JPH07119987B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is directed to a specific layer containing a functional compound which is cleaved in the presence of a reducing substance to selectively exert various photographically advantageous effects. In addition, the present invention relates to a silver halide light-sensitive material which is uniformly, stably and effectively incorporated, and in particular to a black-and-white or color light-sensitive material with improved image sharpness, tone reproduction, color reproduction and easy handling. is there.

(Conventional technology and its problems) A silver halide photosensitive material has many hydrophilic colloid layers such as an undercoat layer, a silver halide photosensitive layer, an intermediate layer, a filter layer, a protective layer and an anti-halation layer on a support. It is provided, and the number of layers tends to increase due to improvements in performance and ease of handling.

Photosensitive materials include, in addition to photosensitive silver halide grains, so-called additives such as sensitizing dyes, development accelerators, antifoggants and stabilizers; dyes, surfactants and antioxidants, especially for color photosensitive materials. In some cases, color couplers, color image stabilizers,
Anti-color mixing agent, UV absorber, polymer latex, etc. such as Research Disclosure DR-17643 and RD1871
Many photographic materials are used as described in No.6. Originally, it is desirable that these materials, especially those directly related to photographic performance, can be contained and fixed independently in various types, but this is not always sufficient. For example, a sensitizing dye and an antifoggant are fixed by being adsorbed on silver halide grains. However, the strength of the adsorption is not sufficient, which is one of the causes of deterioration of stability over time. Also color couplers,
The color image stabilizer, the color mixture preventing agent, etc., have their molecules made hydrophobic and have a ballast group, and fine particles are dispersed and fixed using an oil or a polymer. For this reason, it is one of the factors that the volume is large and the layer film is thick and the image sharpness is deteriorated. On the other hand, in the case of the Fisher type color coupler, a water-soluble group is added to the ballast group and dispersed in an alkaline solution.
Although it was fixed, solid bodies are generated during the production, which is one of the causes of uneven coating and spots, and it is not currently used. Further, there is no good method for fixing dyes, and most of them are contained uniformly in each layer. There is a method of using a mordant layer, but it is difficult to provide it as a specific layer among the layers. Therefore, colloidal silver is currently used in the yellow filter layer and the anti-halation layer.

Many of the fixed materials must be removed from the layer after the image forming process, except for materials that are directly related to the image and its storability, but many are insufficient. For example, dyes and sensitizing dyes are desired to be improved because there are many residual colors.

As a means for solving these problems, a functional compound that cleaves in the presence of a reducing substance and exhibits a photographically advantageous effect is dispersed in water or a hydrophilic colloid solution using water or an organic solvent. Is effective. However, when such a method is industrially carried out, the water or the hydrophilic colloidal dispersion of the above-mentioned functional compound may change its solution viscosity during storage, or may generate an aggregate or a protrusion. There's a problem. Further, since the concentration of the functional compound in the dispersion cannot be increased, the capacity of the dispersion becomes large, resulting in inefficiency in the storage space, transportation and the like.

(Object of the Invention) An object of the present invention is to provide a photographic light-sensitive material in which a functional compound that cleaves in the presence of a reducing substance and exerts a photographically useful effect is uniformly and stably incorporated in a specific layer. It is in.

Other objects of the present invention will be understood from the description of the present specification and the examples.

(Constitution of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing gelatin on a support, wherein the hydrophilic colloid layer is a compound represented by the following general formula (I): It was achieved by including a betaine-type amphoteric surfactant.

General formula [I] The first feature of the present invention resides in the functional compound represented by the general formula [I]. This compound cleaves in the presence of a reducing substance and exhibits a photographically useful function, or the functional compound itself has a photographically useful function, which is cleaved and decomposed to release from a specific hydrophilic colloid layer. can do. Here, the reducing substance does not act as a reducing substance in the normal hydrophilic colloid layer state, for example, acidic or neutral, but acts on the photosensitive material in such a manner that it acts by the image forming processing solution (for example, alkaline developing solution). It may be contained or may be contained in the image forming treatment liquid.

For example, let us explain the case where the PUG group is a dye residue. As an example of the usage in this case, there is a usage in which the functional dye according to the present invention is contained in the protective layer to lower the sensitivity in a specific spectral absorption wavelength region. If this functional dye is uniformly cleaved in the presence of a reducing substance, the dye residue will be eluted from the light-sensitive material into the processing solution and no residual color will be left.

The second feature of the present invention resides in a method of incorporating the functional compound of the present invention into a specific hydrophilic colloid layer of a light-sensitive material.
The functional compound according to the invention comprises at least one water-soluble group,
For example, it has a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a sulfuric acid group or a salt thereof, a phosphoric acid group or a salt thereof, a hydroxyl group, a sulfamide group, or a formamide group. The ballast group has 4 carbon atoms.
Having (C ₄ )) to 18 (C ₁₈ ) aliphatic groups (eg, substituted or unsubstituted linear or branched alkyl groups, alkylene groups, etc., especially aliphatic group-substituted sulfamoyl groups, carbamoyl groups, etc.) Is preferred.

The amphoteric surfactant according to the present invention is a cationic / anionic amphoteric surfactant containing an ammonium group as a cationic group and a group selected from a carboxylic acid group, a sulfonic acid group, a sulfuric acid ester group and a phosphoric acid ester group as an anionic group, Cationic / nonionic amphoteric surfactants such as amine oxides, polyoxyethylene alkylamines, or polyoxyethylene polyamines, and anionic / nonionic amphoteric surfactants such as polyoxyethylenes containing a carboxyl group or a sulfonic acid group. Surfactants can be used. Particularly preferred are cationic / onion type amphoteric surfactants.

The characteristic feature of the dispersion method of the functional compound of the present invention is that it has a solubility in water or a water-soluble organic solvent such as water of about 5% or more, that is, a solubility sufficient to dissolve it in a dispersion medium liquid such as water or a hydrophilic colloid solution. It is dispersed by being dissolved in an organic solvent having a solvent such as alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, dimethylformamide and dimethylsulfoamide.

The amphoteric surfactant may be added to the organic solvent solution side at the time of dispersion or to the hydrophilic colloid solution phase, or may be added after dispersion.

It is preferable to remove these organic solvents by using a volatilization method under a low pressure or an ultrafiltration method after dispersion, and therefore, it is easy to use a solvent having a boiling point of 150 ° C. or less at atmospheric pressure. Unlike the conventionally known so-called "Fisher dispersion", the pH of the dispersion is
Is neutral, preferably acidic. Preferably, the functional compound of the present invention is an organic acid such as citric acid, oxalic acid, acetic acid,
It should be dispersed with tartaric acid, succinic acid, malic acid, etc. It is useful for the chemical stability of the compound itself, the stability of the dispersion, and the prevention of dispersal of the dispersoid. In the dispersion method of the present invention, the counterion of the water-soluble group (anion) is important unlike the so-called “Fisher dispersion”, and especially Na ⁺ ,
K ⁺ , Li ⁺ , NH ₄ ⁺ , Are useful.

After being dispersed in water or a hydrophilic colloid solution as described above, in the former case, be sure to mix it with a hydrophilic colloid solution in the latter case, if necessary, on the support or other coating layer. Apply to.

If necessary, the compound of the present invention can be dispersed in a hydrophilic colloid layer together with a reducing substance. Examples of such reducing substances are described in Japanese Patent Application No. 62-118,519.

In the hydrophilic colloid layer according to the present invention, firstly, since the functional compound of the present invention is directly dispersed in the hydrophilic colloid, the hydrophilic colloid layer is easily attacked by a reducing substance, and the cleavage reaction and subsequent photographic usefulness are efficiently performed. It is easy to recommend leaving the group. Secondly, the functional compound is easily dispersed stably. In addition, it has a relatively low molecular weight and is easy to obtain diffusion resistance to other adjacent layers. Thirdly, there is an advantage that a dispersion medium such as oil is not directly required, so that it can be contained at a high density and a thin layer thickness can be easily obtained.

The method for dispersing the functional compound according to the present invention is used in combination with another so-called oil dispersion method or a dispersion method using a polymer,
It is advantageous for stabilizing oil dispersion and polymer dispersion.

Next, the functional compound of the present invention will be specifically described.

