JPH01147448A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To disperse fine particles stably in a silver halide photographic sensitive material by emulsifying and dispersing an oil-soluble photographically useful material in the presence of a specified compd. CONSTITUTION:A photographically useful material is incorporated into a silver halide photographic sensitive material in the presence of a compd. expressed by formula I. In formula I, each R1 and R2 is a >=4C alkyl group; X is -CH2O-, etc.; each R3 and R4 is an 1-6C alkyl group; B is a divalent group; n is 0 or 1; m is 0 or 1-20; M is a cation. Thus, fine particles of an oil-soluble photographically useful material are dispersed stably in a silver halide photographic sensitive material without causing flocculation of the particles nor deposition of crystals.

Description

[Detailed Description of the Invention] (Industrial Application Field) The stability of an emulsified dispersion of a hydrophobic photographically useful substance is improved,
The present invention also relates to a silver halide photographic material containing an emulsion thereof, which has improved storage stability.

(Prior Art) Inorganic and organic substances have been known as photographically useful substances. Among these, the photographic useful substances include:
There are water-soluble, water-insoluble, and poorly water-soluble types. Photographically useful substances that are water-insoluble or poorly water-soluble and preferably oil-soluble are usually introduced into the hydrophilic colloid layer in finely dispersed form. Representative examples of oil-soluble photographic materials include dye image-forming couplers, dye image-providing redox compounds, ultraviolet absorbers, anti-fading agents, anti-color mixing agents, and their precursors.

Many emulsification and dispersion methods have been proposed for emulsification and dispersion of these oil-soluble photographically useful substances.

For example, U.S. Pat. No. 2,332,027 describes a method using a sulfonated coconut surfactant.
ut fatty alcohol (trade name of DuPont) and a method using triisopropylnaphthalene sulfonate, Japanese Patent Publication No. 39-4293 describes a method using a water-soluble coupler having both a sulfone group or a carboxyl group and a long-chain aliphatic group as an emulsifier. Method used as, Tokuko Sho 4 B
No. 9979 describes a method of using a sulfo group-containing anionic surfactant and an anhydrohexitol fatty acid ester type nonionic surfactant in combination. However, in all of these emulsification and dispersion methods, the particle size of the dispersed particles is delicate immediately after emulsification and dispersion, and while the color density is high, the dispersion stability is poor and the dispersed particles become coarse during the manufacturing process. There was a drawback that

On the other hand, the surface-active polymer disclosed in JP-A No. 53-138726 provides a fine and highly stable dispersion, and most of the crystals of the photographically useful substance are precipitated in the photosensitive material film and on the surface of the photosensitive material. However, it is possible to produce a photographic material using a dispersion in which such a surface-active polymer and some dye image-forming couplers are dispersed in water or in a hydrophilic colloid composition. It has become clear that in some cases, there is a significant decrease in coloring performance (dye image density).

(Problems to be Solved by the Present Invention) Therefore, the first object of the present invention is to provide a photographic element comprising a silver halide light-sensitive material, in which fine particles of an oil-soluble photographic substance are stably dispersed. Our objective is to provide silver photographic materials.

A second object of the present invention is to provide a silver halide photographic material that is stable, has low haze, and has excellent not only coloring performance but also sharpness.

A third object of the present invention is to provide an oil-soluble photographic material for stably dispersing fine particles of an oil-soluble photographically useful substance in a silver halide photographic light-sensitive material without causing aggregation or crystal precipitation of the fine particles. The object of the present invention is to provide a method for dispersing useful substances.

(Means for Solving the Problems) These objects of the present invention can be achieved by containing a photographically useful substance in a silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula (1). It was done.

General formula N) R, -CH(X←-1←CffH60→1-←3)-
In the 6O,M formula, R+ and Rz represent an alkyl group having at least 4 carbon atoms, and the sum of the carbon numbers of R3 and R2 is 30
It is as follows.

R, OR.

, R's and R- represent an alkyl group having 1 to 6 carbon atoms, B represents a divalent group, and n is O or 1. m
represents O or 1-20. Preferably O or 1-10
It is. M represents a cation.

As a specific example of the alkyl group of R+, R mushroom, CaH
q, ChHls, CaH2, C1°R21, C1&H1
3%Cl4H1? , C1&H13, CC15H3, etc.

Specific examples of alkyl groups for R1 and R4 include CH3, Ca
Hs, Cs H? , C4R9, Cb Hrx
etc. Specific examples of the divalent group of B include alkylene groups such as CHz CHz-1←CH,→go,
Specific examples of 0M such as -ccn*- include Na,
Mg, NH4, N(CHs)s, etc.

Next, specific examples of compounds used in the present invention will be shown, but the invention is not limited thereto.

kl ChH,3CHCHi O(C,Hb O)+
m SO3NaNα2 Cb H+5CHCH20(
C3Hb O)m SOz NaC@H1? N(13Cb HI3CHCHg O(Cs H
b O) -SOs NaN(L4 Ch
Hl, CHCHzO(CsHhO) ml CaHI.

(CHt)? SOz Na mζ1 N(L 5 Ch H+ x CHCH! O
S Os N acs H1'1 6 C6H13CHCHz O(CHg)
4 SO3NaCIH5? 7 C+oHz+CHCHg 03Oi N
acm H,.

Na8 C+*HtsCHCHx 0CHt C
Hz SOs NaC+oH*+ Note 10 C6゜Hx+CHCHz O(C3Hh O
) ml CmH+q CHz CHt SOs Na m, 10
Volume 11 c+. Hg, CHCH, O (cz H, O
) er SO, KCs Hly m'y
2Na12C+aHz+CHCH1O(CsHiO
)z(CIli)asOJak13 C+zHzsC
The compounds represented by HCHzO(Cs)I*O)(CHt)gsOaNa) have a large surface tension lowering ability, have low c, m, c, (critical micelle concentration), and contain this compound. The coating solution has features such as no coating failures caused by the formation of insoluble complexes with calcium ions, and photographic films containing this compound can prevent the generation of contaminants in the processing solution. .

