JPH01158439A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make possible to uniformly and stably involve a functional compd. capable of displaying photographically useful effect by being released in the presence of a reducing substance in a specified layer by incorporating a specified compd. and an ampholytic surfactant in a hydrophilic colloid layer. CONSTITUTION:The compd. shown by formula I and the ampholytic surfactant are incorporated in the hydrophilic colloid layer. In formula I, PWR is a group capable of releasing the group (Time)tPUG by being reducing, Time is a group capable of being released as the group (Time)tPUG and then releasing the PUG residual group by a following reaction, (t) is 0 or 1, PUG is a residual group usable to photography. And the compd. contains at least one of a water soluble group in one molecule. Thus, the functional compd. capable of displaying the photographic effect by being released in the presence of the reducing substance is uniformly, stably and effectively involved in the specified layer.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the application of a functional compound that is cleaved in the presence of a reducing substance and selectively exhibits various photographically advantageous effects in a specific layer. It relates to silver halide photosensitive materials that are uniformly, stably, and effectively incorporated into the photosensitive materials, and particularly to black-and-white or color photosensitive materials that have improved image sharpness, tone reproducibility, color reproducibility, and ease of handling. be.

(Prior art and its problems) Silver halide photosensitive materials have 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 antihalation layer on a support. The number of layers tends to increase due to improvements in performance and ease of handling.

In addition to photosensitive silver halide grains, photosensitive materials contain so-called additives such as sensitizing dyes, development accelerators, anti-capri agents, and stabilizers; dyes, surfactants, and antioxidants, especially for color photosensitive materials. In some cases, color couplers, color image stabilizers,
Many photographic materials are used, such as color mixture inhibitors, ultraviolet absorbers, and polymer latexes, as described in Research Disclosure RD-176≠3 and RD/r7/6. Although it is originally desired that these materials, particularly those directly related to photographic performance, be contained and fixed in each layer independently, this is not always sufficient. For example, sensitizing dyes, antifoggants, and the like are fixed by being adsorbed onto silver halide grains. However, the adsorption strength was not strong enough, and the stability deteriorated over time. This is a contributing factor. In addition, color couplers, color image stabilizers, color mixing inhibitors, etc. are made hydrophobic and attached with pallast groups, and are fixed by dispersing them into fine particles using oil or polymers.

For this reason, it is bulky and has a thick layer, which causes deterioration in image sharpness. On the other hand, in the case of Fischer type color couplers, a water-soluble group is attached to the pallast group and dispersed and fixed in an alkaline solution, but solid matter is generated during manufacturing, which can cause uneven coating and the occurrence of spots. Currently I tend not to use it. Furthermore, there is no good way to fix dyes, and most of them are uniformly contained in each layer.

Although there is a method using a mordant layer, it is difficult to provide it as a specific layer among multiple layers. For this reason, colloidal silver is currently used in yellow filter layers and antihalation layers.

Many of the fixed materials, with the exception of materials directly related to the image and its preservation, must be removed from the layer after the imaging process, often insufficiently. For example, dyes and sensitizing dyes tend to leave behind a lot of color, so improvements are desired.

As a means of solving these problems, functional compounds that cleave in the presence of reducing substances and exhibit photographically advantageous effects are dispersed in water or hydrophilic colloid solutions using water or organic solvents. An effective method is to include it. However, when such a method is carried out industrially, the dispersion of the functional compound in water or a hydrophilic colloid may change its solution viscosity or form aggregates or precipitates during storage. There's a problem. Furthermore, since the concentration of the functional compound in the dispersion cannot be increased, the volume of the dispersion increases, resulting in inefficiency in its storage, transportation, etc.

(Objective of the Invention) The object of the present invention is to provide a photographic material in which a functional compound that is cleaved in the presence of a reducing substance and exhibits a photographically useful effect is uniformly and stably incorporated in a specific layer. It is in.

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

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic material having a gelatin-containing hydrophilic colloid layer on a support, in which the hydrophilic colloid layer comprises a compound represented by the following general formula (1). This was achieved by including an amphoteric surfactant.

General Formula [■] The first feature of the present invention lies 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 cleaves and decomposes and separates from a specific hydrophilic colloid layer. can do. Here, the reducing substance is contained in the photosensitive material in a form that does not act as a reducing substance when the hydrophilic colloid layer is in a normal state, for example, acidic or neutral, but is acted upon by an image forming processing solution (for example, an alkaline developer). It may be kept in storage, or it may be included in the image forming processing solution.

For example, let us explain the case where the PUG group is a dye residue. Seven examples of usage in this case include a usage in which the functional dye according to the present invention is contained in a protective layer to reduce the sensitivity in a specific spectral absorption wavelength range. If this functional dye is cleaved very uniformly even in the presence of a reducing substance, the dye residue will be eluted from the light-sensitive material into the processing solution, leaving no residual color.

A second feature of the present invention lies in the method of incorporating the functional compound of the present invention into a specific hydrophilic colloid layer of a photosensitive material.

The functional compound according to the invention has at least one water-soluble group,
For example, it has a sulfonic acid group or its salt, a carboxyl group or its salt, a sulfuric acid group or its salt, a phosphoric acid group or its salt, a hydroxyl group, a sulfamide group, or a formamide group. Also, as a parast group, an aliphatic group having a carbon number of Hiro (referred to as C4) to /r (referred to as CHI) (for example, a substituted or unsubstituted linear or branched alkyl group, an alkylene group, etc., especially an aliphatic group-substituted sulfamoyl group, carbamoyl group, etc.).

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 carboxyl or sulfonic acid groups. Surfactants can be used. Particularly preferred are cationic/anionic amphoteric surfactants.

The dispersion method of the functional compound of the present invention is characterized by a solubility in water or a water-soluble organic solvent such as water of about It is dissolved and dispersed in an organic solvent with a chemical composition, such as alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, dimethylformamide and dimethylsulfamide.

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

These organic solvents may be removed using a dispersion diameter, low pressure volatilization method or an ultra-optimal method. For this reason, it is easy to use those having a boiling point of /J-1170C or less at normal pressure. Unlike the so-called "Fischer dispersion" known in the art, the pH of the dispersion is neutral, preferably acidic. Preferably, the functional compound of the present invention is dispersed with an organic acid such as citric acid, oxalic acid, acetic acid, tartaric acid, succinic acid or malic acid. It is useful for the chemical stability of the compound itself, the stability of dispersions, and the prevention of precipitation of dispersoids. In the dispersion method of the present invention, unlike the so-called "Fisher dispersion", the counter ion of the water-soluble group (anion) is important, and in particular, the counter ion of the water-soluble group (anion)
5) 3NH etc. are useful.

After being dispersed in water or a hydrophilic colloid solution as described above, it is necessary to mix it with a hydrophilic colloid solution in the former case, or as necessary in the latter case, and then coat it on the support or other coated layer. Apply to.

If necessary, the compound of the present invention can be dispersed together with a reducing substance and contained in the hydrophilic colloid layer. Examples of such reducing substances are described in Japanese Patent Application No. 2.2-IIR, RI.

Firstly, the hydrophilic colloid layer according to the present invention is susceptible to attack by reducing substances because the functional compound of the present invention is directly dispersed in the hydrophilic colloid, and is therefore susceptible to efficient cleavage reaction and subsequent photographic usefulness. It is easy to encourage the group to leave. Second, functional compounds tend to be stably dispersed. It still has a relatively low molecular weight, making it easy to obtain diffusion resistance to other adjacent layers. Thirdly, since a dispersion medium such as oil is not directly required, it has the advantage that it can be contained in a high density and that it is easy to obtain a thin layer thickness.

The method of dispersing functional compounds according to the present invention can be used in conjunction with other so-called oil dispersion methods and dispersion methods using polymers,
It is advantageous for stabilizing oil dispersion and polymer dispersion.

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

General formula (1) %formula% In the general formula CI), PWR is US patent φ.

13, 3&'ri or U.S. Patent Publication, /32゜37
No. 7, JP-A No. 7, JP-A-Shojter-1rjJJJ, which contains an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced. It may be equivalent to a portion of the U.S. patent.

, 2J2.107, JP-A No. 69-10/ll'9 or JP-A No. 7/-♂♂2j7, photographic reagents that undergo an intramolecular electron transfer reaction after being reduced. It may correspond to a moiety containing an electron-accepting quinonoid center and a carbon atom that connects it to a photographic reagent in a compound that is eliminated. In addition, single bonds are cleaved after reduction, as shown in Japanese Patent Application Laid-open No. 30, US Pat. It may correspond to a moiety containing an aryl group substituted with an electron-withdrawing group in a compound that releases a photographic reagent and an atom (sulfur atom, carbon atom, or nitrogen atom) that connects it to the photographic reagent. . Also, U.S. Patent Hong, 4! It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group as disclosed in JO, No. 223, or
Those corresponding to the geminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in U.S. Patent No. 410 It may be.

In order to more fully achieve the object of the present invention, among the compounds of general formula (1), those represented by general formula [■] are preferred.

General formula (II) In the general formula [■] EAG corresponds to the PWR shown in general formula (I).

At this time, (Time) t-PUG binds to at least one of Rls R2 or EAG.

The portion corresponding to PWH in general formula (II) will be explained.