General formula [I] PWRTime _t PUG In the general formula [I], PWR is nucleophilically substituted in the molecule after reduction as disclosed in US Pat. No. 4,139,389 or US Pat. No. 4,139,379 and JP-A-59-185333. It may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by a reaction, and is described in U.S. Pat. No. 4,232,107, JP-A-59-1016.
As disclosed in JP-A-49-88257 or JP-A-61-88257, an electron-accepting quinonoid center in a compound that releases a photographic reagent by an intramolecular electron transfer reaction after reduction and the photographic reagent are linked to the quinoid center It may be one corresponding to the portion containing the existing carbon atom. In addition, JP-A-56-1
No. 42530, U.S. Pat.No. 4,343,893, U.S. Pat.No. 4,619,884, and aryl groups substituted with electron-withdrawing groups in compounds that release a photographic reagent when a single bond is cleaved after reduction, and the photographic reagent. It may correspond to a portion containing an atom (a sulfur atom, a carbon atom or a nitrogen atom) connecting with. It may also correspond to a nitro group in a nitro compound that releases a photographic reagent after electron acceptance as disclosed in U.S. Pat.No. 4,450,223 and a portion containing a carbon atom connecting the nitro group and the photographic reagent. , U.S. Pat. No. 4,609,610, which corresponds to the dieminal dinitro moiety in the dinitro compound that β-eliminates the photographic reagent after electron acceptance and the moiety containing the carbon atom connecting it to the photographic reagent. good.

In order to more fully achieve the object of the present invention, among the compounds of general formula [I], those represented by general formula [II] are preferred.

General formula (II) In general formula [II] Corresponds to the PWR represented by the general formula [I].

At this time, (Time) _t -PUG binds to at least one of R ₁ , R _{2 and} EAG.

The part corresponding to PWR in the general formula [II] will be described.

X is an oxygen atom (-O-), a sulfur atom (-S-), an group containing a nitrogen atom (-N (R ₃₎ -) represents a.

R ₁ , R ₂ and R ₃ represent a group other than a hydrogen atom or a mere bond.

An example of the case where R ₁ , R ₂ and R ₃ are groups other than hydrogen atom is shown below.

Alkyl group, aralkyl group (Alkyl group which may be substituted, aralkyl group. For example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylamino Methyl group, ethyl group, 2- (4-dodecanoylaminophenyl) ethyl group, carboxyethyl group, allyl group, 3,3,3-trichloropropyl group, n-
Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, sec-pentyl group, t-pentyl group, cyclopentyl group, n-hexyl group , Sec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, sec-octyl group, t-octyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, sec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc. Alkenyl group (which may be substituted, for example vinyl group, 2-chlorovinyl) Group, 1-methylvinyl group,
2-Cyanovinyl group, cyclohexen-1-yl group, etc.) Alkynyl group (optionally substituted alkynyl group. For example, ethynyl group, 1-propynyl group, 2-ethoxycarbobonylethynyl group, etc.) Aryl group (substituted) Optionally an aryl group, for example, a phenyl group, a naphthyl group, a 3-hydroxyphenyl group, 3
-Chlorophenyl group, 4-acetylaminophenyl group,
4-hexadecanesulfonylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4
-Dimethylphenyl group, 4-tetradecyloxyphenyl group, etc., heterocyclic group (heterocyclic group which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2-pyridyl group, 5- Nitro-2-pyridyl group, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2
-Benzimidazolyl, 2-benzoxazolyl group, 2
-Oxazolyl-2-yl group, morpholino group, etc., acyl group (acyl group which may be substituted, for example, acetyl group, propionyl group, butyroyl group, iso-butyroyl group, 2,2-dimethylpropionyl group, benzoyl) Base,
3,4-dichlorobenzoyl group, 3-acetylamino-4
-Methoxybenzoyl group, 4-methylbenzoyl group, 4
-Methoxy-3-sulfobenzoyl group, etc., sulfonyl group (optionally substituted sulfonyl group. For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group. Group, n-dodecanesulfonyl group, n-hexadecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, 4-n-
Dodecyloxybenzenesulfonyl group, etc., carbamoyl group (optionally substituted carbamoyl group. For example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group. Group, di-n-octylcarbamyl group, 3-
Dodecyloxypropylcarbamoyl group, hexadecylcarbamoyl group, 3- (2,4-di-t-pentylphenoxy) propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n-octadecylcarbamoyl group, etc. ) Sulfamoyl group (sulfamoyl group which may be substituted. For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di-n- Butylsulfamoyl group, methyl-n-octylsulfamoyl group, n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyls group, N-phenyl-N-methylsulfamoyl group, 4 -Decyloxyphenyl sulfamoyl group, methyl Luoctadecyl sulfamoyl group, etc.).

R ₁ and R ₃ are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups and the like.

The carbon number of R ₁ and R ₃ is preferably 1-40. R ₂ is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group described for R ₁ and R ₃ . (The carbon number is preferably 1 to 40) R ₁ , R ₂ , R ₃ and EAG may be bonded to each other to form a ring.

The EAG will be described later.

Further, in order to achieve the object of the present invention, among the compounds represented by the general formula [II], the compounds represented by the general formula [III] are preferable.

General formula (III) In the general formula [III], Corresponds to PWR represented by the general formula [I].

(Time) _t -PUG binds to at least one of R ₄ and EAG.

The part of the general formula [III] corresponding to PWR will be described.

Y is a is preferably a divalent linking group - (C = O) - or -SO ₂ - is. X has the same meaning as described above.

R ₄ represents an atom group which is bonded to X and Y to form a 5- to 8-membered monocyclic or condensed heterocycle including a nitrogen atom.

Specific preferred examples of the portion corresponding to this heterocycle will be described below.

Here, R ⁵ , R ⁶ and R ⁷ are preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁸ is preferably an acyl group, a sulfonyl group or the like.

More particularly preferred examples are listed below (including the binding position of Time _t PUG, but the compound of the present invention is not limited thereto.

Further details will be described later in the specific compound.

EAG represents an aromatic group that accepts an electron from a reducing substance and is bonded to a nitrogen atom. As EAG, a group represented by the following general formula [A] is preferable.

General formula [A] In the general formula [A], Z ₁ is Represents

Vn represents an atomic group forming a 3- or 8-membered aromatic with Z ₁ and Z ₁ , and n represents an integer of 3 to 8.

_{V 3; -Z 3 -, V} 4; -Z 3 -Z 4 -, V 5; -Z 3 -Z 4 -Z 5 -,
V ₆ ; -Z ₃ -Z ₄ -Z ₅ -Z _6- , V ₇ ; -Z ₃ -Z ₄ -Z ₅ -Z ₆ -Z
₇ −, V ₈ ; −Z ₃ −Z ₄ −Z ₅ −Z ₆ −Z ₇ −Z ₈ −.

Z ₂ −Z ₈ are It represents —O—, —S—, or —SO ₂ —, and Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Even if each Sub is the same,
Further, they may be different from each other and may be bonded to each other to form a 3- or 8-membered saturated or unsaturated carbocycle or heterocycle.

In the general formula [A], Sub is selected so that the sum of the hammet substituent constant sigmapara of the substituents is +0.50 or more, more preferably +0.70 or more, and most preferably +0.85 or more.

EAG will be described in more detail.

EAG represents a group that receives an electron from a reducing substance, and is bonded to a nitrogen atom. EAG is preferably an aryl group substituted with at least one electron withdrawing group, or a heterocyclic group.

The substituent bonded to the aryl group or heterocyclic group of EAG can be used for controlling the physical properties of the entire compound. Examples of the physical properties of the entire compound, in addition to adjusting the electron acceptability, for example, water-soluble, oil-soluble, diffusible, sublimable, melting point, dispersibility in binders such as gelatin, reactivity to nucleophilic groups, It can be used to control the reactivity to electrophilic groups.

Next, a specific example of EAG will be given.