The reason for this is presumed to be due to the specific chemical structure containing a double-chain alkyl group and a low molecular weight polyoxyprolene group in the molecule and the surface active behavior based thereon.

These compounds of the present invention represented by general formula (1) are -
For example, Journal
of the AmericanOil Chem
An example of zero-order synthesis that can be synthesized by the method described in rsts 5ociety, volume 42, page 157 is shown below.

Synthesis Example 1 (Synthesis of Compound I) 242 g of 2-hexyldecanol and 9.7 g of caustic soda were placed in a 500 ml flask equipped with an addition stirrer for propylene oxide, a reflux condenser, a thermometer, and a dropping funnel. Heat to °C and stir. Adjust the amount of propylene oxide added dropwise and keep it at 150-160°C while constantly refluxing. After the reaction is complete, remove unreacted propylene oxide and calculate the average number of moles of propylene oxide added from the weight increase (n-
1,1) Cooled to room temperature and neutralized with concentrated hydrochloric acid, dissolved in ether, washed with water to remove inorganic salts, and after distilling off the ether, vacuum distillation was performed using a 5-stage column rectifier. . 1
A fraction of 40 to 145°C/lmmHg (yield 23%) was collected and the composition distribution was investigated using gas chromatography. n=0.0.1%
, n==1.85.1% n=2.14%, n=3.0.
8%, and the average n number was 1.1.

Add 30 g of the above propylene oxide adduct and 50 d of carbon tetrachloride to a 300i flask equipped with a stirrer, temperature needle, calcium chloride tube, and dropping funnel and dissolve. After cooling with water, add 13.5 g of chlorosulfonic acid to 5°C or below. I dripped it while holding it. Stir at the same temperature for 30 minutes, then at room temperature for another 30 minutes. Dilute with 80% ethanol and neutralize with 5% caustic soda aqueous solution. After the solvent is distilled off under reduced pressure, it is redissolved in ethanol and the insoluble inorganic salts are filtered off.Ethanol is distilled off.
a 1i! When the liquid is added to acetonitrile, a precipitate is obtained. Furthermore, when the acenitrile solution was concentrated and washed with hexane, a waxy solid was obtained. Both were confirmed to be the desired products by IR and NMR. Surface tension (1%)
was 25.7 dyne/cm.

The photographically useful substance that can be used in the present invention means any organic compound and organic or inorganic dye and pigment useful for photography. In the present invention, an oil-soluble organic photographically useful substance is used. It is preferable. Here, oil-soluble refers to a substance that dissolves in an organic solvent in an amount of 3% by weight or more at room temperature (approximately 20'C). Furthermore, the term "organic solvent" refers to the organic solvents described in "Solvent Handbook J," and examples of these compounds include methanol, ethanol, isopropanol, butanol, ethyl acetate,
Examples include isopropyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, benzene, toluene, dioxane, acetonitrile, dichloromethane, and chloroform.

Examples of photographically useful substances that can be used in the present invention include dye image-forming couplers, dye image-providing redox compounds, ultraviolet absorbers, electron donors used for the purposes of preventing color mixing, preventing oxidation, preventing fading, forming nucleates, etc. inhibitors and development inhibitors,
Examples include developing agents, nucleating agents, silver halide solvents, bleach accelerators, filter dyes and their precursors, and organic or inorganic dyes and pigments.

a) Couplers Preferred photographically useful materials include dye image-forming couplers that couple with oxidizing products of aromatic primary amine developing agents to form colored or colorless dyes. Yellow, magenta, cyan, and black couplers are useful as couplers that form colored dyes.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. Specific examples thereof include U.S. Patent Nos. 2,407,210 and 2,875,05.
No. 7 and No. 3.265.506, etc. As a two-equivalent yellow coupler, U.S. Patent No. 3,
408゜194, same No. 3,447,928, same No. 3
933.501 and 4,022,620, or Japanese Patent Publication No. 5B-10739, U.S. Patent No. 4,401
．． No. 752, No. 4,326°024, RD1805
3 (April 1979), U.S. Patent No. 1,425,02
0, West German Application No. 2.219,917, No. 2,2
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent No. 61,361, Japanese Patent No. 2,329.587, and Japanese Patent No. 2,433.812. α
- Pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-henzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected couplers of indasolone type or cyanoacedol type, preferably pyrazoloazole type couplers such as 5-pyrazolone type and pyrazolotriazoles. It is preferable that the 5-pyrazolone photovoltaic coupler is a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the coloring dye. , No. 082,
Same No. 2,343,703, Same No. 2,600,788, Same No. 2,908,573, Same No. 3.062.653
No. 3,152,896 and No. 3,936,
It is described in No. 015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
Particularly preferred are the nitrogen atom leaving groups described in US Pat. Further, in the case of a 5-pyrazolone coupler having a ballast group as described in European Patent No. 73.636, a high color density can be obtained.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably the pyrazolo(5,1-C)(1,2,4)) liazoles described in U.S. Pat. (1
Examples include pyrazolopyrazoles described in June 1984). Imidazo(1,2-b)pyrazoles described in European Patent No. 119,741 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and European Patent No. 1
Pyrazolo [1°5-bl (
1,2,4)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Further, specific examples of phenolic couplers include U.S. Patent Sections 2,369,929 and 2,8
No. 01.171, No. 2. 772. No. 162, No. 2,895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus, and U.S. Pat.
No. 758,308, No. 4.126,396, No. 4
, No. 334,011, No. 4,327゜173, West German Patent Publication No. 3,329,729, and Japanese Unexamined Patent Publication No. 1987-1
66956, and U.S. Pat. No. 3,446.
, No. 622, No. 4,333,999, No. 4□ 4
51.559 and 4,427,767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

Naphthol couplers in which the 5-position is substituted with a sulfonamide group, an amide group, etc., described in JP-A No. 60-237448, No. 61-153640, No. 61-14557, etc., have particularly excellent color fastness of developed color images. This is preferable.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color photosensitive materials for photographing. U.S. Patent Section 4,163,670 and Japanese Patent Publication No. 57-3
Yellow-colored magenta couplers such as those described in US Pat. No. 4,004,929 and US Pat.
Typical examples include the magenta-colored cyan couplers described in US Pat. No. 8,258 and British Patent No. 1.146,368.

