JPH0619038A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having a hydrophobic material which is fine and excellent in emulsification dispersireness and aging stability by incorporating a specified compd. into a photosensitive emulsion layer. CONSTITUTION:The photosensitive material has a photosensitive emulsion layer on a supporting body and the layer contains a compd. expressed with formula. In formula, R<1> and R<2> denote hydrogen atom, alkyl groups, aryl groups, or alpha-furyl groups, R<3>, R<5>, R<8> and R<10> denote alkyl groups, aryl groups, alkoxy groups, halogen atoms, acyl groups, amido groups, etc., R<4>, R<6>, R<7> and R<9> denote hydrogen atom, alkyl groups, aryl groups, alkoxy groups, halogen atoms, acyl groups, amido groups, etc., L<1> and L<2> denote chemical bonds or bivalent connecting groups, and M<1> and M<2> denote hydrogen ion, ammonium ion, or metal ions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material excellent in the extremely fine emulsification and dispersibility of a hydrophobic photographically useful substance and in the stability of the extremely fine emulsion over time.

[0002]

2. Description of the Related Art Organic and inorganic photographically useful substances have been conventionally used for silver halide photographic light-sensitive materials. These organic photographically useful substances include those that are readily soluble in water, those that are sparingly soluble in water and those that are insoluble in water.
It is introduced into a hydrocolloid layer such as an undercoat layer or a surface protective layer.

As the poorly water-soluble and water-insoluble photographically useful substances, dye image-forming couplers, dye image-donating redox compounds, ultraviolet absorbers, anti-fading agents, color mixing inhibitors, dyes, and dispersion aids at the time of dispersing the above-mentioned photographically useful substances Representative examples thereof include high-boiling organic substances (dispersion oil) used as agents, dispersion polymers, and the like.

Regarding the fine dispersion of these photographically useful substances, many emulsion dispersion methods have been proposed in the past, and among these methods, the method using a surfactant is widely known. For example,
U.S. Pat. No. 2,332,027, Japanese Patent Publication No. 39-429
No. 3, JP-B-48-9979 and the like, a method using an anionic surfactant, JP-A-48-3093.
No. 3, JP-B 54-24289, JP-B 44-130
No. 11 and the like using a nonionic surfactant, US Pat. No. 2,299,782 using a cationic surfactant, and German Patent 15
47721, JP-A-57-104925, JP-B-4
Examples thereof include a method using a betaine-type surfactant disclosed in No. 9-37531 and the like. Furthermore, regarding these surfactants, Ryohei Oda "Surfactants and their applications""Maki Shoten, 1964, Hiroshi Horiguchi" New Surfactants "(Sankyo Publishing, 1975)," Mac Cation's.
Detergent and Emergence Fires "
(Mc Cation Divisions MC Publishing Company, 1985) ("Mc Cutcheon's Dete
rgents & Emulsifiers '' (Mc Catche on Divisions, Mc P
ublishing Co. 1985)) and the like.

For the above-mentioned reasons, the technique of using a surfactant is indispensable in the production of a photographic light-sensitive material, and as a result, a wide variety of photographic light-sensitive materials contain a large amount of the surfactant. In recent years, in silver halide photographic light-sensitive materials,
Improvement of sharpness by thinning the light-sensitive material, improvement of reaction efficiency of photographically useful substances, resource saving, cost reduction, improvement of photographic performance (for example, improvement of color development in dye image forming couplers, improvement of color mixing prevention performance in color mixing inhibitors, For the purpose of improving the decolorizing property of dyes, etc.), there is an increasing demand for extremely finely dispersing photographically useful substances.

In addition, from the viewpoints of environmental protection, resource saving, cost, simplification of processing equipment, speeding up of processing steps, etc.,
The processing time has been shortened, and in order to achieve these, it is extremely promising to disperse a photographically useful substance that is particularly promising and to increase the dispersed surface area of the photographically useful substance. ing. As a means for preparing an ultrafine dispersion of a photographically useful substance (hereinafter referred to as an ultrafine emulsion), a method of applying a large shearing force in the presence of the above-mentioned surfactant to perform emulsion dispersion is known. Yes,
There are many descriptions in the above patents. However, in these methods, although it is possible to obtain an ultrafine emulsion, the obtained ultrafine emulsion coalesces with time, the particle size increases, and agglomerates when high shear force is applied. The silver halide photographic light-sensitive material is unacceptable for use because it causes gradation changes and surface contamination.