Examples of the aryl group substituted by at least one or more electron withdrawing groups include, for example, 4-nitrophenyl group, 2-nitrophenyl group, 2-nitro-4-N-methyl-Nn-butylsulfur. Phamoylphenyl group, 2-nitro-4-N-methyl-Nn-octylsulfamoylphenyl group, 2-nitro-4-N-methyl-Nn-
Dodecyl sulfamoylphenyl group, 2-nitro-4-
N-methyl-N-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-n-octadecylsulfamoylphenyl group, 2-nitro-4-N
-Methyl-N- (3-carboxypropyl) sulfamoylphenyl group, 2-nitro-4-N-ethyl-N-
(2-Sulfoethyl) sulfamoylphenyl group, 2-
Nitro-4-Nn-hexadecyl-N- (3-sulfopropyl) sulfamoylphenyl group, 2-nitro-4
-N- (2-cyanoethyl) -N-((2-hydroxyethoxy) ethyl) sulfamoylphenyl group, 2-nitro-4-diethylsulfamoylphenyl group, 2-nitro-4-di-n -Butylsulfamoylphenyl group,
2-nitro-4-di-n-octylsulfamoylphenyl group, 2-nitro-4-di-n-octadecylsulfamoylphenyl group, 2-nitro-4-methylsulfamoylphenyl group, 2-nitro-4-n-hexadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N- (4-dodecylsulfonylphenyl) sulfamoylphenyl group, 2-nitro-4- (3-methylsulfamoylphenyl) sulfamoylphenyl group, 4-
Nitro-2-N-methyl-N-n-butylsulfamoylphenyl group, 4-nitro-2-N-methyl-Nn-
Octylsulfamoylphenyl group, 4-nitro-2-
N-methyl-N-n-dodecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N -N-octadecyl sulfamoylphenyl group, 4-nitro-2-N-methyl-N- (3-carboxypropyl) sulfamoylphenyl group, 4-nitro-
2-N-ethyl-N- (2-sulfoethyl) sulfamoylphenyl group, 4-nitro-2-N-n-hexadecyl-N- (3-sulfopropyl) sulfamoylphenyl group, 4-nitro -2-N- (2-cyanoethyl) -N
-((2-hydroxyethoxyethyl) sulfamoylphenyl group, 4-nitro-2-diethylsulfamoylphenyl group, 4-nitro-2-di-n-butylfurfamoylphenyl group, 4-nitro -2-di-n-octylsulfamoylphenyl group, 4-nitro-2-di-n-
Octadecyl sulfamoylphenyl group, 4-nitro-
2-methylsulfamoylphenyl group, 4-nitro-2
-N-hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N- (4-dodecylsulfonylphenyl) sulfamoylphenyl group, 4-nitro-2
-(3-methylsulfamoylphenyl) sulfamoylphenyl group, 4-nitro-2-chlorophenyl group, 2
-Nitro-4-chlorophenyl group, 2-nitro-4-N
-Methyl-Nn-brylcarbamoylphenyl group, 2
-Nitro-4-N-methyl-Nn-octylcarbamoylphenyl group, 2-nitro-4-N-methyl-Nn
-Dodecylcarbamoylphenyl group, 2-nitro-4-
N-methyl-N-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-n-octadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N- (3- Carboxypropyl) carbamoylphenyl group, 2-nitro-4-N-ethyl-N- (2-sulfoethyl) carbamoylphenyl group, 2-nitro-4
-N-n-hexadecyl-N- (3-sulfopropyl)
Carbamoylphenyl group, 2-nitro-4-N- (2-
Cyanoethyl) -N-((2-hydroxyethoxy) ethyl) carbamoylphenyl group, 2-nitro-4-diethylcarbamoylphenyl group, 2-nitro-4-di-n
-Butylcarbamoylphenyl group, 2-nitro-4-di-n-octylcarbamoylphenyl group, 2-nitro-
4-di-n-octadecylcarbamoylphenyl group, 2
-Nitro-4-methylcarbamoylphenyl group, 2-nitro-4-n-hexadecylcarbamoylphenyl group,
2-nitro-4-N-methyl-N- (4-dodecylsulfonylphenyl) carbamoylphenyl group, 2-nitro-4- (3-methylsulfamoylphenyl) carbamoylphenyl group, 4-nitro- 2-N-methyl-N-n
-Butylcarbamoylphenyl group, 4-nitro-2-N
-Methyl-N-n-octylcarbamoylphenyl group,
4-nitro-2-N-methyl-N-n-dodecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-
n-hexadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-n-octadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N- (3-
Carboxypropyl) carbamoylphenyl group, 4-nitro-2-N-ethyl-N- (2-sulfoethyl) carbamoylphenyl group, 4-nitro-2-Nn-hexadecyl-N- (3-sulfopropyl) Carbamoylphenyl group, 4-nitro-2-N- (2-cyanoethyl)-
N-((2-hydroxyethoxy) ethyl) carbamoylphenyl group, 4-nitro-2-diethylcarbamoylphenyl group, 4-nitro-2-di-n-butylcarbamoylphenyl group, 4-nitro-2- Di-n-octylcarbamoylphenyl group, 4-nitro-2-di-n-octadecylcarbamoylphenyl group, 4-nitro-2-methylcarbamoylphenyl group, 4-nitro-2-n-hexadecylcarbamoylphenyl group Phenyl group, 4-nitro-2-
N-methyl-N- (4-dodecylsulfonylphenyl)
Carbamoylphenyl group, 4-nitro-2- (3-methylsulfamoylphenyl) carbamoylphenyl group,
2,4-dimethanesulfonylphenyl group, 2-methanesulfonyl-4-benzenesulfonylphenyl group, 2-n-
Octanesulfonyl-4-methanesulfonylphenyl group, 2-n-tetradecanesulfonyl-4-methanesulfonylphenyl group, 2-n-hexadecanesulfonyl-
4-methanesulfonylphenyl group, 2,4-di-n-dodecanesulfonylphenyl group, 2,4-didodecanesulfonyl-5-trifluoromethylphenyl group, 2-n-decanesulfonyl-4-cyano- 5-trifluoromethylphenyl group, 2-cyano-4-methanesulfonylphenyl group, 2,4,6-tricyanophenyl group, 2,4-dicyanophenyl group, 2-nitro-4-methanesulfonylphenyl group , 2-nitro-4-n-dodecanesulfonylphenyl group, 2-nitro-4- (2-sulfoethylsulfonyl)
Phenyl group, 2-nitro-4-carboxymethylsulfonylphenyl group, 2-nitro-4-carboxyphenyl group, 2-nitro-4-ethoxycarbonyl-5-n-butoxyphenyl group, 2-nitro-4-ethoxy Carobonyl-5-n-hexadecyloxyphenyl group, 2-nitro-4-diethylcarbamoyl-5-n-hexadecyloxyphenyl group, 2-nitro-4-cyano-5-n-
Dodecylphenyl group, 2,4-dinitrophenyl group, 2-
Nitro-4-n-decylthiophenyl group, 3,5-dinitrophenyl group, 2-nitro-3,5-dimethyl-4-n-
Hexadecanesulfonyl group, 4-methanesulfonyl-2
-Benzenesulfonylphenyl group, 4-n-octanesulfonyl-2-methanesulfonylphenyl group, 4-n-
Tetradecanesulfonyl-2-methanesulfonylphenyl group, 4-n-hexadecanesulfonyl-2-methanesulfonylphenyl group, 2,5-didodecanesulfonyl-4
-Trifluoromethylphenyl group, 4-n-decanesulfonyl-2-cyano-5-trifluoromethylphenyl group, 4-cyano-2-methanesulfonylphenyl group, 4
-Nitro-2-methanesulfonylphenyl group, 4-nitro-2-n-dodecanesulfonylphenyl group, 4-nitro-2- (2-sulfoethylsulfonyl) phenyl group,
4-nitro-2-carboxymethylsulfonylphenyl group, 4-nitro-2-carboxyphenyl group, 4-nitro-2-ethoxycarbonyl-5-n-butoxyphenyl group, 4-nitro-2-ethoxycarbonyl- 5-n-
Hexadecyloxyphenyl group, 4-nitro-2-diethylcarbamoyl-5-n-hexadecyloxyphenyl group, 4-nitro-2-cyano-5-n-dodecylphenyl group, 4-nitro-2- an n-decylthiophenyl group,
4-nitro-3,5-dimethyl-2-n-hexadecanesulfonyl group, 4-nitronaphthyl group, 2,4-dinitronaphthyl group, 4-nitro-2-n-octadecylcarbamoylnaphthyl group, 4-nitro-2 -Dioctylcarbamoyl-5- (3-sulfobenzenesulfonylamino) naphthyl group, 2,3,4,5,6-pentafluorophenyl group, 2
-Nitro-4-benzoylphenyl group, 2,4-diacetylphenyl group, 2-nitro-4-trifluoromethylphenyl group, 4-nitro-2-trifluoromethylphenyl group, 4-nitro-3 -Trifluoromethylphenyl group, 2,4,5-tricyanophenyl group, 3,4-dicyanophenyl group, 2-chloro-4,5-dicyanophenyl group, 2-
Bromo-4,5-dicyanophenyl group, 4-methanesulfonyl group, 4-n-hexadecanesulfonylphenyl group,
2-decanesulfonyl-5-trifluoromethylphenyl group, 2-nitro-5-methylphenyl group, 2-nitro-5-n-octadecyloxyphenyl group, 2-nitro-4-N- (vinylsulfonylethyl) -N-methylsulfamoylphenyl group, 2-methyl-6-nitrobenzoxazol-5-yl group and the like.