X represents a group (-N(R3)-) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

R1, R2 and R3 represent a group other than a hydrogen atom or a simple bond.

An example in which R1%R2 and R3 are groups other than hydrogen atoms is shown below.

Alkyl group, aralkyl group. For example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminemethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyA/group, ethyl group, co(cudodecanoylaminophenyl)ethyl group, carboxyethyl group, allyl group, J, j, J-trichloropropyl group, n-propyl group, 1so-propyl group, n-
°butyl group, 1so-butyl group, 5ec-butyl group, t
-butyl group, n- is methyl group, See --A! ! ethyl group, 1--, = methyl group, cycloinctyl group, n-hexyl group, 5ee-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, 5ec-octyl group,
t-octyl group, n-decyl group, n-undecyl group,
n-dodecyl group, n-tetradecyl group, n-interdecyl group, n-hexadecyl group, 5ec-hexadecyl group,
t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc.) alkenyl group (optionally substituted alkenyl group).

For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanvinyl group, cyclohexen-7-yl group, etc.) For example, ethynyl group, 1-propynyl group, coethoxycarobonylethynyl group,・Aryl group (aryl group that may be substituted. Examples: evaporation, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, ≠-acetylaminophenyl group, guhexadecanesulfonylaminophenyl group, Methanesulfonyl≠-nitrophenyl group, 3-nitrophenyl group, Hiro-methoxyphenyl group, Hiro-acetylaminophenyl group, Hiro-,;+'methanesulfonylphenyl group, λ.

≠-dimethylphenyl group, Hiro-tetradecyloxyphenyl group, etc.), heterocyclic group (heterocyclic group that may be substituted. For example, /-imidazolyl group, cofuryl group, copyridyl group, !-nitrocopyridyl group) , 3-pyridyl group, 3.!-dicyano-pyridyl group, !-tetrazolyl group, !-phenyl-7-tetrazolyl group, J-benzthiazolyl group,
2-penzimidazolyl group, cobenzoxazolyl group, cooxazoline-coyl group, morpholino group, etc.), acyl group (optionally substituted acyl group. For example, acetyl group, propionyl group, butyroyl group, 1so- Butyroyl group, -22-dimethylpropionyl group, benzoyl group, 3+p-dichlorobenzoyl group, 3-acetylamino-goomethoxybenzoyl group, ≠-methylbenzoyl group, goomethoxy-3-sulfobenzoyl group, nato), e.g. Eva, methane Sulfonyl group, ethanesphonyl group,
Chlormethanesulfonyl group, Furopanesulfonyl L,
Methanesulfonyl group, n-octanesulfonyl group, n-
dodecanesulfonyl group, n-hexatecanesulfonyl group, benzenesulfonyl group, ≠-toluenesulfonyl group,
μmn-dodecyloxybenzenesulfonyl group, nato)
, le group. For example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis-(comethoxyethyl)carbamoyl group, diethylcarbamoyl group, cyclohexylcarno9moyl group, di-n-octylcarbamyl group, 3-dodecyloxypropylcarbamoyl group , hexadecylcarbamoyl group, J-(2,41-di-t-
intylphenoxy)propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, cyn-octadecylcarbamoyl group, etc.)moyl group. For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group,
Bis-(2-methoxyethyl)sulfamoyl group, 1-7'tylsulfamoyl group, methyl-n-octylsulfamoyl group, n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group Illus group, N-phenyl-N-methylsulfamoyl group, Hiro-
decyloxyphenylsulfamoyl group, methyloctadecylsulfamoyl group, etc.).

R1 and R3 are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups,
An acyl group, a sulfonyl group, etc. are preferred.

The number of carbon atoms in R1 and R3 is preferably l-HiroO.

R2 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group mentioned for R1 and R3.゛(The number of carbons is /-1IO
(preferably) Rt, R2, R3 and EAG may be bonded to each other to form a ring.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, general formula (II)
Among the compounds represented by formula (Ill), those represented by general formula (Ill) are preferred.

General formula (III) In the general formula C1I[), corresponds to PWH shown by the general formula CI).

(Time) t-PUG binds to at least one of R4 and EAG.

The part corresponding to PWH in the general formula [■] will be explained.

Y is a divalent linking group, preferably -(C,=O)- or -502-. X represents the same meaning as above.

R4 represents an atomic group that is bonded to X and Y to form a hill or six-membered monocyclic or condensed heterocycle including a nitrogen atom.

Preferred specific examples of the portion corresponding to this heterocycle are described below.

AG temporary AG AG bA where R5, R6, and R7 are a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R8 is preferably an acyl group, a sulfonyl group, or the like.

More particularly preferred examples are listed below (including the bonding position of Time + -P UG).

However, the compounds of the present invention are not limited thereto.

referee EAG EAG EAG More details will be described later regarding specific compounds.

EAG represents an aromatic group that accepts or takes electrons from a reducing substance and is bonded to a nitrogen atom. As EAG, the following general formula (
A group represented by A) is preferred.

General Formula (A) In General Formula (A), Vn represents an I group that forms a 3- to 6-membered aromatic group together with zl and Z2, and n represents an integer from 3 to 3.

V3 knee z3-1v4 knee Z3-Z4-1v5;-z3
-z4-z5-1V6:-z3-z4-z5-26
% "7: -Z3-24-Z5-26-Z7-1V8 knee z3-z4-z5-z6-zl-z8-.

Sub represents -S-1 or -5o2-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. Sub may be the same or different, or may be bonded to each other to form a ring to six-membered saturated or unsaturated carbocycle or heterocycle.

In general formula [A), the sum of the Hammett substituent constant sigma para of the substituents is 10! θ or more, more preferably +0.
70 or more, most preferably 10.

Select Sub so that fj is greater than or equal to fj.

EAG will be described in more detail.

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

Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire compound. Examples of the physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusivity, etc.
It can be used to adjust sublimability, melting point, dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with electrophilic groups, etc.

Next, a specific example of EAG will be given.

Examples of aryl groups substituted with at least one electron-withdrawing group include Hiro-nitrophenyl group, 2-nitrophenyl group, λ-nitroμ-N-methyl-N-n-butylsulfamoyl group, Phenyl group, 2-nitro-a-N-methyl-N-n-octylsulfamoylphenyl group, 2-nidroly-N-methyl-N-n-
dodecylsulfamoylphenyl group, λ-nitro u-
N-methyl °-N-n-hexadecylsulfamoylphenyl group, 2-nitro-hiro-N-methyl-N-n-octadecylsulfamoylphenyl group, conitroμ-
N-methyl-N-(3-carboxypropyl)sul 7 amoylphenyl group% -2-nitro-g N-ethyl-
N-(+?-sulfoethyl)sulfamoylphenyl group, rhonitro<c-N-n-hexadecyl-N-(J
-sulfopropyl)sulfamoylphenyl group, rhonitro μ-N-(λ-cyanethyl)-N-((J-hydroxyethoxy)ethyl)sulfamoylphenyl group, rhonitrog diethylsulfamoyl 7-enyl group, 2-nitro-googe-n-butylsulfamoylphenyl group, non-nitro-μm di-n-octylsulfamoylphenyl group, 2-nidoba--)-n-octadecylsulfamoylphenyl group, 2-nitro-hiro-methylsulfamoylphenyl group, nitro-i-hexadecylsulfamoylphenyl group, 2-nitro-ψ
-N-,71-1-N-(<c-dodecylsulfonylphenyl)sulfamoylphenyl group, rhonitrocou(3-methylsulfamoylphenyl)sulfamoylphenyl group, ternitro-2-N-mef-N -n
-1-tylsulfamoylphenyl group, Hiro-nitro x-
N-methyl-N-n-octylsulfamoylphenyl group, Hiro-Nidrow λ-N-methyl-N-n-dodecylsulfamoylphenyl group, ≠-nitrox-N-methyl-N-n-hexadecylsulfa moylphenyl group,
Koonitro-, 2-N-methyl-N-n-octadecylsul7amoylphenyl group, l-nitro-J -N-methyl-N-(,?-carboxypropyl)sulfamoylphenyl group, Hiro-nitro-Goo N -ethyl-N-(,
2-sulfoethyl)sulfamoylphenyl group, ≠-nitro 2-N-n-hexadecyl-N-(3-sulfopropyl)sulfamoylphenyl group, Hiro-nidro, z-N-(J-cyanoethyl)-N -((rhohydroxyethoxyethyl)sulfamoylphenyl group, goonitro-2-diethylsulfamoylphenyl group, ternitro-2-di-n-butylsulfamoylphenyl group, ≠-nitrocodi-n-octylsulfamoyl group Phenyl group, Hiro-nidro s-di-n-octadecylsulfamoylphenyl group, μm nitro-J-methylsulfamoylphenyl group, Hiro-nidro 2-n-hexadecylsulfamoylphenyl group, Hiro-nidro 2-N -Methyl-N-(4<-dodecylsulfonylphenyl)sulfamoylphenyl group, ψ-nitro-(3-methylsulfamoylphenyl)sulfamoylphenyl group,
μm nitro-λ-chlorophenyl group, λ-nitro-
Chlorophenyl group, 2-nitro-μmN-methyl-N
-n-7'thylcarbamoylphenyl group, λ-nitro-N-methyl-N-n-octylcarbamoylphenyl group, rhonitro-ψ-N-methyl-N-n-dodecylcarbamoylphenyl group, 2-nitro-q- N-methyl-N-n-hexadecylcarbamoylphenyl group, Konitro μ-N-methyl-N-n-octadecylcarbamoylphenyl group, Konitro p-N-mef-N
-(3-carboxypropyl)carbamoylphenyl group, λ-nitrop-N-ethyl-N -(2-sulfoethyl)carbamoylphenyl group, Konitro≠-N-
n-hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, 2-nitro-N-(2-cyanethyl)-N-((J-hydroxyethoxy)ethyl)carbamoylphenyl group, Konitro Hiro-Shi Ethylcarbamoylphenyl group, 2-nitro-4! -Sea n-
Butylcarbamoylphenyl group, 2-nitro-≠-d-n-octylcarbamoylphenyl group, 2-nitro-gudi-n-octadecylcarbamoylphenyl group, Konitrolymethyl carbamoylphenyl group, Konitroly≠-n-hexadecylcarbamoylphenyl base, 2
-Nitro-Hiro-N-/Chiru N-(tt-dodecylsulfonylphenyl)carbamoylphenyl group, λ-Nitro≠-(3-methylsulfamoylphenyl)carbamoylphenyl group, Coonitro-N-Methyl-N-n
-i thylcarbamoylphenyl group, μ-nitro, 2-
N-Methyl-N-n-octylcarbamoylphenyl group, Hiro-nidror-N-methyl-N-n-dodecylcarbamoylphenyl group, Goonitro-2-N-methyl-
N-n-hexadecylcarbamoylphenyl group, Ternitro-J-N-methyl-N-n-octadecylcarbamoylphenyl group, Hiro-Nidrow 5-N-methyl-N
-(j-carboxypropyl)carbamoylphenyl group, Hiro-nitro r-N-ethyl-N-(2-sulfoethyl)carbamoylphenyl group, Hiro-nitro 2-N-n
-hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, Coonitrolo N-(2-cyanoethyl) -N-([2-hydroxyethoxy)ethyl)
Carbamoylphenyl group, Ternitrokoethyl carhaloylphenyl group, Hiro-nitro-no-di-n-butylcarbamoylphenyl group, ≠-nitro-S-gie-n-
Octylcarbamoylphenyl group, ≠-nitro, 2-
di-n-octadecylcarbamoylphenyl group, hiro-nitrochomethyllupamoylphenyl group, p-nitro-2-n-hexadecylcarbamoylphenyl group, μm
Nitro-J-N-methyl-N-(+-dodecylsulfonylphenyl)carbamoylphenyl group, ≠-nitro5
-(3-methylsulfamoylphenyl)carbamoyl 7x2A4.21μm dimethanesulfonylphenyl group,
λ-methanesulfonyl-benzenesulfonylphenyl LJ-n-octanesulfonyl-+-methanesulfonylphenyl group, ', 2-nf tradecanesulfonyl-μmmethanesulfonylphenyl group, 2-n-hexatecanesulfonyl-μ- methanesulfonylphenyl group,
λ, a-sea n-dodecanesulfonylphenyl group, λ,
Hiro-sidodecanesulfonyl-j-trifluoromethylphenyl group, 2-n-decanesulfonyl-≠-cyano-trifluoromethylphenyl group, Kocyano-Hiro-methanesulfonylphenyl group, j, 4'.