Further, in European Patent Nos. 361,322A and 374,837A, a hydrophobic photographically useful substance is dissolved in a water-miscible organic solvent to prepare an anionic surfactant and a nonionic water-soluble polymer polymer. Disclosed is a method for preparing an ultrafine emulsion by precipitating from an aqueous phase by adding water in the presence of coalescence. However, when the ultrafine emulsion prepared by these methods is used for a silver halide photographic light-sensitive material, it is necessary to remove the water-miscible organic solvent used before coating. The removal of the water-miscible organic solvent is a halogen because it diminishes the stability of the ultrafine emulsion when it is distilled off at a high temperature, and when it is removed at a low temperature by dialysis, ultrafiltration, etc., it significantly impairs the productivity. It was not suitable for the production of silver halide photographic light-sensitive materials. Therefore, there is a strong demand for a technique for obtaining an extremely fine emulsion of a hydrophobic photographically useful substance that does not cause aggregation or coalescence during storage and during production of a photographic light-sensitive material, without removing the water-miscible organic solvent. It was rare.

[0008]

The first object of the present invention
Is to provide a silver halide photographic light-sensitive material having an emulsion in which a hydrophobic photographically useful substance is extremely finely dispersed. A second object of the present invention is to provide a halogenated product in which, during the production process, an emulsion of a hydrophobic photographically useful substance is extremely finely dispersed, and the particles of the fine emulsion are stably dispersed throughout production and storage. It is to provide a silver photographic light-sensitive material. A third object of the present invention is to provide a silver halide photographic light-sensitive material which does not require the use of a water-miscible organic solvent in the process of preparing an extremely fine emulsion of a photographically useful substance in its manufacturing process. It is in.

[0009]

The above problems are characterized in that a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer on a support contains a compound represented by the following general formula (I). And a silver halide photographic light-sensitive material. General formula (I)

[0010]

[Chemical 2]

In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group or an α-furyl group, and may be the same or different. R ¹ and R ² may be linked to each other to form a ring. R ³ , R ⁵ , R ⁸
And R ¹⁰ is an alkyl group, an aryl group, an alkoxy group,
It represents a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group. Also, R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ or R ⁹
And R ¹⁰ may combine with each other to form a ring.
R ³ , R ⁵ , R ⁸ and R ¹⁰ may be the same or different from each other. R ⁴ , R ⁶ , R ⁷ and R ⁹ represent a hydrogen atom or an alkyl group, an aryl group, an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. L ¹ and L
² each represent a chemical bond or a divalent linking group, be the same as each other or may be different. M ¹ and M ²
Represent hydrogen ion, ammonium ion or metal ion, and may be the same or different from each other.

Explaining in more detail, the above general formula (I)
Among them, R ¹ and R ² are preferably hydrogen atom, methyl group,
Substituted or unsubstituted alkyl groups such as ethyl group, n-propyl group, i-propyl group, n-heptyl group, 1-ethylamyl group, n-undecyl group, trichloromethyl group, tribromomethyl group; phenyl group, naphthyl Group, substituted or unsubstituted aryl group such as p-chlorophenyl group, p-methoxyphenyl group, m-nitrophenyl group, or α
-It is a furyl group. R ₁ and R ₂ may be linked to each other to form a ring, for example, a cyclohexyl ring. Of these, R ₁ and R ₂ are particularly preferably hydrogen atoms,
An alkyl group having 1 to 8 carbon atoms, a phenyl group, and an α-furyl group.