Examples of the heterocyclic group include, for example, 2-pyridyl group and 3-
Pyridyl group, 4-pyridyl group, 5-nitro-2-pyridyl group, 5-nitro-N-hexadecylcarbamoyl-2
-Pyridyl group, 3,5-dicyano-2-pyridyl group, 5-
Dodecanesulfonyl-2-pyridyl group, 5-cyano-2
-Pyrazyl group, 4-nitrothiophen-2-yl group, 5
-Nitro-1,2-dimethylimidazol-4-yl group,
3,5-diacetyl-2-pyridyl group, 1-dodecyl-5
Examples thereof include a carbamoylpyridinium-2-yl group, a 5-nitro-2-furyl group, a 5-nitrobenzthiazol-2-yl group, and the like.

Next, Time) _t -PUG will be described in detail.

Time is based on the cleavage of the nitrogen-oxygen, nitrogen-nitrogen, or nitrogen-sulfur bond as a scratch, and the PUG through the subsequent reaction.
Represents a group that releases

The group represented by Time is variously known, and is disclosed in, for example, JP-A-61-1.
47244 (5) page- (6) page, 61-236549 (8) page-
The groups described on page (14) and Japanese Patent Application No. 61-88625 (page 36) -page (44) can be mentioned.

PUG represents a group photographically useful as Time-PUG or PUG.

As a photographically useful group, for example, a development inhibitor, a development accelerator, a nucleating agent, a coupler, a diffusible or non-diffusible dye,
Desilvering accelerator, desilvering inhibitor, silver halide solvent, competitive compound, developing agent, auxiliary developing agent, fixing accelerator, fixing inhibitor, image stabilizer, toning agent, processing dependence improving agent, halftone dot Improver,
It represents a color image stabilizer, a photographic dye, a surfactant, a film hardener, a desensitizer, a contrast enhancer, a chelating agent, a fluorescent whitening agent, an ultraviolet light absorber, etc., or a precursor thereof.

Specific examples of PUG can be selected from the compounds described in the following patent application specifications. For example, Japanese Patent Application No. 60-244873 and Japanese Patent Application No. 6-24
1-88625, Japanese Patent Application No. 61-88623, Japanese Patent Application No. 61-89502, Japanese Patent Application No. 61-136947, Japanese Patent Application No. 62-34953, Japanese Patent Application No. 62-34954
It can be selected from the compounds described in Japanese Patent Application No. 62-34955, Japanese Patent Application No. 62-43704 and the like.

The compound of the present invention has a water-soluble group as described above. The substitution position may be PWR, Time or PUG, but preferably PUG
Is.

Specific examples of the functional compound represented by formula (I) of the present invention are shown below.

Next, the betaine-type amphoteric surfactant of the present invention will be described. The betaine-type amphoteric surfactant means a surfactant having both an anionic functional group and a quaternary nitrogen atom in one molecule, and is further classified into the following groups mainly according to the type of acid group; (1 ) Carboxybetaine type (2) Sulfobetaine type (3) Sulfate type (4) Phosphate ester type Next, specific examples of the anionic / cationic amphoteric surfactant according to the present invention will be given.

However, the present invention is not limited to the following compounds.

As the amphoteric surfactant preferably used in the present invention, a compound represented by the following general formula (IV) can be mentioned.

General formula (IV) In the formula, Rf represents an alkyl group, an alkenyl group or an aralkyl group in which all or part of hydrogen atoms are substituted with fluorine atoms, and the carbon number thereof is 1-18. R ₁ represents a hydrogen atom or a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms. (The total number of carbon atoms of R ₁ and Rf is preferably 24 or less.) A represents a trivalent linking group and B represents a divalent linking group. D represents a betaine group.

In the general formula (IV), a preferable example of the trivalent linking group represented by A is: And so on.

Preferred examples of R ₁ include -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -C ₆ H.
_{13, -C 8 H 17, -C} 10 H 21, -C 12 H 25, -C 18 H 37, and the like. Preferred examples of Rf, -CF _3, -C
₂ F ₅ , -C ₃ F ₇ , -C ₆ F ₁₃ , -C ₈ F ₁₇ , H (CF ₂ CF ₂ ) ₂ −, H (CF ₂ CF ₂ ) ₄ − and the like.

Preferred examples of the divalent group represented by B include -CH ₂ CH _{2
-, - CH 2 CH 2 CH} 2 -, CH 2 CH 2 O) n -CH 2 CH 2 -, (n = 1
~ 30), And so on.

Preferred examples of the betaine group represented by D are: (R ₂ and R ₃ represent an alkyl group having 1 to 6 carbon atoms, and 1 represents 1 to 6) and the like.

Next, specific examples of the fluorinated amphoteric surfactant represented by the general formula (IV) will be given.

The compound represented by the general formula (I) of the present invention may be used in a photosensitive layer or other constituent layers (for example, a protective layer, an intermediate layer, a filter layer, an antihalation layer, an image receiving layer). .

The compounds of general formula (I) according to the invention can be used in a wide range of amounts. The preferred amount used depends on the type of PUG. For example, when PUG is a diffusible dye, it depends on the extinction coefficient of the dye, but it may vary from 0.05 mmol / m ² to 50 mmol / m ² ,
It is preferably used at 0.1 mmol / m ^{2 to} 5 mmol / m ² . When used as a development inhibitor, it is preferably used in an amount of 1 × 10 ^-7 mol to 1 × 10 ^-1 mol, and particularly preferably 1 × 10 ^-3 mol to 1 × 10 ^-2 mol, per mol of silver halide. It is preferably used in the range. When PUG is a development accelerator and a nucleating agent, the same addition amount as that of the development inhibitor is preferable. When PUG is a silver halide solvent, it is preferably used in the range of 1 × 10 ⁻⁵ mol to 1 × 10 ³ mol, and particularly preferably 1 × 10 ⁻⁴ mol to 1 mol of silver halide.
It is in the range of 1 × 10 ¹ mol.

The amphoteric surfactant of the present invention is suitably used in a weight ratio of 1/20 to 10 times, preferably 1/5 to 2 times the amount of the compound of the general formula (I).

The compound represented by formula (I) of the present invention releases a photographically useful group or its precursor by receiving an electron from a reducing substance. Therefore, if the reducing substance is allowed to act uniformly, the photographically useful group or its precursor can be uniformly released or the photographically useful function can be uniformly exhibited. Further, when the reducing substance is converted into an oxidant in an image form, a photographically useful group or its precursor can be released in an inverse image form and a photographically useful function can be exhibited.

The reducing substance may be an inorganic compound or an organic compound, but its oxidation potential is preferably lower than the standard redox potential of silver ion / silver of 0.80V.

Two or more reducing substances may be used in combination. In particular, adjust the ratio of release or development of usefulness of photographically useful groups in the developed and non-developed areas (usually to improve this ratio).
For this purpose, it is preferable to use a compound called an electron donor (ETA) in combination with a compound called an electron donor. As the electron donor, 112 of the above-mentioned European Patent Publication 220,764 is used.
The compounds described as S-1 to S-45 on pages to 124.

Examples of the compound that can be used as the reducing substance in the present invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane amine complexes, and hydroquinones. , Aminophenols, catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-
In addition to amino-5-pyrazolones and the like,
TH Themes, written by THJames
The theory of the photographic process
The reducing agents described in 4th.Ed., pp.291-334 can also be used. In addition, JP-A-56-138,7
The reducing agent precursors described in US Pat. No. 36, 57-40,245 and US Pat. No. 4,330,617 can also be used.