A-) Lycyanophenyl group, λ, Dagucyanophenyl group, Rhonitro μm methanesulfonylphenyl group, 2
-nitro-u-n-)”decanesulfonylphenyl group, 2-nitro-a-(2-sulfoethylsulfonyl)
phenyl group, 2-nitro-hiro-carboxymethylsulfonylphenyl group, 2-nitro-carboxyphenyl group, 2-nitro-μm ethoxycarbonyl-6, -n
-7') xyphenyl group, j-=Dorohiro-ethoxycarobonyl-j -n-hexadecyloxyphenyl L2-ditroterdiethylcarbamoyl-j -fi
-hexadecyloxyphenyl group, conitro-gucciano j-n-dodecylphenyl group, 1.2.4t-dinitrophenyl group, rhonitro-≠-n-7'' silthiophenyl group, 3.!-dinitrophenyl group, Rhonitro 3.!-Dimethyl-Hiro-n-hexatecanesulfonyl group, Hiro-methanesulfonyl-benzenesulfonylphenyl group, +-n-'octanesulfonyl-2-methanesulfonylphenyl group, !-n-tetradecanesulfonylphenyl group -methanesulfonylphenyl group, ≠-n-hexatecansulfonyl-co-methanesulfonylphenyl group, 2, j-cytof-cansulfonyl-μ-trifluoromethylphenyl; 1fL4A-n-decanesulfonyl-2-cyano-yo-trifluoromethyl phenyl group,
≠-cyano-2-methanesulfonylphenyl group, ternitro-2-methanesulfonylphenyl group, coonitro-
2-n-)"decanesulfonylphenyl group, ≠-nitro λ-(2-sulfoethylsulfonyl) phenyl group, Kuhnitro-kho group, carboxymethylsulfonylphenyl group, Kuh-nitro-λ-carboxyphenyl group, ≠-nitro-khoethoxy group n-
hexadecyloxyphenyl group, nitro-2-diethylcarbamoyl-n-hexadecyloxyphenyl group, hiro-nitro-2-cyano-! -n-dodecylphenyl group, l-nitro-2-n-7' sylthiophenyl group, μm nitro-3゜r-dimethyl-2-n-hexadecanesulfonyl group, Hiro-nitronaphthyl group, -1≠-dinitronaphthyl group , μm nitro-n-octadefuryllupamoylnaphthyl group, nitro-2-dioctylcarbamoyl-r-(3-sulfobenzenesulfonylamino)naphthyl group, λ, J, II, J-.

t-pentafluorophenyl group, 2-nitro-≠-benzoylphenyl group, λ, 4L-diacetylphenyl group,
rhonitro-4'-) IJ fluoromethylphenyl group, Coonitro-J-) IJ fluoromethylphenyl group, Coonitro-3-trifluoromethylphenyl group,
J, 4t, j-) lycyanophenyl group, J14'-dicyanophenyl; Ls-p Rorohiro,! -dicyanophenyl group, 2-bromo-hiro.

! -dicyanophenyl group, termethanesulfonyl group, <
<-n-hexadecanesulfonylphenyl group, λ-decanesulfonyl-trifluoromethylphenyl group, 2
-Nitro-yo-methylphenyl group! -Two Toro-n
-octadecyloxy7'22A4, u-nitro-a-
N-(vinylsulfonylethyl) -N-methylsul7
Amoylphenyl group, 2-methyl-nitrobenzoxazol-yl group, etc.

Examples of heterocyclic groups include, for example, 2-pyridyl group, 3-
Pyridyl group, Hiro-pyridyl group, j-nitrocopyridyl group,! -nitro N-hexadecylcarpamoyl-copyridyl group, 3. j-dicyano-2-pyridyl group,!
-dodecanesulfonyl-2-pyridyl group,! -cyano-2-pyrazyl group, hiro-nitrothiophen-2-yl group,
j-nitro/, λ-dimethylimidazole-hiro-yl group, 3. j-diacetyl-2-pyridyl group, l-dodecyl-! -rubamoylpyridinium-2-yl group, j-
Nitro 2-furyl group,! -nitrobenzthiazol-2-yl group, and the like.

Next, +Time)t-PUG will be explained in detail.

Time represents a group that may cause cleavage of a nitrogen-oxygen, nitrogen-nitrogen, or nitrogen-sulfur bond, releasing PUG through a subsequent reaction.

Various groups represented by Time are known, for example, in JP-A No. 6/-/≠72 Hiro≠ (Rep. page-(7), t/-23 of the same).
Zyo Hiro issue (♂) page - (l≠) page, Tokugan Sho A/-r♂6
Examples include the groups described in No. 2j (3t) page - (Hirohiro) page.

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

Photographically useful groups include, for example, development inhibitors, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes,
Desilvering accelerator, desilvering inhibitor, silver halide solvent, competitive compound, developer, auxiliary developer, fixing accelerator, fixing inhibitor, image stabilizer, toning agent, processing dependency improver, halftone dot improver,
Represents color image stabilizers, photographic dyes, surfactants, hardeners, desensitizers, contrast agents, chelating agents, optical brighteners, ultraviolet light absorbers, etc., or their precursors.

Specific examples of PUG can be selected from the compounds described in the following patent applications: For example, patent application 6O-21A'Al
No. 73, Tokugan Sho J/-1#t26, Tokugan Sho J/-rl
'623, Special Application No. 1977-19!02, Special Application No. 1977-19!
/3&? ≠ No. 7, Tokugan Sho ≦ 2-3 Hiroshi No. 53, Tokugan Sho A
2-J4LYj≠ No. 2-J4LYj≠, Japanese Patent Application No. 3, No. 253, Japanese Patent Application No. 37, No. 1988, the applicant filed
It can be selected from the compounds described in the 0-day application specification, etc.

The compound of the present invention has a water-soluble group as described above.

The substitution position may be PWR, Time, or PUG, but is preferably PUG.