R ³ , R ⁵ , R ⁸ and R ¹⁰ are preferably methyl, ethyl, i-propyl, t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms such as tribromomethyl, 1-phenylethyl, 2-phenyl-2-propyl; a phenyl group,
a substituted or unsubstituted aryl group such as a p-chlorophenyl group; -OR "(wherein R" represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms; the same applies hereinafter) A substituted or unsubstituted alkoxy group;
A halogen atom such as a chlorine atom or a bromine atom; an acyl group represented by -COR "; -NR ¹² COR" (wherein R ¹² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; the same applies hereinafter). amide groups; -NR ¹² SO ₂ sulfonamide group represented by R "; -CON carbamoyl group represented by (R ¹²⁾ _2; a or sulfamoyl group represented by _{^{-SO 2 N (R 12) 2}} , particularly preferably Are halogen atoms (chlorine atom, bromine atom) and alkyl groups having 8 or less carbon atoms.

R ⁴ , R ⁶ , R ⁷ and R ⁹ are preferably hydrogen atoms; or methyl, ethyl, i-propyl, t-
Butyl, t-amyl, t-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, tribromomethyl, 1-phenylethyl, 2-phenyl-2-propyl, etc. Substituted alkyl group; substituted or unsubstituted aryl group such as phenyl group and p-chlorophenyl group; -OR "(where R" is a carbon number of 1 to 1)
20 represents a substituted or unsubstituted alkyl group or aryl group. The same shall apply hereinafter), a substituted or unsubstituted alkoxy group; a halogen atom such as a chlorine atom or a bromine atom;
An acyl group represented by —COR ″; —NR ¹² COR ″
(Wherein R ¹² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; the same applies hereinafter); -NR
Sulfonamide group represented by ¹² SO ₂ R ″; -CON
A carbamoyl group represented by (R ¹² ) ₂ ;
₂ N (R ¹² ) ₂ is a sulfamoyl group represented by
Particularly preferred are hydrogen atom, methyl group, ethyl group, methoxy group, chlorine atom and acetyl group.

It is also preferable that R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ and R ¹⁰ are connected to each other to form a substituted or unsubstituted ring, and a particularly preferable ring. An example of the structure is a naphthalene ring.

L ¹ and L ² are not particularly limited, and a divalent organic group or a chemical bond can be used, but preferably, a chemical bond, a substituted or unsubstituted alkylene group (eg, methylene group, Ethylene group, propylene group, trimethylene group, tetramethylene group, hexamethylene group, 2-
Phenylethylene group, etc.), substituted or unsubstituted poly (oxyalkylene) group (for example,-(CH ₂ CH ₂ O))
_{n -, - (CH (CH} 3) CH 2 O) n -, - ((CH
₂ ) ₄ O) _n-, etc., n represents an integer of 1 or more), a substituted or unsubstituted arylene group (for example, p-phenylene group, o-phenylene group, m-phenylene group, 4, 4'-bisphenylene group, etc., and two or more of these divalent organic groups are polar bonding groups (eg, ester bond, carbonamide bond, sulfonamide bond, ether bond, carbonyl bond, sulfonyl bond, etc.). It is also preferably a divalent organic group formed by bonding via. Of these, particularly preferred are chemical bonds, methylene groups, trimethylene groups, tetramethylene groups,
Examples thereof include poly (oxyethylene group) and phenylene group.

M ₁ and M ₂ are preferably hydrogen ions,
Alkali metal ions and the like are preferable, and hydrogen ion, sodium ion, and potassium ion are particularly preferable. Next, specific examples of preferred compounds of the present invention are shown, but the present invention is not limited to these specific examples.

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

General Synthetic Method The anionic surfactant represented by the general formula (I) of the present invention can be obtained by a condensation reaction or an addition reaction between a bisphenol represented by the following general formula (II) and a sulfonic acid derivative. You can General formula (II)

[0034]

[Chemical 18]