Examples of more preferable reducing agents include the following.

3-pyrazolidones and precursors thereof [eg 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 4-hydroxymethyl-
4-methyl-1-phenyl-3-pyrazolidone, 1-m
-Tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-phenyl-4,4-bis- (hydroxymethyl) -3
-Pyrazolidone, 1,4-di-methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-
3-pyrazolidone, 1- (3-chlorophenyl) -4-
Methyl-3-pyrazolidone, 1- (4-chlorophenyl) -4-methyl-3-pyrazolidone, 1- (4-tolyl) -4-methyl-3-pyrazolidone, 1- (2-tolyl) -4-methyl- 3-pyrazolidone, 1- (4-tolyl) -3-pyrazolidone, 1- (3-tolyl) -3-pyrazolidone, 1- (3-tolyl) -4,4-dimethyl-3
-Pyrazolidone, 1- (2-trifluoroethyl) -4,
4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4
-Lauroyloxymethyl-3-pyrazolidone, 1-phenyl-4,4-bis- (lauroyloxymethyl) -3
-Pyrazolidone, 1-phenyl-2-acetyl-3-hyrazolidone, 1-phenyl-3-acetoxypyrazolidone] Hydroquinones and precursors thereof (for example, hydroquinone, tolhydroquinone, 2,6-dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t
-Butyl hydroquinone, t-octyl hydroquinone, 2,5-di-t-octyl hydroquinone, pentadecyl hydroquinone, sodium 5-pentadecyl hydroquinone-2-sulfonate, p-benzoyloxyphenol, 2-methyl-4-benzoyloxy Phenol, 2-t-butyl-4- (4-chlorobenzoyloxy) phenol] In the present invention, combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

A color developing agent is also useful as the reducing substance of the present invention, and a p-phenylene type color developing agent represented by N, N-diethyl-3-methyl-p-phenylenediamine in U.S. Pat. No. 3,531,286. Is listed. Further useful reducing agents are aminophenols described in US Pat. No. 3,761,270. Particularly useful among the aminophenol reducing agents are 4-amino-2,6-dichlorophenol, 4-amino-2,6-dibromophenol, 4-amino-2-methylphenol sulphate,
4-amino-3-methylphenol sulphate, 4-
Examples include amino-2,6-dichlorophenol hydrochloride. Further Research Disclosure Magazine No. 151 N
O.15108, U.S. Pat. No. 4,021,240, 2,6-dichloro-4-substituted sulfonamide phenols, 2,6-dibromo-4-substituted sulfonamide phenols, JP-A-59-11674.
No. 0 describes p- (N, N-dialkylaminophenyl) sulfamine and the like and is useful. In addition to the above phenol-based reducing agents, naphthol-based reducing agents such as 4-
Amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful. Further, as general color developers applicable, the amidohydroxypyrazole derivative described in U.S. Pat. No. 2,895,825, the aminopyrazoline derivative described in U.S. Pat. No. 2,892,714, Research Disclosure June 1980 No. 227-230,
Pages 236-240 (RD-19412, RD-19415) describe hydrazone derivatives. These color developers
They may be used alone or in combination of two or more.

The reducing agent in the present invention can be contained in the hydrophilic colloid layer of the light-sensitive material, preferably together with the functional compound of the present invention, or in the image forming processing solution, preferably in the developing solution or its pre-solution. it can. In the biophotosensitive material, the reducing agent is preferably contained in the same layer by a similar dispersion method under the condition that it does not react as a reducing substance under neutral or weakly acidic conditions. Is preferred. In this case, it is preferable that the reducing agent has a water-soluble group or has an anionic group under the reaction conditions. The reducing agent having a water-soluble group or an anion group can be contained by so-called oil dispersion, polymer dispersion or latex polymer dispersion.

The hydrophilic colloid layer of the present invention may further contain a commonly known anionic or nonionic surfactant.

Further, the compound represented by the general formula (I) of the present invention is a low boiling point organic solvent as well as a high boiling point organic solvent such as phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, and aliphatic carboxylic acids. Acid esters, aniline derivatives and the like can be used as an auxiliary or in combination with the fine particle dispersion.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of silver halide (in the case of spherical grains or grains close to spheres, grain diameter, in the case of cubic grains, ridge length is the grain size and is represented by the average based on the projected area) is preferably 2 μ or less. , Especially preferred is 0.
It is 4μ or less.

The shape of these silver halide grains may be cubic, octahedral, mixed crystal thereof, or tabular as described in JP-A Nos. 58-127921 and 58-113926.

Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed. Further, even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are heterogeneous, and it is described in British Patent 635,841 and U.S. Patent 3,622,318. A so-called conversion type may also be used. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type of which a latent image is formed inside the particles. In the latter case, a positive image can be directly obtained with a nucleating agent or optical fogging.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may coexist.

As the silver halide emulsion, a so-called unripened emulsion (primitive emulsion) which is not chemically sensitized may be used, or may be chemically sensitized. For chemical sensitization, sulfur-containing compounds capable of reacting with active gelatin silver (eg thiosulfates, thioureas, mercapto compounds, rhodanins)
Sulfur sensitization method using a reducing substance (for example, a first tin salt,
Reduction sensitization method using amines, hydrazine derivatives, formamidine sulphines, silane compounds, and noble metal compounds (eg, gold compounds, complex salts of Group VIII metals such as platinum, iridium, palladium, etc.) The noble metal sensitization method or the like can be performed alone or in combination.

As the hydrophilic colloid in which the compound or reducing agent of the present invention is dispersed or the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material, it is advantageous to use gelatin, but other hydrophilic Sex colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin can be used.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, 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. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus,
Thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, India The renin nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid, antistatic, slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). For various purposes such as, for example, various surfactants other than the amphoteric surfactant of the present invention may be included.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chromium yoban, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1 , 3,5-Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (Mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts, etc. can be used. In the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound, urethane derivative, urea derivative, imidazole. Derivatives, 3-pyrazolidones and the like may be included.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or water-soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.
For example, a polymer having, as a monomer component, an alkyl (meth) acrylate, a glycidyl (meth) acrylate, styrene or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid or the like can be used.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes,
It includes styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion used in the present invention, various compounds other than the compound of the present invention may be used for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can That is, azoles {eg benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, pentaazaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid Many compounds known as antifoggants or stabilizers such as benzene sulfonic acid amide, etc. can be added.

The photographic light-sensitive material of the present invention is a color image-forming coupler, that is, a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in color development processing. May be included. The coupler is preferably a non-diffusing coupler having a hydrophobic group called a ballast group in the molecule, or a polymerized coupler. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. The product of the coupling reaction may be colorless and may also contain a colorless DIR coupling compound which releases a development inhibitor.

Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and pyrazolotriazole couplers, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivalo And the like, and cyan couplers include naphthol couplers and phenol couplers.

The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used.

A known anti-fading agent can be used in the photographic light-sensitive material of the present invention. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The above-mentioned various additives are used in the light-sensitive material of the present invention, but various additives other than the above can be used depending on the purpose.

For more information on these additives, see Research Disclosure Item 17643 (December 1978) and Item 18716.
(November, 1979) and the relevant places are summarized in the table below.

The support used in the present invention includes glass, cellulose acetate film, polyethylene terephthalate film, paper,
Examples include baryter-coated paper, polyolefin (eg, polyethylene, polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plates such as aluminum.

These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method.

Any known method can be used for photographic processing of the light-sensitive material, and known processing solution can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either development processing for forming a silver image (black and white photographic processing) or color photographic processing including development processing for forming a dye image can be applied.

The black-and-white developing solution contains known developing agents such as dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol) and the like. They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, LFA Messon's "Photograph Processing Processor Chemistry", published by Focal Press (1966)
226 to 229, U.S. Patents 2,193,015 and 2,592,364,
Those described in JP-A-48-64933 may be used.

The developer may be a development inhibitor such as a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, bromide, iodide, or an organic antifoggant other than the compound of the present invention. , An antifoggant and the like. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agent such as sodium boron hydride, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity imparting agent, polycarboxylic acid type chelating agent described in US Pat. No. 4,083,723, published by West Germany (OLS)
The antioxidant described in 2,622,950 may be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, an organic complex salt of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or a quenching agent. Complex salts of organic acids such as acids, tartaric acid and malic acid; persulfates, permanganates, nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, U.S. Pat.
In addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506 and JP-B-45-8836, the thiol compound described in JP-A-53-65732, various additives can be added.