Specific examples of the functional compound represented by the general formula (1) of the present invention are shown below.

to δU2 (U4M9J2 1j S02N(1;8M1?J2 +20 51J2N(U4Mg)2 +2+2 2μ λj λri 3ψ 3j t N 5 (J31Na Next, the amphoteric surfactant of the present invention will be explained.

Amphoteric surfactants have anionic functional groups in one molecule,
It refers to a surfactant that has two different types of functional groups, a cationic functional group and a nonionic functional group, and is broadly classified into anion/cation type, anion/nonionic group, and cation/nonionic type. Anionic/cationic amphoteric surfactants are further classified into the following groups, mainly depending on the type of acid group: (1) Carboxybetaine type (2) Sulfobetaine type (3) Sulfate ester type (4) Phosphoric acid Ester type (5) Amino acid type (6) Aminosulfonic acid type Next, specific examples of the anionic/cationic type amphoteric surfactant according to the present invention will be given.

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

■ /, C7H15CONH(CH2)3N(CH3)2
(CH2)45O3e, LCgHlgCONH(CH2
)3N(CH3)2 (CH2)4803e■ s C11H23CONH(CH2)3N(CH3)
2 (CH2)45O3ea C13H27CONH
(CH2)3N(CH3)2 (CH2)45O3ej
:C15H3ICONH(CH2)3N(CH3)2
(CH2)45O3e■ 1- Cl0H21N(CH3)2 (CHz)as
O3eF C14H29N(CH3)2 (CH2)
3803e9 CtsH3aN”(CHa)z(CH
z) asOae/ /Cl2H25N(CH3)2CH
2CH(OH)CH2SO3ex o, C13H27
CONH(CH2)3N(CH3)2CH2COde2
/, CBH FN (CH3)2CH2COO02,
2, Cl0H21N(CH3)2CH2COOeko3,
C1□H25N(CH3)2CH2CoO0s tt,
Cl2H25N(CH3)2CH2CH2CH2C
OOea r Cl2H25N(C2H5)2CH2
COOex y C10H21N(CH3)2CH2C
J o of H20PO3e, (42H25N(CH3)2CH2CH20
PO3eΦ j 'A C9H19SO2NH(CH2)3N(CH
3) 2 (CH2)45O3e3s C11H23S
O2NH(CH2)3N(CH3)2 (CH2)48
03eΦ 3 J, C13H27SO2NH(CH2)3N(C
H3)2 (CH2)4SO3””J7. (41H2
3S02NH(CH2)3N(CH3)2CH2COO
Next, examples of cationic/nonionic and anionic/nonionic surfactants will be given.

However, the present invention is not limited to these.

・C1+Hz+C0NH<Cud3 N(CH
3)z↓ ・CLJts N(CHx)z ↓ ・CI! H! 5o(CH,Cl20)I%CHICH1
OCHICOOH・C+J3sO(CHzCHzO)+
sCHtCHgOCHzCOOH・C+zlhsO(C
HzClhO)+oCHzCHx 03(hH・C+a
HiyO(CHtCHzO)+5CHtCHzO5Os
H and others, Takao Karime, “Special Functional Surfactants” (19
1986, ■CMC), co-authored by Ryohei Oda and Hiroshi Temple,
Amphoteric surfactants described in Synthesis of Surfactants and Their Applications (1957, Maki Shoten) can be used.

Further examples of the amphoteric surfactant preferably used in the present invention include compounds represented by the following general formula (IV).

General Formula (IV) R2 In the formula, Rf represents an alkyl group, an alkenyl group, or an aralkyl group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and has 1 to 18 carbon atoms. R5 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 in R1 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 general formula (IV), preferred examples of the trivalent linking group represented by A include: C113, CtHs, C113, CtHs, C113, CtHs,
3Hffs c61111% CsH+t
5CIJl1%-c, □1 amount tss C+alls?
, etc. A preferable example of Rf is C
F3, C2F,, C1Fv, II (CF 2CF
Z) z-1)l (CF zcP 2) 4- and the like.

A preferred example of the divalent group represented by B is CHzC
Hg-1CHzCHzCHz-1+CHzCLhr C
HtCH, t-1 (n=1 to 30), +CHz CH
Examples include Ohr CH3(Jh (n = 1 to 30), ?CI(, l, etc.).

Preferred examples of the betaine group represented by D are R and R.

an alkyl group having 1 to 6 carbon atoms, l represents 1 to 6)
.

Examples include.

Next, specific examples of the fluorine-containing amphoteric surfactant represented by the general formula (TV) will be given.

H3 H3 ■■ 1h n=5 Clh C8゜I3 H3 ■-13 Ht The compound represented by the general formula (I) of the present invention may be used in the photosensitive layer or in other constituent layers (for example, a protective layer, an intermediate layer). layer, filter layer, antihalation layer, image receiving layer).

The compounds of general formula (1) according to the invention can be used in a wide range of amounts. The preferred usage amount varies depending on the type of PUG. For example, when PUG is a diffusible dye, it depends on the extinction coefficient of the dye, but it ranges from 0.01 mmol/m2 to jo mmol/m2, preferably 0.01 mmol/m2. /misomol/12-j mm is used. When it is a development inhibitor, it is preferably used in an amount of /-x10-7 mol to /X10-1 mol, particularly preferably from /x10-3 mol to /x10-2 mol per mol of silver halide. It is preferable to use the range.

Further, when PUG is a development accelerator and a nucleating agent, the amount added is preferably the same as that of the above-mentioned development inhibitor. When PUG is a silver halide solvent, 1 mole of silver halide/×
It is preferably used in the range of /θ-5 mol to /x103 mol, particularly preferably /X10-4 to /¥. 10"
It is in the molar range.

The amphoteric surfactant of the present invention is preferably /710-10 times the amount of the compound of general formula (1) by weight, preferably t/Z-X
It is appropriate to use double the amount.

The compound represented by the general formula (1) of the present invention releases a photographically useful group or its precursor by accepting electrons from a reducing substance. Therefore, by uniformly applying a reducing substance, it is possible to uniformly release a photographically useful group or its precursor or to uniformly exhibit a photographically useful function. Furthermore, if a reducing substance is converted into an oxidant in an imagewise manner, a photographically useful group or its precursor can be released in a reverse imagewise manner, or a photographically useful function can be expressed.

The reducing substance may be an inorganic compound or an organic compound, but its oxidation potential is preferably lower than the standard oxidation-reduction potential of silver ion/silver O0♂oV.

Two or more reducing substances may be used in combination.

In particular, compounds known as electron transfer agents (ETA) and electron transfer agents are used for the purpose of controlling (usually to improve) the ratio of the release or development of photographically useful groups in the developed and non-developed areas. It is preferable to use a compound called a donor in combination. As this electron donor, the above-mentioned European Patent Publication No. 220
．． No. 744C, ll, pages 2 to 24I, S -t,
This is a compound described as S-Hiroyo.

Examples of compounds that can be used as reducing substances in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, inzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, llan-amine complexes, Hydroquinones, aminophenols, catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, ≠
-Aminoyo-pyrazolones, etc., as well as The Theory of the Photographic Po-1 by T. H. James
=su(The theory of thepho)
tographic process) 4! th,
Ed,, 2ri l~334! The reducing agents described in 2. can also be used.

Also, JP-A No. 36-/31.7JJ, J7-Hiro 0.
2≠! No., U.S. Pat. No. 330. The reducing agent precursor described in No. t/7 can also be used.

Examples of highly preferable reducing agents include the following.

3-pyrazolidones and their precursors [e.g.
-phenyl-3-pyrazolidone, l-phenyl≠,≠
-dimethyl-3-pilaf' IJton, Hiro-hydroxymethyl-Hiro-methyl-l-phenyl-3-pyrazolidone, /-m-)dyl-3-pyrazolidone, 'P F
Zyl-3-pyrazolidone, /-phenyl-Hiro-methyl-
3-Birasoliton, l-phenyl-termethyl-3-pyrazolidone, l-phenyl-≠, lig-su-(hydroxymethyl)-3-pyrazolidone, /,≠-dimethyl-3-pyrazolidone, Hiro-methyl-3-pyrazolidone, ≠
, ≠-dimethyl-3-pyrazolidone, / -(J-chlorophenyl)-tt-/fruj-hirazolidone,
l-(Hiro-chlorophenyl)-μm methyl-3-pyrazolidone, /-(≠-tolyl)-≠-methyl-3-pyrazolidone, 1-(2-tolyl)-gumethyl-3-pyrazolidone, /-(≠-tolyl) -3-pyrazolidone, 1-
(3-tolyl)-3-pyrazolidone, /-(J-)lyl)-hiro9μm dimethyl-3-pyrazolidone, /-(,2
゜-Trifluoroethyl)-p,ta-dimethyl-3-
Pyrazolidone! -Methyl-3-pyrazolidone, l,!
-diphenyl-3-pyrazolidone, /-phenyl-≠-
Methyl-Hiro-stearoyloxymethyl-3-pyrazolidone, l-phenyl-Hiro-methyl-7-2 uroyloxymethyl-3-pyrazolidone, l-phenyl-≠, ≠-
Bis-(lauroyloxymethyl)-''3-pyrazolidone, l-phenyl-2-acetyl-3-pyrazolidone,
l-phenyl-3-acetoxypyrazolidone] hydroquinones and their precursors [e.g. hydroquinone, tornohydroquinone, co.