Synthetic Examples The preferred synthetic examples of the compounds represented by formula (I) of the present invention are shown below, but the present invention is not limited to these synthetic examples. Synthesis Example-1 (Synthesis of Exemplified Compound A-3) In a 300 ml three-necked flask equipped with a cooling tube, 1,
1-bis [6- (1-hydroxy-2-ethyl-5-n
-Hexyl) phenyl] ethane 42.3 g (0.1 mol), toluene 20 ml, potassium hydroxide 11.2 g
(0.2 mol) was added and vigorously stirred at room temperature to dissolve. This solution was heated to 50 ° C., and it was confirmed that the solution became viscous.
(0.2 mol) was added and stirred for 20 minutes. 8 reaction liquids
After heating to 5 ° C, the mixture was vigorously stirred for 2 hours, 10 ml of toluene was added, and the mixture was further vigorously stirred at 85 ° C for 2 hours, and toluene 5 was added again.
ml was added and the reaction was continued for 4 hours. The reaction solution was cooled to room temperature, and 1500 ml of methanol was added to completely dissolve it. The solution was purified by filtration, and 2 l of acetone tolyl was added to precipitate crystals. The crystals were collected by filtration and dried to obtain 62.6 g (yield 82.0%) of pale yellowish white crystals (Exemplary Compound A-3).
The structure of the compound is IR, ¹ H-NMR, ¹³ C-NMR,
Confirmed by elemental analysis and mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound A-11) 1,1 in a 300 ml three-necked flask equipped with a cooling tube.
-Bis [6- (1-hydroxy-2-methyl-5-tert
-Octyl) phenyl] ethane 44.7 g (0.1 mol), toluene 20 ml, sodium hydroxide 8.0 g
(0.2 mol) was added, and with vigorous stirring at room temperature,
Heated to 50 ° C. Add 27.2 butanesaltone to this solution.
g (0.2 mol) was added and vigorous stirring was continued for 20 minutes, then the reaction solution was heated to 85 ° C. and reacted for 2 hours. To the reaction solution was added 10 ml of toluene and the reaction was continued for 2 hours, then 5 ml of toluene was added again and the reaction was carried out at 100 ° C. for 2 hours. The reaction solution was cooled to room temperature, 1200 ml of methanol was added to dissolve it, and after filtration and purification, 2 l of acetone tolyl was added to precipitate crystals. The crystals were collected by filtration and dried to give 64.4 g (yield 82.3%) of pale yellow crystals (Exemplary Compound A-11).
Got The structure of the compound is IR, ¹ H-NMR, ¹³ C-N
Confirmed by MR, elemental analysis and mass spectrum.

Synthesis Example 3 (Synthesis of Exemplified Compound A-10) In a 300 ml three-necked flask equipped with a cooling tube, 1,
1-bis [6- (1-hydroxy-2-methyl-5-te
rt-octyl) phenyl] ethane 44.7 g (0.1 mol), toluene 50 ml, potassium hydroxide 11.2 g
(0.2 mol) was added and heated to 50 ° C. to completely dissolve it. 11.6 g of propylene oxide in this solution
(0.2 mol) was added at room temperature and reacted at 30 ° C. for 2 hours, then 46.5 g (0.8 mol) of propylene oxide was added again, reacted at 30 ° C. for 4 hours, and further heated to 70 ° C. Then, the reaction was continued for 1 hour. The solvent was distilled off from the obtained reaction solution under reduced pressure, and 20 ml of toluene was newly added to the residue to completely dissolve it, and then 27.2 g (0.2
Mol) was added and the reaction was carried out at 85 ° C. for 2 hours. 10 ml of toluene was added to this reaction solution and the reaction was allowed to proceed at 85 ° C. for 6 hours. The reaction solution is cooled to room temperature and methanol 100 is added.
0 ml was added, and the filtrate after dissolution and filtration purification was separated and purified by a column chromatogram to obtain the desired exemplary compound A-1.
0, 111.3 g (yield 79.8%) was obtained. The resulting A-1 was a slightly yellow and transparent wax-like compound. The structure of the compound was confirmed by IR, ¹ H-NMR, ¹³ C-NMR, elemental analysis and mass spectrum.

The other compounds of the present invention can be synthesized by the same or similar synthetic method as the above synthetic method.
The compound represented by the general formula [I] used in the present invention is
Although it can be synthesized as a single substance by the above-mentioned synthesis method, it is not always necessary to obtain it as a single substance, and even if it is a mixture, there is no problem in practical use, and a feature of improving performance may be obtained in some cases. The compound represented by the above general formula (I) used in the present invention is
It is also preferable to use a mixture of two or more compounds represented by the general formula (I) having different structures.