The washing process may be carried out in one tank, but in most cases it is 2
It is carried out by a multi-stage countercurrent washing method of more than a tank. The amount of water in the washing step can be arbitrarily set according to the type and purpose of the color light-sensitive material. For example, Journal of Motion Picture and Television Engineering 64: 248-253 (May 1955) Issue) "Water Florents in Immagion Worthing of
Motion Picture Film (Water Flow Rates i
n Immersion-Washing of Motion Picture Film, SRGol
It can also be calculated by the method described in dwasser).

When reducing the amount of water to be washed, the occurrence of bacteria and mold becomes a problem, but as a reaction therefor, washing water with reduced calcium and magnesium described in Japanese Patent Application No. 61-131632, a bactericidal agent and an antibacterial agent. , For example, the Journal of
Antibacterial and Anfunningal Agents (J.Antibact.Antifug.Agents) vol.11, No.5, p
207 to 223 (1983) and compounds described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Chemistry") can be added. A chelating agent such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid may be added as a water softener.

When the amount of washing water is reduced, the amount of water used is usually 100 ml to 200 ml per 1 m ^{2 of the} color light-sensitive material, but a range of 200 ml to 1000 ml is particularly preferably used in order to achieve both color image stability and water saving effect. .

The pH in the washing step is usually in the range of 5-9.

The photographic elements of this invention are also advantageously used in color image forming processes in which the imagewise diffusible dye is formed or released and then diffused and then fixed.

In the color image forming method described above, a method of developing using a developer at a temperature near room temperature [color diffusion transfer method] (for example, described in Belgian Patent 757,959), heat development in a substantially water-free state What [heat development method] (for example, European Patent 76492A2 and JP-A-58-79247, 59-218443,
There are various forms such as those described in Japanese Patent Application No. 60-79709), and the photographic element of the present technology can be used in any of them.

The dye-donating substance useful in the above-mentioned color image forming method is a compound in which PUG is an image-forming dye in the general formula (1), but a compound represented by the general formula [X] may also be used.

General formula [X] Dy-Y Here, Dy represents a dye portion (or a precursor portion thereof), and Y is a dye-providing substance represented by the general formula [X] as a result of development.
Represents a substrate having the functionality of changing the diffusivity of the compound represented by.

Here, “diffusivity changes” means (1) general formula [X]
The dye-providing substance represented by the formula (1) is originally non-diffusible and changes to diffusible or a diffusible dye is released, or (2) the general formula [X ] It means that the dye-donor substance represented by Further, this change may occur due to the oxidation of Y or the reduction thereof depending on the nature of Y.

As an example in which the "diffusion property is changed" by the oxidation of Y, first, p-sulfonamidonaphthols (including p-sulfonamidophenols) are disclosed in JP-A-48-33,826 and 53-5.
0,736, European Patent No. 76,492 has specific examples),
o-sulfonamidophenols (including o-sulfonamidonaphthols: JP-A-51-113,624 and JP-A-56-12642)
No. 56, No. 56-16130, No. 56-16131, No. 57-4043, No. 57-
650, US 4,053,312, and European Patent No. 76,492 for specific examples), hydroxysulfonamide heterocycles (Japanese Patent Laid-Open No. 51-104,343, European Patent No. 76,492 for specific examples), 3 -Sulfonamidoindoles (JP-A-51-1
04,343, 53-46,730, 54-130,122, 57-85,0
55, and European Patent No. 76,492 for specific examples), α-
Sulfonamide ketones (JP-A-53-3,819, JP-A-54-48,
534 and European Patent No. 76,492). Specific examples thereof include so-called dye-releasing redox substrates.

As another example, Y is a type in which a dye is released by an intramolecular nucleophilic attack after being oxidized, as disclosed in JP-A-57-20,735 and JP-A-59-59.
Intramolecular assist type substrates described in No. 65839 are mentioned.

Another example is a substrate that releases a dye by an intramolecular ring closure reaction under basic conditions, but does not substantially release the dye when Y is oxidized (JP-A-51-63,618). There is a specific example in the issue). Further, as a modified form of this, a substrate in which the isoxazolone ring undergoes ring rewinding by a nucleophile to release a dye is also useful (specific examples are described in JP-A-49-111628 and JP-A-52-4819).

Another example is a substrate in which the dye moiety is released by dissociation of an acidic proton under basic conditions, but the dye is not substantially released when Y is oxidized (JP-A-53-69,033). No. 54-130927).

It is also possible to use a compound which undergoes a redox reaction with a silver halide or an organic silver salt at a high temperature, and as a result, the mobility of the compound having a dye part is changed, which is disclosed in JP-A-59-16505.
It is described in No. 4.

Further, a dye-donor substance which releases a mobile dye upon reaction with silver ions in the light-sensitive material is described in JP-A-59-180548.

The image-receiving element may be provided on a support separate from the light-sensitive element or may be a film unit associated with the light-sensitive element.

A typical form of the film unit is a form in which the image receiving element and the photosensitive element described above are laminated on one transparent support, and it is not necessary to peel the photosensitive element from the image receiving element after the completion of the transferred image. Is. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (here, "an infrared light-sensitive emulsion layer is an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more. A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the layer containing the dye-donating substance so that the transferred image can be viewed through the transparent support. Complete development in the light A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer for the purpose of enabling the light-sensitive element, and if necessary, at a suitable position so that all or a part of the light-sensitive element can be separated from the image-receiving element. A release layer may be provided (such an embodiment is described, for example, in JP-A-56-67840 and Canadian Patent 674,082).

Further, in another form in which peeling is not required, a photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. A mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support, and a mode in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,718. On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. In more detail, in a preferable embodiment of the peelable film unit, the support has a light-reflective layer on the back surface thereof, and at least one image-receiving layer is coated on the surface thereof. The photosensitive element is coated on a support having a light-shielding layer, and the photosensitive layer coating surface and the mordant layer coating surface do not face each other before the exposure is completed, but the photosensitive layer is exposed after the exposure (for example, during the development process). It is designed so that the coated surface is scratched back and overlaps with the coated surface of the image receiving layer. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. The photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

Any of the above-mentioned forms can be applied to both the color diffusion transfer system and the heat development system. In the former case, however, a pressure-rupturable container (processing element) containing an alkaline processing liquid is further combined. May be. In particular, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, this processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of an intermediate layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element or the photosensitive element.

On the other hand, in the thermal development type film unit, the support,
It occurs when a heat generating layer containing fine particles of gold layer, conductive particles such as carbon black or graphite is provided at an appropriate position of a light-sensitive element or an image-receiving element, and electricity is applied for heat development or diffusion transfer of dye. You may use the Jewil heat. A semiconductive inorganic material (for example, silicon carbide, molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used instead of the conductive particles.

Next, the present invention will be described in more detail based on examples.

Example 1 (Preparation of Emulsion A) An aqueous solution of silver nitrate and an aqueous sodium chloride solution containing 0.5 × 10 ⁻⁴ mol of ammonium hexachlororhodium (III) chloride per mol of silver were adjusted to pH in a gelatin solution at 35 ° C. by the double jet method. Mix while controlling to 6.5.
A monodisperse silver chloride emulsion having an average grain size of 0.07 μm was prepared.

After the particles are formed, soluble salts are removed by a flocculation method well known in the art, and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 1-phenyl are used as stabilizers. -5-Mercaptotetrazole was added. Gelatin contained in 1 kg of emulsion is 55 g, and silver is 10
It was 5g. (Emulsion A) (Preparation of Photosensitive Material) To the emulsion A, a nucleating agent, a nucleation accelerator, and a dye for enhancing safelight safety as shown below are added, Next, polyethyl acrylate latex (14mg /
m ² ), and further adding 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt as a hardening agent to give 1 m ²
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 3.5 g per unit area, and gelatin (1.3 g / m ² ) was further added to the silver halide emulsion layer.
(0.1 g / m ² ), as a coating aid, a protective layer containing the following three surfactants, stabilizers and matting agents was applied and dried. (Sample 1).

Stabilizer Thioctic acid 6 mg / m ² Matting agent Polymethylmethacrylate (average particle size 2.5 μ) 50 mg / m ² Compound 2 of the present invention was used by preparing a dispersion according to the following procedure.