Specific examples of the dye-forming couplers and mask-forming colored couplers mentioned above include Japanese Patent Application Laid-Open No. 61-251841.
Compounds described in the publication (yellow-forming couplers (y-l) to (Y-20) described on pages 11 to 21, magenta-forming couplers (M-1) to (M-22), cyan-forming couplers ( Examples include C-1) to (C-21) and colored couplers for forming a mask (L-1) to (L-4).Furthermore, cyan couplers for forming a mask (L-1) to (L-4) as shown below can be mentioned.
Examples include C-1) to (C-3) and mask-forming colored couplers (L-1) to (L-3).

Other types of couplers include couplers that release a development inhibitor or its precursor in response to the amount of developed silver during development (DIR couplers), couplers that release nucleating agents or development accelerators (DAR couplers), and electron donors. Couplers of the type that emit can also be used as photographically useful materials in the present invention.

Colorless couplers or colorless DIR couplers can also be used. Examples of coupler residues that do not substantially form dyes include indanone type and acetophenone type coupler residues.

Also, JP-A No. 60-185950, No. 61-23374
No. 1, No. 61-238057, No. 61-251847
No. 61-251848, No. 62-24252, and No. 62-56962, in which a photographically useful group is released from the coupling position of a coupler through a redox reaction with an oxidized form of a developing agent. Couplers can also be used as photographically useful materials.

Two or more of the above couplers and the like can be used in combination in the same layer in order to satisfy the characteristics required of a photosensitive material.

b) Dye image-providing compounds Other photographically useful substances that can be used in the present invention include dye image-providing redox compounds used in color diffusion transfer photosensitive materials. As known to those skilled in the art, this compound includes:
They can be negative or positive working and are initially mobile or immobile in the photographic element when processed with alkaline processing compositions.

Negative-working dye image-providing compounds useful in the present invention include couplers that react with oxidized color developing agents to form or release dyes, specific examples of which are U.S. Pat.
No. 550 and Canadian Patent No. 602,207.

Preferred negative-working dye image-providing compounds for use in the present invention include dye-releasing redox compounds that release dyes by reacting with developing agents or electron transfer agents in an oxidized state. Japanese Patent Publication No. 48-33826,
It is described in No. 51-113624, No. 54-54021, No. 56-71072, etc. In addition, immobile positive-working dye image-providing compounds that can be used in the present invention include those that do not accept any electrons (i.e., are not reduced) or that do not accept at least one electron during photographic processing under alkaline conditions. There are compounds that release a diffusible dye after being absorbed (ie, reduced).

Additionally, dye developing agents are available as positive-working dye image-providing compounds that are initially mobile under alkaline photographic processing conditions, and are useful in the present invention. Typical examples are Special Publication No. 48-32130 and No. 55-227.
It is described in No. 80 etc.

The dyes formed from the dye image-providing compounds used in this invention may be ready-made dyes, or alternatively may be dye precursors that can be converted into dyes in photographic processing steps or additional processing steps to form the final image. The dye may or may not be metallized. Typical dye structures useful in the present invention include azo dyes, azomethine dyes, anthraquinone dyes,
Mention may be made of metallized or non-metallized phthalocyanine dyes. Among these, azo-based cyan, magenta and yellow dyes are particularly important.

Further, as a type of dye precursor, a dye-releasing redox compound having a dye moiety that temporarily shifts light absorption in a photosensitive element can also be used in the present invention.

Particularly preferred dye image-providing compounds for use in the present invention include dye-releasing redox compounds (DRR-compounds), specific examples of which are disclosed in the above-mentioned JP-A No. 48-3382.
No. 6, No. 51-113624, No. 54-54021, and No. 56-71072. A specific example of a redox nucleus that is cross-oxidized by silver halide development and releases a diffusible dye under alkaline conditions is N HSO! D)' e etc. Another type of particularly preferred dye image-providing compounds are those belonging to the positive type, JP-A-53-1108
No. 27, No. 53-110828 and No. 56-1643
No. 42, specific examples of this type of redox core include the following.

Next, as a specific example of the dye-releasing redox compound, the compound (2
(DR-1) to (DR-14) described on pages 3 to 25
) can be mentioned.

Next, some of the dye developing agents that can be used in the present invention (DD-
1) (DD-2) (DD-3) C) Organic or inorganic dyes and pigments Dyes or pigments used in the present invention include azo-based, azomethine-based, oxonol-based, cyanine-based, phthalocyanine-based, quinacridone-based, Organic or inorganic dyes and pigments such as anthraquinone, dioxazine, indigo, perinone/perylene, titanium oxide, cadmium, iron oxide, chromium oxide, carbon black, etc. are used conventionally as coloring agents. Any of the known dyes or mixtures thereof may be used. These dyes and pigments in the present invention can be used in any state such as an aqueous paste state or a powder state immediately after production.

In particular, U.S. Pat.
The present invention is useful for dispersing oil-soluble dyes represented by the following general formula (11) described in No. 4630 and No. 61-205934.

General formula (II) R1 Rz (wherein, R+ and Rz may be the same or different,
Hydrogen atom, halogen atom, alkyl group, alkoxy group,
It represents a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group, a sulfamoyl group, a nitro group, or an alkoxycarbonyl group.