The compound represented by the general formula (I) of the present invention is added to at least one of the silver halide emulsion layers or other constituent layers of the photographic light-sensitive material. Preferred examples of other constituent layers include a surface protective layer, a back layer, an intermediate layer, and an undercoat layer. Particularly preferable as a place of addition is a silver halide emulsion layer, a surface protective layer, an intermediate layer and the like. Photographically useful materials that can be used in the present invention mean any organic compound and organic or inorganic dyes and pigments useful in photographic applications.
In the present invention, it is preferable to use an oil-soluble organic photographically useful substance. Oil solubility here means room temperature (20 ° C)
In the above, a compound which dissolves in an organic solvent in an amount of 3% by weight or more. Further, the organic solvent means an organic solvent described in "Solvent Handbook" and the like, examples of which include methanol, ethanol, isopropanol, butanol, ethyl acetate, isopropyl acetate, butyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, Examples thereof include cyclohexanone, benzene, toluene, dioxane, acetonitrile, dichloromethane and chloroform.

The hydrophobic photographically useful substances which can be used in the present invention include dye image-forming couplers, dye image-donating redox compounds, antistain agents, antifoggants, ultraviolet absorbers,
Anti-fading agent, anti-color-mixing agent, nucleating agent, dye image stabilizer, silver halide solvent, bleaching accelerator, dye for filters and precursors thereof, dyes, and for dispersion used as a medium for dispersing these Examples of the description of these compounds include oil and dispersion polymers. Research Disclosure No. 17643, No. 18716, N
o. No. 307105 and the like are mentioned. a) Dye image-forming coupler A compound which forms a colored or uncolored dye by coupling with an oxidation product of an aromatic primary amine developing agent is called a coupler. Yellow, magenta, cyan and black couplers are useful as the coupler.

Typical examples of the yellow coupler which can be used in the present invention include oil-protective acylacetamide couplers. Specific examples thereof include US Pat. Nos. 2,407,210 and 2,407,210.
875,057 and 3,265,506. Two-equivalent yellow couplers include U.S. Pat. Nos. 3,408,194 and 3,447,92.
No. 8, No. 3,933, 501 and No. 4,02
Oxygen atom-releasing yellow couplers described in JP-A No. 2,620, and JP-B-58-10739, US Pat. Nos. 4,401,752, and 4,326,024.
Issue, Research Disclosure 18053 (1979)
April, 2004), U.S. Patent No. 1,425,020, West German Application Publication Nos. 2,219,917, and 2,261,361.
No. 2,329,587 and 2,433.
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A No. 812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while the α-benzoyl acetanilide type coupler can obtain a high color density. Of these,
For example, US Pat. Nos. 3,933,501 and 4,02
No. 2,620, No. 4,326,024, No. 4,4
No. 01,752, No. 4,248,961, Japanese Patent Publication No. 5
8-10739, British Patent No. 1,425,020,
U.S. Pat. No. 1,476,760 and U.S. Pat. No. 3,973,9.
No. 68, No. 4,314, 023, No. 4,511,
Those described in 649, European Patent 249,473A, and the like are preferable.

Examples of magenta couplers that can be used in the present invention include oil-protected couplers of indazolone type or cyanoacetol type (preferably 5-pyrazolone type and pyrazoloazole type such as pyrazolotriazoles). 5-pyrazolone type capillar is 3-
A coupler in which the position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
No. 062,653, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, in the case of the 5-pyrazolone type coupler having a ballast group described in EP 73,636, a high color density can be obtained.