-dimethylhydroquinone, t-butylnohydroquinone, co! -di-t-butyl Ihydroquinone, t-
Octylhydroquinone, 2. j-di-t-octylhydroquinone, k-notadecylno-hydroquinone, j--
Sodium entadecylhydroquinone-2-sulfonate, p-penzoyl oxydiphenol, comethyl≠
-benzoyloxyphenol, 2-t-71'thyl-
p-(p-chlorobenzoyloxy)phenol] Combinations of various reducing agents can also be used in the present invention, such as those disclosed in U.S. Pat. No. 3,03, rt.

Color developing agents are also useful as reducing substances in the present invention and are described in U.S. Pat. No. 3,13/.

No. 2tt describes p-phenylene color developers represented by N,N-diethyl-3-methyl-p-phenylenediamine. Further useful reducing agents include amine phenols, which are described in US Pat. No. 3.7t/, 270. Particularly useful amine phenol reducing agents include ≠-amino-λ,6-dichlorophenol, Hiro-amino-2,t-dibromophenol, ≠-amino-comethylphenol sulfate, ≠-amino-3-
Methylphenol sulfate, ≠-amino2,
A--) Chlorophenol hydrochloride, etc. Furthermore, Research Disclosure Magazine LT1 No. JF
x/j10! , U.S. Patent No. 1t, 02/.

No. 2IAO contains 2,6-dichloro-p-substituted sulfonamidophenol, 2. t-dibromo-4(-substituted sulfonamidophenol, JP-A Showa Zy-1167 Hirotheta
p-(N,N-dialkylaminophenyl)sulfamine and the like are described in this issue and are useful. In addition to the heptol-based reducing agents described above, naphthol-based reducing agents such as Hiro-amino-naphthol derivatives and ≠-substituted sulfonamide naphthol derivatives are also useful. Furthermore, as a general color developer that can be applied, US Patent No. 2. #the law of nature!
Aminohydroxypyrazole derivatives described in , Zakota No. 2, US Pat. The aminopyrazoline derivatives described in No. 2,71It are also published in Research Disclosure Magazine l.
Hydrazone derivatives are described in June issue 227-230. These color developers 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 raw photosensitive material, preferably together with the functional compound of the present invention, or in the image forming processing solution, developer solution, or its pre-solution. can. In the raw photosensitive material, the reducing agent is preferably contained in the same layer under neutral or weakly acidic conditions so that it does not react as a reducing substance, and by the same dispersion method as the functional compound of the present invention. is preferable. In this case, it is preferable that the reducing agent has a water-soluble group or an anionic group under the reaction conditions. A reducing agent having a water-soluble group or anionic group can also 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.

In addition to low boiling point organic solvents, the compound represented by the general formula (1) of the present invention can also be used in high boiling point organic solvents such as phthalic acid esters, esters of phosphoric acid or phosphonic acid, benzoic acid esters, aliphatic carbon Acid esters, aniline derivatives, etc. can be used as aids or in combination with fine particle dispersions thereof.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. This silver halide includes silver chloride, silver bromide, mixed silver halide,
For example, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

The average grain size of silver halide (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter; in the case of cubic grains, the grain size is taken as the wavelength, and expressed as an average based on the projected area) is:
It is preferably 2μ or less, and particularly preferably O0≠μ or less.

The shape of these silver halide grains is cubic crystal, octahedral, mixed crystal form, or JP-A No. 2003-272312, J1-
//j The octopus may be in any shape such as a flat plate as described in the number.

Alternatively, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is similar to the inside, there are also grains with a layered structure with different interior and exterior structures, as well as those in British Patent No. 13, No. 4T1, and U.S. Patent No. 3. t2λ.

It may also be of a so-called conversion type as described in No. 311. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. In the latter case, a positive image can be obtained directly using a nucleating agent or optical fogging.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present.

The silver halide emulsion may be a so-called immature emulsion (primitive emulsion) which is not chemically sensitized, or it may be chemically sensitized. For chemical sensitization, active gelatin and sulfur-containing compounds that can react with silver (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines) are used.
Sulfur sensitization method using reducing substances (e.g. stannous salts,
Reduction sensitization using amines, hydrazine derivatives, formamidine sulfines, silane compounds), noble metals using noble metal compounds (e.g. gold compounds, and complex salts of group Ⅰ metals of the periodic table such as platinum, iridium, palladium, etc.) Sensitization methods and the like can be carried out alone or in combination.

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

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

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin can be used.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine color L hemicyanine dyes, styryl dyes, and hemioquinol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, cochoxazolidine-2,
4! -dione nucleus, thiazolidiy-,2,4! −j such as dione nucleus, rhodanine nucleus, thiobarbyl acid group, etc. −J
Member heterosegmental ring nuclei can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants other than the amphoteric surfactant of the present invention may be included for various purposes.

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, etc.), aldehydes (formaldehyde, geltaraldehyde, etc.)
, N-methylol compounds (dimethylol urea, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (/, J, j-1-lyacryloyl-hexahydro-S-triazine, i,3-vinylsulfonyl-1-furo A/-lunato), Active halogen compounds (co-, goo-dichloro-bu-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, etc.)
, N-carbamoylpyridinium salts ((/-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts, and the like can be used. In the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium salt compounds, urethane derivatives, and urea derivatives. , imidazole derivative,
It may also contain 3-pyrazolidones and the like.

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 dimensional stability.

For example, a polymer containing alkyl (meth)acrylate, glycidyl (meth)acrylate, styrene, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. as a monomer component can be used.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemio, quinol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion used in the present invention, various compounds other than the compounds of the present invention may be used for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or stabilizing the photographic performance. be able to. namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. mercapto Thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-j
- mercaptotetrazoles), mercaptopyrimidines, mercaptotriazines, etc.): thioketo compounds such as oxadolinthione; azaindenes (such as triazaindenes, metaazaindenes);
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and the like.

The photographic light-sensitive material of the present invention contains a color image-forming coupler, that is, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative or an amine phenol derivative) in a color development process. You may. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule, or a polymerized coupler. The coupler may be either monoequivalent or monoequivalent to silver ion. Colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR) are also used.
coupler). Moreover, the product of the coupling reaction is colorless, and a colorless DI that releases a development inhibitor is used.
It may also contain an R coupling compound.

For example, as a magenta coupler! - Pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, pyrazolotriazole couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides), etc. Examples of cyan couplers include naphthol couplers and phenol couplers.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

In order to introduce the coupler into the Rogge/Silver Fide emulsion layer, known methods such as those described in US Pat. No. 322,0.27 can be used.

Known antifading agents can be used in the photographic material of the present invention. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

In addition to the various additives mentioned above, various additives can be used in the photosensitive material of the present invention depending on the purpose.

These additives are described in more detail in Research Disclosure Item/7; , the relevant locations are summarized in the table below.

l Chemical sensitizers Page 23 Right column 2 Sensitivity increasing agents Same as above Brighteners 2 Hiro Page 7 Anti-stinting agents Page 2J right column Tro page left to right column ♂
Dye image stabilizer page 25 Hardener page 1 page left column 10
Binder, page 26 Same as above//Plasticizer, lubricant, page 27, page 6, right column, supports used in the present invention include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (e.g. polyethylene, polypropylene). etc.) Laminated paper, polystyrene film, polycarbonate film, metal plates such as aluminum, etc.

These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.

For photographic processing of light-sensitive materials, any known method can be used, and known processing solutions can be used. Also, the processing temperature is usually from lr 'c to zo 0
selected between c but below 1t0c or ro
The temperature may exceed 0C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied.

The black and white developer contains known developing agents such as dihydroxyincenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone), and aminephenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, Hiroshi-
Amino-N, N-diethylaniline, 3-methyl-Hiro-
Amino-N, N-diethylaniline, Hiro-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N
-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (/
No. 22z-Kokota, U.S. Patent 2. /ri3,
0/J issue, 2,392.3g7, JP-A-Sho+, r-a
Those described in No. +233 may also be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants other than the compounds of this invention. , an antifoggant, and the like. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming cazolers, and competitive oak 2. -, fogging agent such as sodium boron hydride, /-co-developing agent such as phenyl-3-pyrazolidone, viscosity-imparting agent, U.S. Pat. No. 4', C#3
．． The polycarboxylic acid chelating agent described in No. 723, the antioxidant described in OLS, Z, A22, R50, and the like 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 6 with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (ill), cobalt (II), chromium (■), and copper (It), peracids, quinones, and nitroso compounds. for example,
Ferricyanide, dichromate, organic complex salts of iron (III) or cobalt (I), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /3-diamino-λ-prononoltetraacetic acid, or citric acid. , complex salts of organic acids such as tartaric acid and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, ethylenediamine sodium iron(I[I) acetate, and ammonium ethylenediaminetetraacetate iron(III) are particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, US Pat.
No. 0, same! , 21A/, No. 766, Special Publication Show 1Aj-
In addition to the bleaching accelerators described in Japanese Patent Publication No. tjet, Japanese Patent Publication No. Sho IAj-1136, and the thiol compounds described in Japanese Patent Application Laid-open No. Sho 3=gj732, various additives can also be added.