R3 and R may be the same or different and represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or a sulfonyl group; A 5- to 6-membered ring may be formed. XSY may be the same or different,
Represents an electron-withdrawing group. ) d) Ultraviolet absorber Ultraviolet absorbers suitable for carrying out the present invention are disclosed, for example, in Japanese Patent Publication No. 41-21687, Japanese Patent Publication No. 48-5496, and Japanese Patent Application Laid-open No. 48-54.
No. 7-1026, British Patent No. 1293.982, etc., among which oil-soluble ultraviolet absorbers are particularly preferred.

e) Other photographically useful substances that can be used in the present invention Other photographically useful substances that can be used in the present invention include those that donate at least one electron to an oxidized dye-donating compound or an oxidized form of a color developing agent. It is an electron donor (hereinafter referred to as rEDJ) that can Valid EDs are T and H.

James, The Theory of the Photographic Process
There is a compound having a Kenda II-PI iz partial structure as described in Chapter 11 of the 4th edition. Compounds belonging to this group include hydroquinones, catechols, 0-aminophenols, and p-aminophenols. It is desirable that the ED compound used in the present invention has low diffusivity when incorporated into a photosensitive material layer. Low-diffusible or non-diffusible hydroquinones, pyrogallols, and the like are widely used as color mixing inhibitors, antioxidants, anti-fading agents, and the like. Specific examples of these compounds include 2.5-di-n-octylhydroquinone, 2,5-1-di-t-pentadecylhydroquinone, n-dodecyl gallic acid ester, and p-laurylamide pyrogallol.

ED precursors that can be used in the present invention include compounds suitable for use in combination with positive-working dye image-providing compounds. Examples include U.S. Pat.
These include saccharin type compounds as described in US Pat. No. 263,393 and active methine type compounds as described in US Pat. No. 4,278,750.

Other photographically useful substances that can be used in the present invention include antifogging agents such as mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptothiadiazoles, benzotriazoles, and imidazoles. Developing agents such as p-phenylenediamines, hydroquinones, p-aminophenols; Auxiliary developing agents such as pyrazolidones; Nucleating agents such as hydrazines and hydrazides; Halogens such as hypo Examples include silver oxide solvents; bleach accelerators such as aminoalkylthiols; and dyes such as azo dyes and azomethine dyes. Further, a precursor of the above-mentioned photographically useful substance, or a photographically useful substance further having a redox function in which the above-mentioned photographically useful substance is released as development progresses, such as the above-mentioned dye material for color diffusion transfer light-sensitive materials, etc. , DIR- or D
AR-hydroquinones can also be mentioned as good photographically useful substances. The above-mentioned photographically useful substances may be bonded via a timing group, and such a timing group can be used to release a photographically useful substance by an intramolecular ring-closing reaction described in JP-A-54-145135. British Patent No. 2,072,363, Japanese Unexamined Patent Publication No. 1983
JP-A-57-17 which releases a photographically useful substance by intramolecular electron transfer as described in JP-A No. 154234, etc.
9842, etc., which releases photographically useful substances with desorption of carbon dioxide gas, or JP-A No. 59-9
Examples include those described in No. 3442 that release photographically useful substances with the removal of formalin.

In the present invention, a photographically useful substance maintained in a solution state by any of the following methods is mixed with water or an aqueous hydrophilic colloid solution in the presence of the surface-active polymer of the present invention. Prepare a fine dispersion. If necessary, to further refine the size of the dispersion particles,
A disperser as described below may also be used.

In addition, in order to further increase the stability of the resulting dispersion, the water-immiscible low-boiling organic solvent or water-miscible organic solvent used to make the photographically useful substance into a solution state was distilled or
More preferably, it may be removed by vacuum distillation, ultrafiltration, or other known methods.

First, in the present invention, it is preferable that the photographically useful substance be heated and melted before the emulsification and dispersion operation, or dissolved in an organic solvent and used in the form of a liquid.

Compounds that can be directly emulsified by melting are limited to compounds with a melting point of about 90°C or less.

A high boiling point organic substance (
That is, the so-called oil content is effectively insoluble in water and has a boiling point of 190°C or higher at normal pressure. This type of organic substance includes carboxylic acid esters, phosphoric acid esters,
It can be selected from carboxylic acid amides, ethers, fers, anilines, substituted hydrocarbons, and surface-inactive hydrophobic organic polymers. Specific examples include di-n-butyl fucuric acid ester, di-isooctylfural ester, dicyclohexyl fucuric acid ester, dimethoxyethylfural ester, di-n-butyl adipate, di-isooctyl azelenoic acid. Esters, tri-n-butyl citrate, butyl laurate, di-n-sebacate, triphenyl phosphate, tricresyl phosphate, tricyclohexyl phosphate, tri-n-butyl phosphate, tri-isooctyl phosphate, N , N-diethylcaprylic acid amide, N,N
-dimethyl palmitic acid amide, n-butyl-m-pentadecyl phenyl ether, ethyl-2,4-tert
-butylphenyl ether, 2,5-di-L-amylphenol, N,N-di-n-butyl, 2-n-butoxy,
Examples include 5-t-octylaniline, chlorinated paraffin, polyethyl acrylate, and diethylene glycol-adipate polyester.

Depending on the type of the photographically useful substance, it may be emulsified or precipitated and dispersed by dissolving it only in the following low-boiling organic solvents or water-miscible organic solvents without using the above-mentioned high-boiling organic substances.

The present invention is thus particularly useful where high-boiling point organic solvents are not used or only in small quantities.

In the present invention, in order to dissolve the oil-soluble photographically useful substance, in addition to the above-mentioned high-boiling point substances, a low-boiling point organic solvent that is immiscible with water (having a boiling point of 130°C or less at 1 atm) or a water-miscible There are many advantages to using organic solvents. Examples of such organic solvents include propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, 5eC-butyl alcohol, methyl ethyl ketone, 2-pentanone, 3
- Pentanone, cyclohexanone, dimethylformamide, dimethylsulfoxide are examples. The preferred amount of the organic solvent used is 0.1 to 100 times the weight of the oil-soluble photographically useful substance to be dispersed.