The pyrazoloazole-based couplers include pyrazolobenzimidazoles described in US Pat. No. 3,369,879 and pyrazolo [5,1-c] [described in US Pat. No. 3,725,067. 1,2,4] triazoles, Research Disclosure 24220 (1
Pyrazolopyrazoles described in Jun. 984). The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 and European Patent No. 119,86 in view of the small amount of yellow sub-absorption of the color forming dye and the light fastness.
The pyrazolo [1,5-b] [1,2,4] triazoles described in No. 0 are preferred. Of these, particularly US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636 and US Pat. No. 3,061,43.
2, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure N.
o. 24230 (June 1984), JP-A-60-43.
No. 659, No. 61-72238, No. 60-35730.
No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,54
0,654, 4,556,630, International Publication W
Those described in O88 / 04795 and the like are preferable.

Cyan couplers that can be used in the present invention include oil protect type naphthol type and phenol type couplers. US Pat. No. 2,474,293
Naphthol couplers described in US Pat. Nos. 4,052,212 and 4,146,396,
No. 4,228,233 and No. 4,296,20
A representative example is an oxygen atom-releasing type diequivalent naphthol coupler described in No. 0. Further, specific examples of the phenol-based coupler are described in US Pat. No. 2,369,929.
No. 2, No. 2,801,171, No. 2,772,16
2, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 3,772,002. Phenolic cyan coupler having a group, US Pat. No. 2,772,162
No. 3, No. 3,758,308, No. 4,126,39
No. 6, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729 and 2,5-diacylamino-substituted phenol couplers described in JP-A-59-166956 and US Pat. Nos. 3,446,622 and 4 , 333, 999,
Nos. 4,451,559 and 4,427,76
Phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in No. 7 and the like.

JP-A-60-237448 and JP-A-61-1
53640, 61-14557 and the like 5
Naphthol-based couplers in which the -position is substituted with a sulfonamide group, an amide group or the like are particularly excellent in the fastness of a color image.
It is preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in 1) and the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used.

Of these, US Pat. No. 4,052,2
No. 12, No. 4,146, 396, No. 4,228,
No. 233, No. 4,296,200, No. 2,36
9,929, 2,801,171, 2,7
72, 162, 2, 895, 826, 3,
772,002, 3,758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patent 12
No. 1,365A, No. 249,453A, U.S. Pat. No. 3,446,622, No. 4,333,999, No. 4,775,616, No. 4,451,559,
No. 4,427,767, No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658 and the like are particularly preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like. Examples of the coupler in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237,
British Patent No. 2,125,570, European Patent No. 96,5
70 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is described in RD17643, VII to F and the same No. 307105, Patents described in Section VII-F, JP-A-57-151944, 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,96.
Those described in No. 2 and No. 4,782, 012 are preferable. In addition, R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A-61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using the tabular silver halide grains described above. When added, its effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
No. 2340, JP-A Nos. 1-44940 and 1-4568.
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , Couplers releasing a ligand described in U.S. Pat. No. 4,555,477, couplers releasing a leuco dye described in JP-A-63-75747, fluorescent dyes described in U.S. Pat. No. 4,774,181. And a coupler that emits Two or more of the above-mentioned couplers can be used in combination in the same layer in order to satisfy the properties required of the light-sensitive material.

B) Dye image donating redox compound As another photographically useful substance which can be used in the present invention, there is a dye image donating redox compound used in a color diffusion transfer method light-sensitive material. This compound, as known to those skilled in the art,
Negative or positive working and initially mobile or immobile in the photographic element when processed with an alkaline processing composition. Negative-type dye image-donor 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. 3,227,550 and Canada. It is described in Japanese Patent No. 602,207 and the like.

Preferred negative-working dye image-donating compounds for use in the present invention are dye-releasing redox compounds, which react with an oxidizing developing agent or an electron transfer agent to release a dye. A specific example is JP-A-48-3.
No. 3826, No. 51-113624, No. 54-540.
21 and 56-71072. The non-movable positive-working dye image-donating compound that can be used in the present invention does not receive any electrons (that is, is not reduced) during photographic processing under alkaline conditions, or receives at least one electron. Some compounds release a diffusible dye after being released (ie, reduced).