The washing process is sometimes carried out in one tank, but in most cases it is carried out in two tanks.
It is carried out using a multi-stage countercurrent water washing method with more than one tank.

The amount of water in the washing process can be set arbitrarily depending on the type and purpose of the color photosensitive material, but for example, Journal of Motion Picture and Television Engineering, Vol.
"Water Flow Rates in Immersion Watching of Motion Picture Film" (Month issue)
Immersion-Washing of Moti
on Picture Film.

It can also be calculated by the method described in S., R. Goldwasaer.

When reducing the amount of water used for washing, the growth of bacteria and mold becomes a problem.
Washing water with reduced calcium and magnesium levels, bactericides and fungicides, such as antibacterial agents and fungicides, such as antibacterial agents and antibacterial agents, such as those described in Specification No.
ifug, Agents) vol.

//, &! , p. 207 to 23 (19r3) and the compound described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi) can be added.

In addition, chelating agents such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can also be added as water softeners.

When reducing the amount of water used for washing, the amount of water used is usually 10,100 ml to 200 ml per m2 of color photosensitive material, but a range of 200 ml to 7,000 ml is particularly preferred from the viewpoint of achieving both color image stability and water saving effect. It will be done.

The pH during the washing process is normal! It is in the range of ~ri.

The photographic elements of this invention are also advantageously used in color imaging processes in which imagewise diffusible dyes are formed or released and then diffused and then fixed.

The above color image forming methods include those in which development is performed using a developer at a temperature near room temperature [color diffusion transfer method] (for example, the method described in Belgian Patent No. 7J7, ?!), and those in which the image is developed in a substantially moisture-free state. [Thermal development method]
(For example, European Patent 76≠22A2 and Japanese Patent Application Laid-Open No.
Hiro 7, same! ? Although there are various forms such as those described in JirlAg No. 3 and Japanese Patent Application No. 70-70-1970, etc., the photographic element of the present technology can be used in any of them.

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

General formula [X] 7-Y where Dy represents a dye moiety (or its precursor moiety), and Y represents a dye-donating substance general formula [X] as a result of development.
represents a functional substrate that changes the diffusivity of the compound represented by

Here, "diffusivity changes" means (1) General formula [X]
The dye-donating substance represented by is originally non-diffusible and changes to diffusive, or a diffusible dye is released, or (2) the general formula [X
] means that the dye-donating substance is changed to non-diffusibility. Further, depending on the nature of Y, this change may occur due to oxidation or reduction of Y.

Examples of changes in diffusivity due to oxidation of Y include:
p-sulfonamide naphthols (including p-sulfonamide phenols: JP-A Akihiro f-, No. 33,126,
Specific examples are described in No. 33-60,736, European Patent No. 1j, and Kou No. 22), 0-sulfonamidophenols (including O-sulfonamide naphthols: JP-A-Shoj/
-//J.

No. 62, No. 74-/u4 Kou 2, No. 54-/4/30
No., jA-/l/3/, j7-4!0 Hiro 3, Tafu tjO, U, S, ≠, Oj3゜3/λ, European Patent No. 1A, ≠22. Examples will be described tomorrow), hydroxysulfonamide heterocycles (Specific examples will be described in JP-A-KOKAI Shozi-io≠, 3-Ko No. 3, European Patent No. 1 O, and ≠ RI No. 2)
, 3-sulfonamide indoles (JP-A-Shoj/-10
≠, 3g No. 3, same j3-Hiroshi 1. , No. 730, same j≠−7
No. 30,122, No. 67-11,011, European Patent No. 14. Specific examples are described in Hirotako No.), α-sulfonamide ketones (specific examples are described in JP-A No. 63-J, ♂/ri, Hiro-Hirot, No. 53, and European Patent No. 16 Geter). Mention may be made of so-called dye-releasing redox substrates such as (with examples).

Another example is JP-A-57-20.7Jj, which releases a dye by intramolecular nucleophilic attack after Y is oxidized.
Examples include intramolecularly assisted substrates described in JP-A-19-61139.

Another example is a substrate that releases a dye through an intramolecular ring-closing reaction under basic conditions, but substantially no longer releases a dye when Y is oxidized (JP-A-Sho!). /-4j, j/♂ has a description of a specific example). Furthermore, as a modified version of this, a substrate in which the inoxacilone ring undergoes ring rewinding by a nucleophilic reagent and releases a dye is also useful (JP-A-Sho Geter///, No. 1, J2-Hirl).
Specific examples are listed in the number).

Another example is a substrate in which the dye moiety is released by dissociation of acidic protons under basic conditions, but when Y is oxidized, virtually no dye is released. 13-Ari, No. 033, same μ-/30 octopus 7
Specific examples are given in the issue).

Furthermore, compounds that undergo redox reactions with silver halides or organic silver salts at high temperatures, resulting in a change in the mobility of the compound having a dye moiety, can be used.
It is described in No. 1jOj≠.

Further, regarding dye-donating substances that release mobile dyes by reaction with silver ions in photosensitive materials, JP-A-10-10!
Hiro is listed in the number.

The image-receiving element may be provided on a separate support from the photosensitive element or may be a film unit embedded with the photosensitive element.

A typical form of film unit is that the above-mentioned image receiving element and photosensitive element are laminated on one transparent support, and after the transferred image is completed, the photosensitive element is peeled off from the image receiving element. This is an unnecessary form. More specifically, the image-receiving element comprises at least one mordant layer, and in preferred embodiments 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;
Each of the above-mentioned emulsion layers is composed of a yellow dye-providing substance, a magenta dye-providing substance, and a cyan dye-providing substance, respectively. An emulsion layer that is sensitive to light of IAOnm or higher). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye-donating substance-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a peeling layer may be provided at an appropriate position so that all or part of the multi-photosensitive element can be peeled off from the image receiving element. θ and Canadian patent t7 Hiro, Or2).

In another form that does not require peeling, the photosensitive element described above is coated on one transparent support, a white reflective layer is coated on it, and an image-receiving layer is further laminated thereon. A mode in which an image-receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled off from the image-receiving element, is described in U.S. Pat. No. 3,730.7Ir. has been done.

On the other hand, there are two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports.
One is a peelable type, and the other is a peelable type. To explain these in detail, a preferred embodiment of the peelable film unit has a light-reflecting layer on the back surface of the support, and at least one image-receiving layer coated on the surface thereof. In addition, the photosensitive element is coated on a support having a light-shielding layer, and the surface coated with the photosensitive layer and the mordant layer do not face each other before the end of exposure, but after the end of exposure (for example, during development) the surface coated with the photosensitive layer does not face each other. It is devised so that it bends tightly and overlaps the surface on which the image-receiving layer is applied. Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the image receiving element.

In a preferred embodiment of the peel-free 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-blocking layer, The surface coated with the photosensitive layer and the surface coated with the mordant layer are stacked facing each other.

All of the above-mentioned forms can be applied to both the color diffusion transfer method and the heat development method, but especially in the former case, a container (processing element) containing an alkaline processing liquid and rupturable under pressure is also combined. You can. In particular, in a peel-free film unit in which an image-receiving element and a photosensitive element are laminated on one support, the processing element is preferably placed between the photosensitive element and a cover sheet placed thereon.

Further, in the case where a photosensitive element and an image receiving element are separately coated on two supports, it is preferable that the processing element is placed between the photosensitive element and the image receiving element at the latest during development processing. Depending on the form of the film unit, the processing element preferably contains a light blocking agent (such as carbon black or a pH-dependent dye) and/or a white pigment (such as titanium oxide). Furthermore, in color diffusion transfer film units, a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is preferably incorporated into the cover sheet, the receiver element, or the photosensitive element. .

On the other hand, in a heat-developable film unit, a support,
A heat-generating layer containing fine metal particles, carbon black, graphite, or other conductive particles is provided at an appropriate position on the photosensitive element or image-receiving element to generate Joule heat when electricity is applied for thermal development or diffusion transfer of dyes. You may also use 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 explained in more detail based on examples.

Example 1 (Preparation of emulsion A) Silver nitrate aqueous solution and per mole of silver o, z x 1o-
A sodium chloride aqueous solution containing 4 mol of ammonium rhodium hexachloride (I[I) acid was mixed with 3!
pH 4.0 in gelatin solution at 0C. A monodispersed silver chloride emulsion with an average grain size of 0.07 μm was prepared by mixing the mixture while controlling the grain size so that the grain size was 0.07 μm.

After particle formation, soluble salts were removed by 70 curation method well known in the art and stabilizers such as Hiro-hydroxy-4-methyl-7,3°3a, 7-titraazaindene and/-phenyl- -Mercaptotetrazole was added. The gelatin contained in the emulsion/kg was 55 g/OJg of silver. (Emulsion A) (Preparation of light-sensitive material) The following nucleating agent, nucleation accelerator, and dye that enhances safelight safety are added to the emulsion A, and the nucleating agent, nucleation accelerator CR, safelight dye 3 2r, 0 Next, polyethyl acrylate latex (l≠m g
/ m 2 ), and 2. II-dichloro-t-hydroxy/, 3. Z-) Add riazine sodium salt to 7 m2 p3. A silver halide emulsion layer is coated on a polyethylene terephthalate transparent support so that the silver amount is zg, and gelatin (1
, 3 g/m2), the compound of the present invention, 2 (o, i
g/m2), and a protective layer containing the following three surfactants, stabilizers, and matting agents as coating aids was coated and dried. (sample/).