In the present invention, the hydrophilic organic colloid layer in which a dispersion of a photographically useful substance exists and the photosensitive silver halide emulsion layer are:
It is preferable to have a water permeability relationship.

Examples of emulsifying equipment used to carry out the present invention include a high-speed stirring type dispersion machine having a large shearing force, a dispersion machine applying high-intensity ultrasonic energy, and the like. Specifically, there are colloid mills, homogenizers, capillary emulsifiers, liquid sirens, electromagnetic strain ultrasonic generators, emulsifiers with Ballmann whistles, and the like. Preferred high-speed stirring type dispersing machines for use in the present invention include Daysilver, Polytron, Homomixer, Homoblender, Kedaymill, and Jet Agitator, in which the main part that performs dispersion rotates at high speed (500°C) in the liquid.
~15.00 Orpm, preferably 2.000-4.0
The high-speed stirring type dispersing machine used in the present invention is a type of dispersing machine that produces 0 rpm), and is also called a day silver or high-speed impeller dispersing machine, and is disclosed in Japanese Patent Application Laid-Open No. 55-129136.
As described in the same issue, a preferred example is an impeller in which serrated blades are alternately bent vertically on a shaft that rotates at high speed.

Various processes can be followed in preparing oil-in-water dispersions (hereinafter referred to as "aqueous dispersions") of photographically useful materials in accordance with the present invention. When dissolving a photographically useful substance in an organic solvent, one or more of the above-mentioned high-boiling organic substances, water-immiscible low-boiling organic solvents, and water-miscible organic solvents may be used. It is dissolved in a multi-component mixture and then dispersed in water or an aqueous hydrophilic colloid solution in the presence of the compound represented by the general formula (1) of the present invention. In this case, the compound of the present invention is allowed to coexist in at least one of a solution containing a photographically useful substance, water, or an aqueous hydrophilic colloid solution.

The method of mixing the oily liquid containing the photographically useful substance with the aqueous liquid may be the so-called forward mixing method in which the oily liquid is added into the aqueous liquid while stirring, or the reverse mixing method, but especially the back mixing method. One of these methods, the phase inversion method, is preferred in that it provides a finer aqueous dispersion.

The amount of the compound used in the present invention is determined by the type and amount of the photographically useful substance, high-boiling point organic substance, low-boiling point a solvent or water-miscible organic solvent used, and the type and amount of the surfactant used in combination in some cases. Although the optimum amount varies depending on factors such as the above, the usable range is 0.
．． 1 to 300 %, preferably 0. It is 2 to 50% by weight.

In the present invention, the oil-soluble photographically useful substance can be stably dispersed either in water or in a hydrophilic colloid composition, but it is preferable to disperse it in a hydrophilic colloid composition.

As the hydrophilic colloid in the hydrophilic colloid composition used in the present invention, binders or protective colloids commonly used in silver halide photographic materials are used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin,
Proteins such as casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly N-vinyl bimeridone, polyacrylic acid, and polymethacrylate. A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acids, polyacrylamide, polyvinylimidazole, polyvinylpyrazole sugars.

In addition to lime-treated gelatin, acid-treated gelatin may be used as the gelatin, and gelatin hydrolysates and gelatin enzymatically decomposed products may also be used. Those obtained by reacting various compounds such as bromoacetic acid, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are used.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. RD 17123 (July 1978), or by utilizing trichromatic coupler mixtures such as those described in U.S. Patent No. 4,126,461 and British Patent No. 2.102.
The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming coupler described in, for example, No. 136. Films for plate making such as lithography film or scanner film, X-ray film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, 00M or regular micro film, silver salt diffusion transfer type photosensitive materials and prints The present invention can also be applied to out-type photosensitive materials.

The compound of the present invention can also be used in the field of information recording materials other than silver halide photosensitive materials. For example, it can be used as a dispersant for leuco dyes for heat-sensitive recording materials, or as an emulsifier for preparing various microcapsules such as microcapsules for pressure-sensitive recording materials and microcapsule toners for electrophotography. It can also be used as a dispersant for magnetic materials used in magnetic recording materials.

<Effects of the Invention> When an oil-soluble photographic substance is emulsified and dispersed in the presence of the compound represented by the general formula (1) of the present invention, ■ the dispersed particles are fine, and ■ the obtained dispersion is stable. In particular, when a dye image-forming coupler or a dye image-providing redox compound is dispersed and used in a silver halide light-sensitive material, it is particularly important to have excellent storage stability. It has advantages such as: less deterioration due to crystallization of useful substances in the film and coalescence of dispersed particles, and (2) harmlessness not only in terms of photographic performance but also in the manufacturing process.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of Sample 101) 22 g of an oil-soluble dye (CPd-1) having the following structural formula, 23 g of a BD compound (Cp d-2), and 5 g of anionic surfactant 5AA-1 were mixed with tricresyl phosphorif 24 g of ethyl acetate and 130 g of ethyl acetate are heated and dissolved at 60°C. In this solution, 16% d was heated and dissolved at 50°C.
630 g of gelatin aqueous solution was added with stirring, and then stirred for 30 minutes using a high-speed stirring impeller. Then 37
An emulsion was prepared by diluting with 0 cc of water and stirring for 10 minutes.

(SAA-1) CH (Preparation of sample 102) Anionic surfactant 5AA in the preparation method of sample 101
Sample 101 was produced in the same manner as sample 101 except that -1 was changed to 5AA-2.

(SAA-2) C,H,,0CO-CH.

Cs HI? OCOCH303N? (Preparation of sample 103) Anionic surfactant 5AA in the preparation method of sample 101
Sample 101 was prepared in the same manner as Sample 101, except that Example Compound 5 of the present invention was used instead of -1.

(Preparation of Sample 104) Sample 104 was prepared in the same manner as Sample 101 except that Compound No. 3 of the present invention was used in place of the anionic surfactant 5AA-1.