Further, there is a dye developing agent as a positive-working dye image-donor compound which is mobile from the beginning under alkaline photographic processing conditions, and this is effective in the present invention. Typical specific examples thereof are described in Japanese Examined Patent Publication Nos. 48-32130 and 55-22780. The dye formed from the dye image-donor compound used in the present invention may be a ready-made dye or, alternatively, a dye precursor that can be converted into a dye in a photographic processing step or an additional processing step, and the final image The dye may or may not be metallized. Representative dye structures useful in the present invention include metallized and non-metallized dyes such as azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes. Of these, azo cyan, magenta and yellow dyes are particularly important.

A dye-releasing redox compound having a dye portion in which light absorption is temporarily shifted in the light-sensitive element can also be used in the present invention as a kind of dye precursor. Particularly preferred dye image-donating compounds for use in the present invention are first the dye releasing redox compounds (DR
R-compound), specific examples of which are described in JP-A-48-
No. 33826, No. 51-113624, No. 54-54
021 and 56-71072. Specific examples of the redox mother nucleus that is cross-oxidized by the development of silver halide and releases a diffusible dye under alkaline conditions include:

[0054]

[Chemical 19]

[0055]

[Chemical 20]

Etc. Another type of particularly preferable dye image-providing compound is that belonging to the positive type.
No. 3-110827, No. 53-110828 and No. 5
No. 6-164342, specific examples of this type of redox nucleus include the following.

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

Next, specific examples of the dye-releasing redox compound include the compounds described in JP-A-61-251841 ((DR-1) to (DR-1) described on pages 23 to 25).
(DR-14)).

C) Ultraviolet Absorber Suitable ultraviolet absorbers for carrying out the present invention are, for example, Japanese Patent Publication Nos. 42-21687, 48-5496, and JP-A-4.
7-1026, British Patent 1,293,982 and the like. Of these, oil-soluble ultraviolet absorbers are particularly preferable.

D) Organic or Inorganic Dyes The dyes or pigments used in the present invention include azo, azomethine, oxonol, cyanine, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigo and perinone. -There are organic dyes and inorganic dyes such as perylene-based, titanium oxide, cadmium-based, iron oxide-based, chromium oxide, and carbon black, and other known dyes that have been conventionally used as colorants or a mixture thereof is used. You can These dyes and pigments in the present invention can be used in any state such as an aqueous paste state or powder state immediately after production. In particular, U.S. Pat. No. 4,420,555 and Japanese Patent Laid-Open No. 61-204630.
The present invention is useful for dispersing oil-soluble dyes represented by the following general formula (II) described in JP-A No. 61-205934 and the like.

E) Other photographically useful substances Other photographically useful substances which can be used in the present invention are such that at least one electron can be donated to an oxidative dye-donor compound or an oxidant of a color developing agent. Electron donor (hereinafter referred to as "ED"). Valid ED
As T. H. James, The Theory of the P
hotographic Process) Fourth Edition, Chapter 11 There are compounds having a partial structure of Kendall-Pliz. The compounds belonging to this group include hydroquinones, catechols, o-aminophenols, p-aminophenols and the like. The ED compound used in the present invention preferably has low diffusivity when incorporated in a light-sensitive material layer. Low diffusivity or non-diffusible hydroquinones, pyrogallols, etc.
Widely used as anti-color mixing agent, antioxidant, anti-fading agent, etc. Specific examples of these compounds include 2,5
-Di-n-octylhydroquinone, 2,5-di-t-
Examples include pentadecyl hydroquinone, gallic acid n-dodecyl ester, and p-laurylamide pyrogallol.

The ED precursor which can be used in the present invention includes compounds suitable for use in combination with a positive type dye image-providing compound. Examples thereof include saccharin-based compounds as described in US Pat. No. 4,263,393 and US Pat. No. 4,278,75.
There are active methine-based compounds as described in No. 0.

