2?1st protective layer UV absorber C-1...0, 14 g/++2?
Ultraviolet absorber C-2...0.22g/+m
Gelatin layer containing 2 15th layer: 2nd protective layer polymethyl methacrylate particles (diameter 1.5ALL1)...0.05 g/m2 silver iodobromide emulsion (silver iodide 2 mol% average grain size 0.07 In addition to the above composition, gelatin hardening agent C-15 was added to each gelatin layer containing 0.30 g/a+2
or a surfactant was applied.

The multilayer color negative photographic material thus produced was designated as Sample 101.

The compounds used to prepare this sample are shown below.

cmi UV absorber polymer (molecular weight about 20,000 to about 50,000) C-3 coupler C-4 coupler C-5 coupler C-6 coupler C-7 coupler C-8 coupler? (average molecular weight approximately 30,000) C-9 coupler C-10 coupler C-11 coupler C-12 coupler C-13 coupler C-14 coupler C-15 gelatin hardener CH2=CH-3O2CH2-CONH (CH2) 2-
-NHCOCH2・302-CH=CH21 Sosen dye■ 5 mg of the FR compound shown in Table 1 was added to the fifth layer of sample 101.
A sample was prepared in the same manner as sample 101 by adding /a+2. These samples are referred to as samples 201, 301 and 401.

In addition, various color stain inhibitors shown in Table 1 were added to the sixth layer (intermediate layer) of Samples 201, 301 and 401 at l x 10
-'mol/112 added, samples 201.301 and 40
A sample was prepared in the same manner as in Example 1.

These samples are referred to as samples 202-207, 302-304, and 402-404.

Samples 101, 202-207, 301-304 and 4
01 to 404 were wedge exposed to red light and subjected to the following development process.

Development process (processing temperature 38°C) l, color development 3 minutes 15 seconds 26 bleaching 6 minutes 30 seconds 3, washing with water 3 minutes 15 seconds 4, fixing 6 minutes 30 seconds 5, washing with water 3 minutes 15 seconds 6, stability 3 minutes The composition of the treatment liquid used in each 15 second treatment step is as follows.

h5nuU sodium nitrilotriacetate 1. og Sodium Sodium 4.0g Sodium Carbonate
30, 0g potassium bromine 1.
4g hydroxylamine sulfate am 2. +g4-(
N-ethyl-N-β-hydroxyethyl acetate
Ammonium bromide 160.0 g Aqueous ammonia (28%) 25. Sodium iron salt of ethylenediaminetetraacetate 130, Og Glacial acetic acid 14. Add 0ml 1l water and add 19-tetrapolyline sodium 2.0g sodium chloride
4.0g ammonium thiosulfate (70%) 175.0- Sodium bisulfite 4.6g Add water
1 sentence formalin 3.0-add water
The cyan color density and magenta color density of the developed sample were measured using a red filter and a green filter, respectively. At the exposure amount where the cyan coloring density becomes the cyan minimum coloring density + 1.0, how much the magenta coloring density increased from the magenta minimum coloring density was determined, and the magenta color mixture in the cyan coloring area was investigated.

The results are shown in Table 1.

From Table 1, it can be seen that the color stain inhibitor of the present invention has the ability to extremely effectively prevent an increase in color mixing resulting from the addition of an FR compound, compared to conventional agents.

Example 2 A sample was prepared by adding 5 mg/m2 of FR compound 1-23 to the fifth layer of sample 101 of Example 1. This is designated as sample 501.

In addition, color stain preventive agent 1 was added to the fifth layer (emulsion layer) of sample 501.
A sample was prepared by adding 1.5XlO-S mol/-m2. This will be referred to as sample 502.

Samples lot 501 and 502 were each exposed to a wedge of white light and then developed in the same manner as in Example 1, and the minimum cyan color density was measured using a red filter.

The minimum cyan color density of sample 101 was 0.25, but this increased to 0.35 in sample 501, in which an FR compound was added to the highest sensitivity red-sensitive layer (fifth layer). On the other hand, in sample 502 in which the color stain preventive agent of the present invention was further added to the fifth layer, the minimum cyan coloring density was 0.28.
It has been found that the color cast caused by the FR compound is effectively prevented by the color stain inhibitor of the present invention.

From the results of Examples 1 and 2, the color stain preventive agent represented by the general formula (I) of the present invention can be added to the intermediate layer to prevent color cast (color mixing), and when added to the emulsifier to prevent color cast, i.e. It can be seen that color staining is effectively prevented.

Patent applicant Fuji Photo Film Co., Ltd. Representative
People Patent Attorney Nozomu Watanabe Twisting
Patent Attorney Yo Ishii - Koitozogosho 1j Shop Niji (Method) February 27, 1985

Claims (1)

[Scope of Claims] A silver halide photographic photosensitive material having at least one silver halide emulsion layer on a support and containing at least one coupler that reacts with an oxidized product of a color developing agent to form a dye. In the material, a compound that releases a caprase agent or a precursor thereof in response to the amount of developed silver during development;
1. A silver halide photographic light-sensitive material, characterized in that it contains a color stain inhibitor represented by the following general formula (I). General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms,
Halogen atom, carboxyl group or sulfo group that may form a salt, or substituted or unsubstituted alkyl group, aryl group, acylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carbamoylamino group, alkoxycarbonylamino group group, aryloxycarbonylamino group, carbamoyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group or sulfonyl group, R
^1 and R^2 may be taken together to form a carbocycle. One of X^1, X^2, X^3 and X^4 is
represents a hydroxyl group, two of the remaining represent a hydroxyl group or a sulfonamide group, and the remaining one represents R^1
and represents any of the above atoms or groups shown as R^2. However, when X^1, X^2 and X^3 simultaneously represent hydroxyl groups, R^1, X^2, X^3 and X^
When 4 simultaneously represents a hydroxyl group, R^2 is the above R^
Among the atoms or groups shown as 1 and R^2, it is other than carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group. Further, the total number of carbon atoms in R^1, R^2, X^1, X^2, X^3 and X^4 is 10 or more. )