Surfactant addition amount (mg/m2) 03Na (4F17SO2NCH2COOK 2.
r3H7 Stabilizer Thioctic acid Matting agent Polymethyl methacrylate (average particle size J, jμ) 2.0 Compound 2 of the present invention was used by preparing a dispersion according to the following procedure.

Solution I Add solution ■ little by little while stirring the solution ■ at so 0c.

The pH of the finished solution was 4A.

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

(Evaluation of Performance) (1) Stability of Dispersion The results of stability tests for the dispersion used in Example 7 and the dispersion used in Comparative Sample A are shown in Table 1. The dispersion used in Comparative Sample A significantly decreased in viscosity, increased turbidity, and started precipitation during aging at tao 0c, whereas the dispersion in Example 7 of the present invention , hardly changes.

(2) Coated surface condition of samples When each dispersion was used after aging at ≠o 'C, no abnormality was observed in Example -/, but the surface of Comparative Sample A was rippled. Abnormalities occurred, and precipitates were partially observed.

(3) Photographic properties A sample using the dispersion aged for several days at the uo 0c described above was printed on a Dainippon Screen Meisho printer P-60.
Step 7: Expose through an optical wedge and apply 3r of next developer.
It was developed for 20 seconds, fixed in a conventional manner, washed with water, and dried.

As a result, in comparison sample A, a strong ripple-like abnormality was observed in the blackened area, resulting in an image that was not suitable for practical use, but in the sample of Example-7, no abnormality was observed at all.

Developer hydroquinone 3j.0g N-methyl-p-aminophenol //, bisulfate o, rg sodium hydroxide /J, 0g potassium triphosphate 7 hiro, og potassium sulfite
tao, og ethylenediaminetetraacetic acid tetrasodium salt /, 0g potassium bromide ≠, ogj-methylbenzotriazole o, tg3-diethylamino-7
,2-Propanediol l, add 0g water /1 (pH=11.t) Example-2 In Example-/, as an amphoteric surfactant in the dispersion,
Compound &j 1. The same procedure as in Example 1 was carried out except that Arg was used in the type and amount shown in Table 2.

As a result, both the viscosity change and the mechanical stability of the dispersion
As shown in Table 2, the results were good. The coated surface condition and photographic properties of the sample were also good.

Example 3 In Example 1, Compound μ, Compound 6, and Compound ? instead of Compound 20 in Liquid I of the dispersion were used. , compound 16 and
The same procedure was performed except that Compound 17 was used.

All exhibited good dispersion stability, coated surface condition, and photographic properties.

Example - On a cellulose triacetate film support with Hiro undercoat,
A multilayer color photosensitive material of the present invention having each layer having the composition shown below was prepared.

(Composition of photosensitive material) The coating amount is expressed in g/m2 of silver for silver halide, colloidal silver, and coupler, and the coating amount is expressed in g/m2 of silver in the same layer. Expressed in moles of water.

1st layer: Antihalation layer black colloidal silver Silver coating amount Q8.2 Gelatin λ・2UV-/(ultraviolet absorber) O1/UV-J (ultraviolet absorber) O-2 Cpd-/ 0.0jSo
l v-/ (UV-/, UV-2 dispersion oil)
o, otSo 1 v-2 (UV-/
XUV-2 dispersion oil) 0.0/So 1
v-J (oil for dispersing Cpd-/) o, or second layer:
Intermediate layer fine grain...Silver halogenide (AgBr with average grain size 0.07p) Silver coating amount 0.7 gelatin
/, 0Cpd-2 (color mixture prevention agent) O-2 3rd layer: 1st red-sensitive emulsion layer (1st RL) Silver iodobromide emulsion (AgIlo, 0 molt, internal high AgI type, equivalent sphere diameter o, rμ, Coefficient of variation of equivalent sphere diameter 21re4,
Platy grains, diameter/thickness ratio 3°, silver coating amount 0.7 Silver iodobromide emulsion (AgIJ, O morch, internal high AgI type,
Equivalent ball diameter 0. jμ, coefficient of variation of equivalent sphere diameter 2J%, plate-shaped particles, diameter/thickness ratio 3° Silver coating amount 0.6 Gelatin 2°0SD-
/(sensitizing dye) μ, yo (sensitizing dye)
0.3 x 10-4 mol EXC-/(coupler)
0. jjEXC-2 (DIR coupler)
0.0/EXC-3 (colored coupler) 0.
0JS o 1 v-/ (EXC-/X2.3 dispersion oil) O-2 S o 1 v-J (EXC-/, 2.3 dispersion oil) O-2 th layer: 2nd red Sensitive emulsion layer (RL) Silver iodobromide emulsion (AgIlo, 0 molt, internal high AgI type, equivalent sphere diameter/, θμ, coefficient of variation of equivalent sphere diameter 30%, plate-like grains, diameter/thickness ratio.

Silver coating amount /・O Gelatin /, JSD-
t (sensitizing dye) 3×to-48D-2 (sensitizing dye)/YC10-4 SD-3 (sensitizing dye) o, 3×1O-4SD-μ (sensitizing dye) 0.3×10- 4 mol EXC-t (coupler)
0.02EXC-J (colored coupler)
o, 06EXC-da (coupler 3 0.
/-2S o 1 v-/ (EXC-/, j, Hiroshi's dispersion oil) 0. /CoS o l
v-2 (EXC-/, j, da dispersion oil)
O0/koth! Layer: Intermediate layer gelatin /, Jcpa-
≠ (color mixture prevention agent) 0.2 Layer: First green-sensitive emulsion layer (first GL) Silver iodobromide emulsion (AgIlo, omolti, internal high AgI type, equivalent sphere diameter o, rμ, equivalent sphere diameter) Coefficient of variation 2r%, plate-like grains, diameter/thickness ratio 3°, silver coating amount 0.2 Silver iodobromide emulsion (AgI, g, o mole, internal high AgI type, equivalent sphere diameter 0.4-μ, equivalent sphere Coefficient of variation in diameter: 2 Ochi, plate-shaped particles, diameter/thickness ratio: 3° Silver coating amount θ, / Gelatin /, 4LSD
-, j (sensitizing dye) zxlo-4 SD-A (sensitizing dye) 2X10-4 SD-7 (sensitizing dye) / X/ 0-0-
4EX/(Cub 5-) o, tir EXM-2 (DIR coupler) o, otEXM-, t
(Color) 'Cub 5-) o, otSo l v-/ (
EXM-/X2,! dispersion oil)
o, Co 1st layer: 2nd green-sensitive emulsion layer (Co GL) Silver iodobromide emulsion (AgIlo, 0 molt, internal high iodine type, equivalent sphere diameter 0.2tμ, coefficient of variation of equivalent sphere diameter sr4, plate shaped particles, diameter/thickness ratio 3° Silver coating amount o, t Gelatin 00jSD-1
(Sensitizing dye)1. ! ×1O-48D-1 (sensitizing dye)
-/, &X/? -48D-7 (sensitizing dye) 0.7
X10-4EXM-i (coupler) 0.
2jEXM-j (colored coupler) o, os
S o l v-/ (EXM-/, dispersion oil of 3) 0. '/jth layer: Intermediate gelatin 7.0th layer:
3rd red-sensitive emulsion layer (No. JRL) Silver iodobromide emulsion (average grain size /, !, Agl 10°O morch, internal high AgI type, equivalent sphere diameter /, jμ, coefficient of variation of equivalent sphere diameter 32 inches, plate shaped particles, diameter/thickness ratio 6.0) Silver coating amount o, r Gelatin 1. ko5D-t
(Sensitizing dye>1x10-4 SD-2 (sensitizing dye) o, txlo-4SD-J (sensitizing dye) o, 2xt□-4EXC-a (coupler
) o, orEXC-j (coupler)
(1), (1)7S o I V-/ (
El:XC-u,! dispersion oil)
0. /λS o l v-J (EXC-41,!
dispersion oil) 0. /Co 10th layer: Functional silver halide emulsion layer (FL) Silver iodobromide emulsion (A
gIio, omolti, internal high AgI type, equivalent sphere diameter/, j
μ, coefficient of variation of equivalent sphere diameter 21%, spherical particle, diameter/thickness ratio l.

O) Silver coating amount 0. ! g gelatin θ, jgSD-7
(Sensitizing dye>tx) □-4 EXY-2 0,00/gS
o l v −/ (EXY-J dispersion oil)
o, oo1g 1st g layer: 3rd green-sensitive emulsion layer (jGL) silver iodobromide emulsion (Agl 10.0 molti, internal high AgI type, equivalent sphere diameter/, jμ, coefficient of variation of equivalent sphere diameter 32%, plate shaped particles, diameter/thickness ratio t.

O) Silver coating amount /,! Gelatin /, μ5D-
z (sensitizing dye) axto-4 SD-j (sensitizing dye) o, r×10-4 5D
-7 (sensitizing dye) o, rxto-4EXM-≠ (coupler) o, ■sEXM-t (color)'
Kabuy-)o, o3EXC-tt,
o, ootS o 1 v-/ (EX
M-44, /, EXC-g dispersion oil)
o, 2 amphoteric surfactant Aj O,031
g Gelatin □, j For this layer, a dispersion was prepared using the following formulation and used for coating.