Add Solution I little by little while stirring Solution II at 50 ° C.

The pH of the finished solution was 5.4.

(Preparation of Comparative Sample) Comparative Example A was prepared in the same manner as in Example 1 except that the amphoteric surfactant of the liquid II was excluded as the dispersion.

(Evaluation of Performance) (1) Stability of Dispersion Table 1 shows the results of stability tests of the dispersion used in Example-1 and the dispersion used in Comparative Sample A. The dispersion used in Comparative Sample A had a large decrease in viscosity and an increase in turbidity during the aging at 40 [deg.] C., and started to break, whereas the dispersion of Example-1 of the present invention. Is almost unchanged.

(2) Coated surface state of sample When each dispersion was used after aging at 40 ° C. for 4 days, no abnormality was observed in Example-1, but in Comparative Sample A, the surface was rippled. Occurred, and some extrudates were observed.

(3) Photographic property A sample using the dispersion aged at 40 ° C. for 4 days was used as a bright room printer P-607 manufactured by Dainippon Screen Co., Ltd.
Then, expose it through an optical wedge, and use the next developer at 38 ℃, 20
Second development, fixing by a usual method, washing with water and drying.

As a result, in comparative sample A, a strong ripple-like anomaly was observed in the blackened portion, resulting in an image that could not be used practically, but in the sample of Example-1, no abnormality was observed at all.

Developer Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 13.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid tetrasodium salt 1.0 g Potassium bromide 4.0 g 5 -Methylbenzotriazole 0.6 g 3-diethylamino-1,2-propanediol 15.0 g Water was added 1 (pH = 11.5) Example-2 In Example-1, as an amphoteric surfactant of the dispersion,
Compound No. 3 (1.68 g) was used in the types and amounts shown in Table-2, and otherwise the same as in Example-1.

As a result, both the viscosity change of the dispersion and the mechanical stability,
It was good as shown in Table-2. The coated surface state and photographic properties of the sample were also good.

Example-3 In Example-1, Compound 4 , Compound 6 , Compound 8 , Compound 16, and Compound 17 were used in place of Compound 2 in Solution I of the dispersion, and the others were the same. I went to.

All of them showed good dispersion stability, coated surface condition and photographic property.

Example 4 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material of the present invention composed of each layer having the following composition was prepared.

(Composition of light-sensitive material) The coating amount is the amount expressed in g / m ^{2 of} silver for silver halide, colloidal silver and couplers, and for sensitizing dyes, it is mol per mol of silver halide in the same layer. It is shown by the number.

1st layer: Anti-halation layer Black and white colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 (UV absorber) 0.1 UV-2 (UV absorber) 0.2 Cpd-1 0.05 Solv-1 (UV-1, UV-2 Dispersion oil) 0.01 Solv-2 (UV-1, UV-2 dispersion oil) 0.01 Solv-3 (Cpd-1 dispersion oil) 0.08 Second layer: intermediate layer Fine grain silver halide (average grain size 0.07) μAgBr) Silver coating amount
0.15 Gelatin 1.0 Cpd-2 (Anti-color mixing agent) 0.2 Third layer: First red-sensitive emulsion layer (first RL) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
0.8μ, variation coefficient of equivalent sphere diameter 28%, plate-like grain, diameter / thickness ratio 3.0) Silver coating amount 0.7 Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type, equivalent sphere diameter)
0.5μ, coefficient of variation of equivalent spherical diameter 26%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.5 Gelatin 2.0 SD-1 (sensitizing dye) 4.5 × 10 ^-4 mol SD-2 (sensitizing dye) 1.5 x 10 ^-4 mol SD-3 (sensitizing dye) 0.4 x 10 ^-4 mol SD-4 (sensitizing dye) 0.3 x 10 ^-4 mol EXC-1 (coupler) 0.55 EXC-2 (DIR coupler) 0.01 EXC -3 (colored coupler) 0.03 Solv-1 (EXC-1, 2, 3 dispersion oil) 0.2 Solv-3 (EXC-1, 2, 3 dispersion oil) 0.2 4th layer: second red-sensitive emulsion Layer (2nd RL) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of equivalent spherical diameter 30%, plate-like particles, diameter / thickness ratio 4.3) Silver coating amount 1.0 Gelatin 1.3 SD-1 (sensitizing dye) 3 × 10 ^-4 SD-2 (sensitizing dye) 1 × 10 ^-4 SD-3 (sensitizing dye) 0.3 × 10 ^-4 SD-4 (sensitizing dye) 0.3 × 10 ^-4 mol EXC-1 (coupler) 0.09 EXC-3 (colored coupler) 0.06 EXC-4 ( Coupler) 0.12 Solv-1 (EXC-1, 3, 4 dispersion oil) 0.12 Solv-2 (EXC-1, 3, 4 dispersion oil) 0.12 Fifth layer: intermediate layer Gelatin 1.3 Cpd-4 (color mixture) Inhibitor) 0.2 6th layer: 1st green emulsion layer (1st GL) Silver iodobromide emulsion (10.0 mol% AgI, high internal AgI type, equivalent spherical diameter)
0.8μ, coefficient of variation of equivalent sphere diameter 28%, plate-like grain, diameter / thickness ratio 3.0) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type, equivalent sphere diameter)
0.5μ, coefficient of variation of equivalent spherical diameter 26%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.1 Gelatin 1.4 SD-5 (sensitizing dye) 5 × 10 ^-4 SD-6 (sensitizing dye) 2 × 10 ^-4 SD-7 (sensitizing dye) 1 × 10 ^-4 EXM-1 (coupler) 0.48 EXM-2 (DIR coupler) 0.06 EXM-5 (colored coupler) 0.06 Solv-1 (EXM-1, 2, Dispersion oil of 5) 0.2 7th layer: 2nd green emulsion layer (2nd GL) Silver iodobromide emulsion (10.0 mol% AgI, internal high iodine type, equivalent spherical diameter 0.25μ, variation coefficient of equivalent spherical diameter) 28%, tabular grains, diameter / thickness ratio 3.0) Silver coating amount 0.6 Gelatin 0.5 SD-5 (sensitizing dye) 3.5 × 10 ⁻⁴ SD-6 (sensitizing dye) 1.4 × 10 ⁻⁴ SD-7 (enhancing) Sensitizing dye) 0.7 × 10 ^-4 EXM-1 (Coupler) 0.25 EXM-3 (Colored coupler) 0.05 Solv-1 (EXM-1, 3 dispersion oil) 0.15 Eighth layer: Intermediate layer Gelatin 1.0 Ninth layer: Third red-sensitive emulsion layer (3rd RL) Silver iodobromide milk (Average particle size 1.5, AgI10.0 mol%, internal high Ag
Type I, equivalent sphere diameter 1.5μ, variation coefficient of equivalent sphere diameter 32%, plate particles, diameter / thickness ratio 6.0) Silver coating amount 0.8 Gelatin 1.2 SD-1 (sensitizing dye) 2 × 10 ^-4 SD-2 (Sensitizing dye) 0.6 × 10 ^-4 SD-3 (Sensitizing dye) 0.2 × 10 ^-4 EXC-4 (Coupler) 0.08 EXC-5 (Coupler) 0.07 Solv-1 (Dispersion oil of EXC-4, 5 ) 0.12 Solv-2 (EXC-4, 5 dispersion oil) 0.12 Layer 10: Functional silver halide emulsion layer (FL) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent) Diameter
1.5μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 1.0) Silver coating amount 0.5g Gelatin 0.5g SD-7 (sensitizing dye) 6 × 10 ^-4 EXY-2 0.001g Solv- 1 (EXY-2 dispersion oil) 0.001g Eleventh layer: third green emulsion layer (third GL) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
1.5μ, coefficient of variation of equivalent spherical diameter 32%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.5 Gelatin 1.4 SD-5 (sensitizing dye) 2 × 10 ^-4 SD-6 (sensitizing dye) 0.8 × 10 ^-4 SD-7 (sensitizing dye) 0.8 × 10 ^-4 EXM-4 (coupler) 0.15 EXM-1 (colored coupler) 0.03 EXC-4 0.005 Solv-1 (EXM-4, 1, EXC-4 Dispersion oil) 0.2 12th layer: Yellow filter layer (YF) Compound of the general formula [I] of the present invention 4 0.05 g Amphoteric surfactant No. 3 0.035 g Gelatin 0.5 This layer is prepared by the following formulation. It was prepared and used for application.