The emulsified dispersion samples 101 to 104 thus obtained were allowed to age at 40''C and changes in particle size were measured.

In addition, after storing it in a refrigerator (6°C) for 2 days, it was dissolved at 40°C, and after standing at 40°C for 2 days, the sample was collected on a slide and examined for the presence or absence of crystallization using a polarized light microscope. Ta.

These results are shown in Table-1.

Example-2 (Preparation of sample 201) 38 g of cyan coupler (C-1) and the following compound (Cpd
-3) 4g, and anionic surfactant, the above 5AA-2
4 g of the solution was dissolved in 120 g of ethyl acetate by heating at 60°C. To this solution, 300 g of a 14% gelatin aqueous solution heated and dissolved at 50° C. was added with stirring, and then stirred for 30 minutes using a high-speed stirring impeller. Then 540c
After diluting with water in Step c, the emulsion was prepared by stirring for 10 minutes.

(Preparation of Sample 202) Sample 202 was prepared in the same manner as Sample 201 except that 4 g of the anionic surfactant 5AA-2 in the preparation method of Sample 201 was replaced with the same amount of 5AA-3.

(SAA-3) (Preparation of sample 203) Anionic surfactant 5A in the preparation method of sample 201
Sample 201 was prepared in the same manner as Sample 201 except that the same amount of the exemplified compound Nα14 of the present invention was used in place of A-2.

Emulsified dispersion samples 201 to 203 thus obtained
The particle refinement and stabilization were evaluated using the same method as shown in Example 1, and the results are shown in Table 2.

Example 3 A photosensitive material for color printing was prepared by applying photosensitive layers consisting of the first layer to the seventh layer on a paper support laminated on both sides with polyethylene.

The polyethylene on the side to which the first layer is applied contains titanium dioxide and a trace amount of gun blue.

(Structure of Photosensitive Layer) The numbers corresponding to each component indicate the coating amount expressed in units of g/rd, and for silver halide, the coating amount is expressed in terms of silver.

1st layer (blue sensitive layer) Silver chlorobromide emulsion (see Table 1) ・・・・・・・・・ Silver 0.30 Yellow coupler (*1) ・・・・・・・・・・・・
・0.70 Same as above solvent (TNP) ・・・・・・
・・・・・・0.15 gelatin ・
・・・・・・・・・・・・0.10 2nd layer (middle layer) Gelatin ・・・・・・・・・・・・
0.90G-L-octylhydroquinone ・・・・・・・・・・・・0
．． 05Solvent as above (TNP)・・・・・・・・・
...0.10 3rd F! (Green sensitive layer) Silver chlorobromide emulsion (see Table 1) ・・・・・・・・・・・・0.45 Magenta coupler (*2) ・・・・・・・・・・・・
0.35 Same as above solvent (TOP) ・・・・・・・・・
...0.44 Antifading agent ($3/$4) ...0510.10 Gelatin ...1. 00
4th layer (UV absorbing intermediate II UV absorber (*5/*6/=7) ・・・・・・・・・・・・0.0610.2510.2
5 Same as above solvent (TNP) ・・・・・・・・・・・・
・・0.20 gelatin ・・・・・・
・・・・・・1.5 5th layer (red sensitive layer) Silver chlorobromide emulsion (see Table 1) ・・・・・・・・・1i0.20 Cyan coupler (IS/*9') ・・・・・・・・・・・・・0.210.2 Coupler solvent (TNP/DBP) ・・・・・・・・・・・・0. 1010. 20 Gelatin ・・・・・・・・・・・・0
．． 9 6th layer (UV absorbing intermediate N) UV absorber (*5/*5/*7) ・・・・・・・・・・・・0.0610.2510.2
5 Same as above solvent (DBP) ・・・・・・・・・・・・
・・0.20 gelatin ・・・・・・
・・・・・・1. 5 7th layer (protective layer) Gelatin ・・・・・・・・・・・・
1.5 Here, DBP is dibutyl phthalate, TOP
is tri(n-octyl) phosphate and TNP is tri(n-octyl) phosphate.
n-nonyl) phosphate.

(*8) C1! .

In addition, sodium 2-hydroxy-4,6-dichloro-S-triazate was used as a hardening agent, and 4
-Hydroxy-6-methyl-(1°3.3a7)tetraazaindene was added.

($9) l”, +□1.
(0, The structural formula of the compound such as a coupler used in Nut Emission 11 is as follows.

CI+ 3 (*tl) (*12) Mazenk coupler ($14) Color image stabilizer A 1:3:3 mixture (molar ratio) of (Preparation of sample 3010) In the layer structure shown above, the first layer and the second layer.

No. 31. 4th layer, 5th layer, 6th layer coupler, G1-
5AA-1 was used for emulsifying and dispersing octylhydroquinone, a UV absorber, and a high boiling point oil. The amount used was 5% by weight of each hydrophobic additive.

(Preparation of Sample 302) Sample 302 was prepared in the same manner as Sample 301, except that 5SA-3 was used in equimolar amounts instead of 5AA-1 in Sample 301.

(Preparation of Sample 303) Sample 303 was prepared in the same manner as Sample 301 except that exemplified compound 4 was used in equimolar amounts instead of 5SA-1 in Sample 301.

One week after coating, these samples were exposed to light for 0.5 seconds through an optical wedge at room temperature, and then treated as shown below. After storage, the samples were exposed and processed in the same way and subjected to sensitometry using a reflected optical path, and the results are shown in Table 3.

Processing Process Temperature Time Color development
33°c 3 minutes 30 seconds bleach fixing 33°c
Wash with water for 1 minute and 30 seconds, dry at 24-34°C for 3 minutes, and dry at 80° for 1 minute.The components of each treatment solution are as follows.