■Liquid compound Hiroshi J, 0g dimethylformamide j, , r m1lu liquid amphoteric surfactant Aj 2.1g gelatin! , μg citric acid
0, /jgH20100m1 ro While stirring the solution (2) at 0c, the solution (2) was added.

13th layer: Intermediate layer gelatin 0. jgCpd
-20,/g So 1 v-/ (Cpd-1 dispersion oil) 0. /First layer: First blue-sensitive emulsion layer (first BL) Silver iodobromide emulsion (AgIj
. 3 molti, internal high iodine type, equivalent sphere diameter 0.7 μ, coefficient of variation of sphere equivalent diameter, 2/%, octahedral grains) Silver coating amount 0.2 Silver iodobromide emulsion (AgIj, O molti, internal high iodine type,
Equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 22 tahedral particles) Silver coating amount o, i Gelatin /, 2SD-r
(Sensitizing dye) EXY-4 EXY-/(Coupler) 0.7 EXY-2 (DIR coupler) 0.03S o
l v-/ (EXY-/, 2 dispersion oil)
θ, j 1st 13th: 2nd blue-sensitive emulsion, zBL) Silver iodobromide emulsion (AgIlo, 0 molt, internal high AgI type, equivalent sphere diameter/, 0μ, coefficient of variation of equivalent sphere diameter 30 inches, Platy particles, diameter/thickness ratio ψ.

O) Silver coating amount O0≠ Gelatin 0.3SD-r
(Sensitizing dye) 2x10-4 dispersion oil)
0.2 16th layer: Intermediate layer fine-grained silver iodobromide (AgI2 molten, uniform type, equivalent sphere diameter Q
, /3μ) Silver coating amount 0. Hirogelachi 7 0. Google q7th layer:
Third blue-sensitive emulsion layer (No. JBL) Silver iodobromide emulsion (AgI/Hiroshi, Omolti, internal high AgI type, equivalent sphere diameter λ, lμ, coefficient of variation of equivalent sphere diameter 30%, plate-like grain, diameter/ Thickness ratio j.

O) Silver coating amount /, 4 Gelatin /, /5D-
ff (sensitizing dye) /, jxlo-4EXY-i
(Coupler) 0.2 So 1 v-/ (EXY-/ dispersion oil)
0.7 Hiro 1st male layer: 1st protective layer gelatin 7/, J'uY'
(Mostly 7) Ei'! X size
(UV-/, 2 dispersion oil) 0.0/1st layer: 2nd protective layer fine particles...Silver halogenide (AgBr with average particle size 0.07)
) Silver coating amount 0.3 gelatin
0.7 Polymethyl methacrylate particles (diameter i, sμ) 0.2 W-/(charge control agent) 0.02H-/
(Hardening agent) O1≠Cpd-, t(
Formaldehyde scavenger) l, O (Structural formula of compound used in Examples) EXM
-UV-t (n) C15H31 SD-/ SD-, z SD-J SD-Hiro2H5 SD-z SD-4 SD-7 SD-♂ Solv-7 Solv-λ Solv-3 Solv-HiroCpd-/ Cpd-2 Cpd-3 Cpd-Hiro Cpd-t C8F17S02NHCH2C) (2CH20CH2C
H2♂(CH3)3H-/CH2=CH8O2CH2CONH-CH3I CH2=CH5O2CH2CONH-CH2 The transparency and surface condition of the film coated and dried on the cellulose triacetic acid film support were observed. No defects due to poor dispersion were observed.

The obtained coated material was processed into a size of 31 mm for camera photography. Using the obtained sample, a color rendition chart manufactured by Macbeth was photographed under a light source with a color temperature of 0. This was subjected to color development using the following processing steps to obtain a negative film.

Furthermore, I printed it on Fujicolor "s/" ()/Itek Paper) to obtain a color photograph.

Color developer diethylenetriaminepentaacetic acid 1. O7-Hydroxyethylidene-7゜l-diphosphonic acid Co.0 Sodium sulfite ≠, O Potassium carbonate
30.0 Potassium Bromide
/, potassium iodide
/ , J mg hydroxyamine
2. ≠ Hiro-(N-ethyl-N-β-hydroxyethylamine)-2 monomethylaniline sulfate Hiro! Add water to 1l (add potassium hydroxide and add lo, y) Bleach solution> Ethylene diamine chloride acetate ferric ammonium salt 100 g Ethylene diamine acetate disodium salt, io, og aqueous ammonia 7 ml Ammonium nitrate 70.0 g bromide ammonium
Add 710g water
/lpH't
Fixer> Ethylenediamine μ acetic acid disodium salt /, 0g Sodium sulfite, og Sodium bisulfite, Ammonium thiosulfate aqueous solution (70%) / Add 7ml water /lpHt,g Washing liquid> Tap water (Calcium 27ml/l, Magnesium 1/l
(contains 0 mg/l) Stabilizing solution> Formalin (37% w/v) 2 ml
0.3 g of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) was added to the mixture.As a result of 11 sensitometry, no defects due to poor dispersion of the compound according to the present invention were observed.

Example-5 Silver nitrate aqueous solution and silver 1 in gelatin aqueous solution kept at 38°C
1 per mole. lXl0-' mol of rhodium hexachloride(1)
An aqueous sodium chloride solution containing ammonium acid was added over 15 minutes by a double jet method to prepare monodisperse silver chloride cubes with an average particle size of 0.08 μm. After particle formation, soluble salts are removed by the croquelation method well known in the art, and 4-hydroxy-6 is added as a stabilizer.
-Methyl-1,3,3a,? -tetraazaindene and 1-ph5-5-mercaptotetrazole were added. 1 kg of emulsion contains 55 g of gelatin and 10 g of silver.
It was 0g.

Add 1 hydrazine compound (1) represented by the following formula to this emulsion.
1 mg/rrr, compound (2) at 20 mg/rd, compound (3) at 6/rr, compound (4
) 20a+g/a, compound (5) was added as a dye to further enhance safelight safety, and then 0.8g/% of polyethyl acrylate latex was added as a hardening agent.
2-bis(vinylsulfonylacetamido)ethane 14
5 g/m was added and coated on a polyethylene terephthalate support to give a silver amount of 3.8 g/n. Furthermore, 0.8 g/m of gelatin was added to the top layer of compound (6).
85 ■/bo, 1,5-dihydroxy-2-benzaldoxime 30 mg 10f, thioctic acid 6 ■/bo, polyethyl acrylate latex 140 mg/rd,
Protection 1-1 was applied by adding 10 mg/rrf of sodium dodecylbenzenesulfonate as a coating aid.

Compound (1) Compound (4) SO,Na Compound (6) Further, on the protective layer-1, gelatin 0.6 μ/I and the compound represented by the general formula (1) of the present invention (Example-2) were added to O. ,1
g/rrf, sodium dodecylbenzenesulfonate as coating aid 16/nf, N-perfluorooctanesulfonyl-N-probylglycine potassium salt 3
(2)/B. Polymethyl methacrylate (average particle size: 2.5 μm) 40 μ/Bo was added as a matting agent, and protective layer-2 was coated.

In addition, compound example-2 represented by general formula (1) of the present invention
prepared a gelatin dispersion using the following procedure.

A solution of 10 g of Compound Example 2 dissolved in 20-N,N-dimethylsulfamide was mixed with 17 g of Compound IV-1 of the general formula (IV) of the present invention and 0.0 g of citric acid. 6 with 57g added,
The mixture was mixed with 465 g of a 5 wt % aqueous gelatin solution at 50° C. while stirring to obtain a dispersion. The pH of the finished solution was 5.3.

(Preparation of comparative sample) Comparative sample A was prepared in the same manner as above except that compound IV-1 was not used. Performance evaluation is Example-1
It was done in the same way.

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

Example-6 The compound of the general formula (IV) of the present invention shown in Table-4 was used in the dispersion of Compound Example-2 of the general formula (I) of Example-5, and the other conditions were the same as in Example-5. A dispersion was obtained.

Then, it was applied onto 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, and also have good coating surface condition and photographic properties.

Example-7 In Example-5, Compound Examples-4, -6, and Compound Example-2 in the gelatin dispersion of the compound of general formula (1)
-81, 16, and -17 were used in the same manner.

All exhibited good dispersion stability, coated surface condition, and photographic properties.

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

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (3)

[Claims] (1) In a silver halide photographic material having a gelatin-containing hydrophilic colloid layer on a support, the hydrophilic colloid layer contains a compound represented by the following general formula (I) and an amphoteric surfactant. A silver halide photographic material characterized by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, PWR represents a group that releases ▲There are mathematical formulas, chemical formulas, tables, etc.▼ when reduced, and Time is ▲mathematical formula , chemical formula, table, etc. ▼ represents a group that releases a PUG residue in a subsequent reaction, t represents 0 or 1, and PUG represents a photographically useful residue. Contains at least one water-soluble group in one molecule. ] (2) The photographic material according to claim 1, wherein the water-soluble group in the compound represented by formula (I) is a sulfonic acid, a carboxylic acid, or a salt thereof. (3) The photographic material according to claim 1, wherein the amphoteric surfactant is a betaine type surfactant.