Liquid I Compound 4 3.0 g Dimethylformamide 5.8 ml Liquid II Amphoteric surfactant No. 3 2.1 g Gelatin 5.4 g Citric acid 0.15 g H ₂ O 100 ml Liquid I was added while stirring liquid II at 50 ° C.

13th layer: intermediate layer Gelatin 0.5g Cpd-2 0.1g Solv-1 (oil for dispersing Cpd-2) 0.1 14th layer: 1st blue emulsion layer (1st BL) Silver iodobromide emulsion (AgI8.3 Mol%, internal high iodine type, spherical equivalent diameter 0.7μ, coefficient of variation of spherical equivalent diameter 21%, octahedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 3.0 mol%, internal high iodine type, spherical equivalent) Diameter 0.3μ, coefficient of variation of equivalent spherical diameter 22%, octahedral grain) Silver coating amount 0.1 Gelatin 1.2 SD-8 (sensitizing dye) 3 × 10 ^-4 EXY-1 (coupler) 0.7 EXY-2 (DIR coupler) 0.03 Solv-1 (EXY-1, 2 dispersion oil) 0.5 15th layer: Second blue-sensitive emulsion layer (2nd BL) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of equivalent spherical diameter 30%, plate-like particles, diameter / thickness ratio 4.0) Silver coating amount 0.4 Gelatin 0.3 SD-8 (sensitizing dye) 2 × 10 ^-4 EXY-1 (coupler) 0.3 Cpd- 3 0.1 Solv-1 (oil for dispersing Cpd- and Exy-13) 0.2 16th layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent spherical diameter 0.13)
μ) Silver coating amount 0.4 Gelatin 0.4 17th layer: Third blue-sensitive emulsion layer (3rd BL) Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent spherical diameter)
2.1μ, coefficient of variation of equivalent spherical diameter 30%, plate-like particles, diameter / thickness ratio 5.0) Silver coating amount 1.4 Gelatin 1.1 SD-8 (sensitizing dye) 1.5 × 10 ^-4 EXY-1 (coupler) 0.2 Solv- 1 (EXY-1 dispersion oil) 0.14 18th layer: 1st protective layer Gelatin 1.8 UV-1 (UV absorber) 0.1 UV-2 (same as above) 0.2 Solv-1 (UV-1, 2 dispersion oil) ) 0.01 Solv-2 (UV-1, 2 dispersion oil) 0.01 19th layer: 2nd protective layer Fine grain silver halide (AgBr with average grain size 0.07) Silver coating amount
0.3 Gelatin 0.7 Polymethylmethacrylate particles (diameter 1.5 μ) 0.2 W-1 (charge control agent) 0.02 H-1 (hardener) 0.4 Cpd-5 (formaldehyde scavenger) 1.0 (Structure of compounds used in Examples formula) The transparency and surface condition of the film coated and dried on the cellulose acetate triacetate support were observed. No defects due to poor dispersion were observed.

The coating material obtained was processed into a 35 mm size for camera photography. Using the obtained sample, a color rendering chart manufactured by Macbeth was photographed under a light source with a color temperature of 5500 ° K. This was subjected to color development processing in the next processing step to obtain a negative film.

Furthermore, it was printed on Fuji Color Paper (high-tech paper) to obtain color photographs.

Color developer Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxyamine 2.4 4- (N-ethyl-N-β-hydroxyethyl) amino)
2-Methylaniline Sulfate 4.5 Add water 1 (10.7 with potassium hydroxide) <Bleaching solution> Ethylenediaminetetraacetic acid ferric ammonium salt 100g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonia water 7ml Ammonium nitrate 10.0g Odor Ammonium chloride 150g Add water 1 pH 6.0 <Fixer> Ethylenediamine tetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Sodium bisulfite 4.6g Ammonium thiosulfate aqueous solution (70%) 175ml Add water 1 pH 6.6 <Wash solution> Tap water (including calcium 27 mg / l, magnesium 10 mg / l) <Stabilizer> Formalin (37% w / v) 2 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water added As a result of printing on 1 color paper, no defect due to poor dispersion of the compound according to the present invention was observed.

Example-5 An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.1 × 10 ⁻⁴ mol of ammonium hexachlororhodium (III) chloride per mol of silver were added to a gelatin aqueous solution kept at 38 ° C. by a double jet method for 15 minutes. , Monodisperse average particle size 0.08μ
A silver chloride cube was prepared. After the particles are formed, soluble salts are removed by a crocculation method well known in the art, and 4-hydroxy-6-methyl-1,3,
3a, 7-Tetraazaindene and 1-phenyl-5-mercaptotetrazole were added. The gelatin contained in 1 kg of the emulsion was 55 g and the silver was 100 g.

The hydrazine compound (1) represented by the following formula was added to this emulsion 11
mg / m ² , compound (2) 20 mg / m ² , compound (3) 6 mg /
m ² , the compound (4) 20 mg / m ² as a nucleation accelerator, and the compound (5) as a dye for enhancing safelight safety were added, and then polyethyl acrylate latex was added at 0.8 g / m 2.
^2. 145 mg / m ² of 2-bis (vinylsulfonylacetamido) ethane was added as a hardener and coated on a polyethylene terephthalate support so that the silver amount was 3.8 g / m ² . Further 0.8 g / m ² of gelatin thereon, compound (6) 85 mg / m ^2, 1,5-dihydroxy-2-benzaldoxime a 30 mg / m ^2, thioctic acid 6 mg / m ^2, polyethyl acrylate The protective layer-1 was coated by adding 140 mg / m ^{2 of} latex and 10 mg / m ^{2 of} sodium dodecylbenzenesulfonate as a coating aid.

Further, on the protective layer-1, 0.6 mg / m ² of gelatin, 0.1 g / m ^{2 of} the compound represented by formula (I) of the present invention (Example-2),
Sodium dodecylbenzene sulfonate as coating aid
16 mg / m ² , N-perfluorooctanesulfonyl-N-
Propylglycine potassium salt 3 mg / m ² , polymethylmethacrylate as matting agent (average particle size 2.5 μ) 40 mg /
adding m ^2, and coated with a protective layer 2.

In addition, the compound example represented by the general formula (I) of the present invention-2
Prepared a gelatin dispersion by the following procedure.

A solution prepared by dissolving 10 g of Compound Example-2 in 20 ml of N, N-dimethylsulfoamide was used as a compound of the general formula (IV)
6.5 wt% gelatin aqueous solution with 7 g and citric acid 0.57 g 46
5 g was mixed with stirring at 50 ° C. to obtain a dispersion. The pH of the finished liquid was 5.3.

(Preparation of Comparative Sample) Comparative sample A was prepared in the same manner as above except that the compound of IV-1 was not used. The performance was evaluated by the same method as in Example-1.

As is clear from the results of Table 3, Sample-1 of the present invention has good stability of the dispersion, good coating surface condition, and no influence on the photographic image.

Example-6 The compound of the general formula (I) of the example-5 is used in the dispersion of the example-2 of the invention, the compound of the general formula (IV) shown in Table-4 is used, and otherwise the same as the example-5. To obtain a dispersion. Then, it was coated on a polyethylene terephthalate support in the same manner as in Example-5. The results are shown in Table-4.

As is clear from Table 4, Samples 6-1 to 6-5 of the present invention have good stability of the dispersion, good coating surface condition, and good photographic property.

Example-7 In Example-5, instead of the compound example-2 of the gelatin dispersion of the compound of general formula (I), the compound examples-4, -6,
The same procedure was performed using -8, 16, and -17.

All of them showed good dispersion stability, coated surface condition and photographic property.

Example-8 In Example-4, IV-1 was used as the 12th layer amphoteric surfactant.
A sample was prepared in the same manner as in Example 4 except that was used. Similar results were obtained as in Example-4.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing gelatin on a support, wherein the hydrophilic colloid layer is a compound represented by the following formula (I) and a betaine-type amphoteric surfactant. And a silver halide photographic light-sensitive material. General formula (I) PWRTime _t PUG 2. The photographic light-sensitive material according to claim 1, wherein in the compound represented by formula (I), the water-soluble group is sulfonic acid, carboxylic acid or a salt thereof.