Color developer water 800d diethylenetriaminepentaacetic acid 3°0g benzyl alcohol 15m! diethylene glycol
10d Sodium sulfite 2.
0g potassium bromide 0.5g potassium carbonate 30.0gN-ethyl-N-(
β-Methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Fluorescent brightener (4,4'-distilpene type) 1.0g Add water
1000dpH (25℃)
10.10 Bleach-fix solution water 400d ammonium thiosulfate (70% volume) 150d sodium sulfite 18g ethylenediaminetetraacetic acid iron (I [I) ammonium 55g ethylenediaminetetraacetic acid 2Na 5g Add water
1000dpH (25℃) 6.7
0 When exposed to high-temperature conditions, the particle size of the emulsion in the blue-sensitive layer itself increases, resulting in a decrease in the conversion rate to coloring dye. It has been found that the reduction in reflective optical density due to the increase in light scattering due to the coarsening of the emulsion particle size contributes to a reduction in yellow density. However, it is clear that when the surfactant of the present invention is used, such a decrease in yellow density can be kept to an extremely small level.

Example-4 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in g/rd units of silver for halogenated i-trifluoride and colloid i-conjugate, and the amount expressed in g/% unit for couplers, additives, and gelatin. The sensitizing dye is expressed in moles per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below.

However, if there are multiple benefits, one of them is listed as a representative.

UV, ultraviolet absorber, S o I v r high boiling point organic solvent, ExF; dye, ExS; sensitizing dye, ExC
; Cyan coupler, ExM ; Magenta coupler, EX
Y: Yellow coupler, Cpd: Additive 1st layer (antihalation layer) Black colloidal silver...0.15 Gelatin...2.9UV-]
...0.03UV-2...0.06 UV-3...0.07 Solv -2・=0. 08 ExF-1...0.01 ExF-2...0.01 2nd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol% uniform Equivalent sphere diameter 0
．． 4μ Number of fluctuations in sphere equivalent diameter: 37%, plate-like particle diameter/
Thickness ratio 3.0) Applied SBL amount...
・0. 4 Gelatin...0.8
ExS-1...2.3X10-'ExS-2...1.4X10-'ExS-5...2.3X10-' ExS-7-8,0XIO-6 ExC-1...0. 17 ExC-2...0.03 ExC-3...0.13 Third layer (mid-sensitivity red-sensitive emulsion N) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2:
Internal height Agl of 1, equivalent sphere diameter 0.65 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like particle, diameter/thickness ratio 2.0)
Coated silver amount...0.65 Silver iodobromide emulsion (Ag 14 mol%, uniform Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3. 0) Coated silver amount...0.1 Gelatin...1.0ExS-1'
-2X10-'ExS-2=1.2X10-'ExS-5...2X10-' ExS-7...7X10-b Ex C-1-0,31 ExC-2・0. OI ExC-3・0. 06 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:1
Internal height Agl Equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount...0.9 Gelatin...0.8ExS-1 =1
．． 6xlO-'EχS-2...1.6X10-'ExS-5...1.6X10-'ExS-7-6Xl0-' ExC-1・0. 07 ExC-4...0.05 Solv -1-0,07 Solv-2-0,20 Cpd-7...4.6X10-' 5th layer (middle layer) Gelatin...0,6UV- 4-0,
03 UV-5...0.04 Cpd-1...0.1 Polyethyl acrylate latex...0.08 Solv -1
-0,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol% uniform type. Equivalent sphere diameter 0.
4μ, equivalent ball diameter 0.7μ, coefficient of variation of equivalent ball diameter 37%,
Plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount...0.18 Gelatin...0.4ExS-3...
・2X10-'ExS-4...7X10-'ExS-5・txlo-' ExM-5-=0. 11 ExM-7・0. 03 ExY-8...0.01 Solv -1-0,09 Solv -4-0,01 7th layer (medium-sensitivity green-sensitive emulsion N) Silver iodobromide emulsion (Ag1 6 mol%, core-shell ratio 1: l
Surface height AgT type, legal equivalent type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/thickness ratio 4.0
) Coated silver amount...0.27 Gelatin...0.6ExS-3・
2xl Q-4 ExS-4-7X10-'ExS-5=4X10-' ExM-5 -0. 17ExM-7・
0.04 ExY-8=・0.02 Sol Sea 1 ...0.14 Solv
-4-0,02 8th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 18.7 mol%, silver ratio 3:4:2
Multilayer structure particles, Agl content of 24 mol, 0 mol, 3 mol% from the inside, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6) Coated silver Amount...0.7 Gelatin...0.8ExS-4-5
,2xlO-'ExS-5...lXl0-'ExS-8...0.3XIQ-' ExM-5-0.1 ExM-6...0.03 ExY-8...0.02 ExC -1-0,02 ExC-4-=0. 01 Solv -1-0,25 Solv -2-0,06 Solv -4-0,OL Cpd-7...lXl0-' 9th layer (middle layer) Gelatin...0.6Cpd-1.
・・0.04 Polyethyl acrylate latex ・・0.12S o l
v-1.=0. 02 10th layer (donor layer for interlayer effect on the Red Angry layer) Silver iodobromide emulsion (Ag1 6 mol%, internally high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter) 25%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.68 Gelatin...1.0ExS-3-6
X10-' EχM-10...0.19 Solv -1-0,20 11th layer (yellow filter layer) Yellow colloidal silver...0.06 gelatin
...0.8Cpd -2...0.
13 Solv 1 -0. 13Cpd
-1...0.07 Cpd -6...0.002 H-1...0.13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform -Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15, plate-shaped particles,
Diameter/thickness ratio 7.0) Coated silver amount...0.3 Silver iodobromide emulsion (Agl 3 mol%, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 30%, plate shaped particles, diameter/thickness ratio 7.0) Coated silver amount...0.15 Gelatin...1. 8ExS-6-
9X10-' ExC-1-0,06 ExC-4-=0. 03 ExY-9-0,14 ExY-11-0,89 Sold -1-0,42 13th layer (middle layer) Gelatin...0.7ExY-12.
・・0.20 Solv −1・=0. 34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, multi-twin plate-like grains) , diameter/thickness ratio 2.0) Coated silver amount...0.5 Gelatin...0. 5ExS-6・
=IX10-'ExY-9-0. 01ExY-11-
0.20 ExC-1...0.02 Solv -1・''0.10 15th N (first protective layer) Fine grain silver bromide emulsion (Ag1 2 mol%, uniform-Agl type,
Equivalent sphere diameter 0.07μ) Coated silver amount...0.12 Gelatin...0.9UV-4・0.
I l UV-5...0.16 Solv-5-0,02 H-1...0.13 Cpd-5...0.10 Polyethyl acrylate latex...0.09 16th layer ( Second
Protective layer) Fine grain silver bromide emulsion (Ag1 2 mol%, uniform Agl type, equivalent sphere diameter 0.07
μ) Coated silver amount...0.36 gelatin
...0.55 polymethyl methacrylate particles 1.5μ...0.2 H-1...0.17 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3 (
0.07g/b) Surfactant Cpd-4, (0.03g
/n? ) was added as a coating aid.

The hydrophobic additives for each layer were added after being emulsified and dispersed in gelatin. In this case, 5AA-2 was used as the emulsifying surfactant, and the amount added was 10% by weight of the hydrophobic additive.

UV-]
UV-4CHl CHl H 5olv -2 xF-1 h-CHrCHt-CHz-CHs (2-CHz-CHz-CHt-CHaxF-2 /-m- I xS-1 TT) U Gohe xS-2 xS-3 SOs N-SO.

Ex-4 ExS-5 Hz OsK ExS-6 zils ExC-3ExM-5 ExC-4 Cpd-1 Cpd-6 Co-OCa Hq Cpd-3pd-4 (Preparation of sample 402) Emulsifying surfactant of sample 401 It was produced in the same manner as Sample 401 except that the compound of the present invention was used as Nα5.

For the sample made in this way, after coating (A)
Stored at room temperature for 1 week and CB) 50°C, 70%
The samples were stored for one week, exposed using a tungsten light source, and subjected to the following treatments. Sensitometry and polarized light microscopy were performed to determine the presence or absence of crystal precipitation.

The results are shown in Table-4.

38 °C 1 color development・・・・・・・・・・・・3 minutes 15
Second 2 Bleaching・・・・・・・・・・・・6 minutes 3
0 seconds 3 Washing with water 3 minutes 15 seconds 4 Fixing 6
Minute 30 seconds 5 Washing with water・・・・・・・・・・・・・・・
3 minutes 15 seconds 6 Stable・・・・・・・・・・・・・・・
・Processing for 3 minutes and 15 seconds" U-sukebun color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 3
0.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-
N-β monohydroxyethylamino) -2-methylaniline sulfate 4.5g Add water IN Bleach solution Ammonium bromide 160.0g Aqueous ammonia (
28%) 25.0d ethylenediamine-tetraacetic acid sodium iron salt 130.0g glacial acetic acid 14.0d Add water
II! .

Fixer Sodium Tetrapolyphosphate 2.0g Sodium Sulfite 4.0g Ammonium Thiosulfate (70%
) 175.0d Sodium bisulfite Add 4.6g water
11 Stabilized formalin 8.0 Add water
11 Procedural Amendment 1. Display of incident Showa tco year long-awaited JOt2PJ
No. 2, Title of the invention Silver halide photographic material 3,
Relationship with the case of the person making the amendment Patent applicant contact information 〒10
6 2-26-30, Nishi-Azabu, Minato-ku, Tokyo 4, Subject of the amendment ``Claims'' column and ``Detailed Description of the Invention'' column 5 of the specification, ``Claims of Claims'' in the description of the amendment The description in the section “Range” will be amended as shown in Attachment-7.

The description in the "Detailed Description of the Invention" section of the specification is amended as follows.

l) 3rd page/line "subtle" "Minute" and correct it.

2) Row 1 of the 1st page "subtle" "Minute" and correct it.

3) Correct all pages 7 to +r as shown in the attached sheet -λ.

Attachment-7 Claims In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, a photographically useful substance used in the photographic light-sensitive material is represented by the following general formula (1). A silver halide photographic light-sensitive material characterized by containing at least a compound dispersed in the presence of /a.

Single role type [1] RICH (-X) (C3H60 leak-B) lower-80
In the 3M formula, R1 and R2 represent an alkyl group having at least 100 carbon atoms, and the sum of the carbon numbers of R1 and R2 is 3θ or less.

, and R3 and R4 represent an alkyl group having 1- and -g carbon atoms.

B represents a covalent group, and n is θ or /.

m represents θ or /~-〇.

M represents a cation.

Attachment-ko43 C6Hl3CHCH2Q(C3,H50)msO
3NaA4' C6Hl3CHCH20(CaH60
)m(CH2)7SOsNaC8HIT Li1 At C6Hl3CHCH20SO3Na8H17 At C6Hl3CHCH20(CHz)4sOaN
a8H17 47C1oH21CHCH20SO3NaC8H17 A/ Cl2H25CHCH20CH2CH2SO3
Na10H21 C8H17 to Ha A/'CxoHzlQ(Q(zo(CsHsO
)mQ(zC)IzSO3NakoA//C1oHzlCHCH20(CaHgO)r
lsO3/I6/co Cl0H21CHCH20(C
3H60) a (CH2) 4SO3Na island

Claims (1)

[Scope of Claims] In a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the photographically useful substance used in the photographic light-sensitive material is at least one compound represented by the following general formula [I]. A silver halide photographic light-sensitive material, characterized in that it contains a silver halide photographic material dispersed in the presence of one type of compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 and R_2 represent an alkyl group having at least 4 carbon atoms, and the sum of the carbon numbers of R_1 and R_2 is 30 or less. X represents -CH_2O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_3 and R_4 represent an alkyl group having 1 to 6 carbon atoms. B represents a divalent group, and n is 0 or 1. M represents 0 or 1-20. M represents a cation.