Other photographic useful substances which can be used in the present invention are represented by, for example, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptothiadiazoles, benzotriazoles and imidazoles. Antifoggants and development inhibitors; developing agents such as p-phenylenediamines, hydroquinones, p-aminophenols; auxiliary developing agents represented by pyrazolidones; nucleating agents such as hydrazines and hydrazides; hypo And the like; bleaching accelerators such as aminoalkyl thiols; 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 of releasing the above-mentioned photographically useful substance with the progress of development, such as the above-mentioned dye material for color diffusion transfer photosensitive material. To D
IR- or DAR-hydroquinones can also be mentioned as good photographically useful substances. The photographically useful substances described above may be bound via a timing group,
As such a timing group, JP-A-54-145 is known.
Releasing a photographically useful substance by an intramolecular ring closure reaction described in 135, British Patent No. 2,072,36
No. 3, those releasing a photographically useful substance by intramolecular electron transfer described in JP-A No. 57-154234 and the like,
Those which release a photographically useful substance with desorption of carbon dioxide as described in JP-A-57-179842 or the photographically useful with release of formalin as described in JP-A-59-93442. Examples include substances that release substances.

F) Oil for Dispersion and Polymer for Dispersion As the high boiling point organic substance (dispersion oil) used for suppressing the precipitation of crystals when the oil-soluble photographically useful substance is finely dispersed in an aqueous medium, Practically insoluble in water, boiling point 1 at normal pressure
It is preferably 90 ° C. or higher. Examples of this type of organic substance include carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, phenols, anilines, substituted hydrocarbons, and surface-inert hydrophobic organic polymers. You can choose. Specific examples thereof include di-n-butyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, di-n-butyl adipate, diisooctyl azelenate, tri-n-butyl citrate, and laurate. Butyl acid, di-n-butyl sebacate, tricyclohexyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, N, N-diethylcaprylic acid amide, N, N-dimethylpalmitic acid amide, n- Butyl- (m-pentadecyl) phenyl ether, ethyl- (2,4-di-tert.
-Butyl) phenyl ether, 2,5-di-tert-amylphenol, 2-n-butoxy-5-tert-octylaniline, chlorinated paraffin, poly (methyl methacrylate), poly (ethyl methacrylate), poly (ethyl acrylate) , Poly (cyclohexyl methacrylate), poly (N-tert-butyl acrylamide), poly (N-tert-octyl acrylamide), and the like.

In the present invention, in order to dissolve the oil-soluble photographically useful substance, in addition to the above-mentioned high-boiling point organic substance, a low-boiling point organic solvent immiscible with water (having a boiling point of 130 ° C. or less at 1 atm), Alternatively, a water-miscible organic solvent may be used.
In order to increase the stability of the obtained dispersion, the water-immiscible or water-miscible organic solvent used for bringing the photographically useful substance into a solution state is distilled, more preferably vacuum distillation or ultrafiltration, and the like. You may remove by a well-known method. As those organic solvents, for example, propylene carbonate,
Examples thereof include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, dimethylformamide, and dimethol sulfoxide. The preferred amount of the organic solvent used is 0.1 to 100 times the weight of the dispersed oil-soluble photographically useful substance.

In the present invention, a photographically useful substance kept in a solution state by any of the following methods is mixed with water or a hydrophilic colloid aqueous solution in the presence of the surface active polymer of the present invention to obtain a photograph. A fine dispersion of the useful substance is prepared. If necessary, a disperser as described below may be used to further reduce the size of the dispersion particles. Examples of the emulsifying apparatus used to carry out the present invention include a high-speed stirring type disperser having a large shearing force and a disperser giving high-strength ultrasonic energy. Specifically, there are a colloid mill, a homogenizer, a capillary type emulsifying device, a liquid siren, an electromagnetic distortion type ultrasonic generator, and an emulsifying device having a Paulman whistle. The high-speed stirring type disperser preferred for use in the present invention is a dissolver, a polytron, a homomixer, a homoblender, a kedi mill, a jet agitator, and the like.
5,000 rpm, preferably 2,000-4,000 rp
m) type of disperser. The high-speed stirring type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser. It is also a preferable example to mount an impeller bent vertically on the.

In preparing an oil-in-water type dispersion of photographically useful substances (hereinafter referred to as "aqueous dispersion") according to the present invention, various processes can be followed. When dissolving a photographically useful substance in an organic solvent, the above-mentioned high-boiling point organic substance,
It is dissolved in a water-immiscible low-boiling organic solvent or a water-miscible organic solvent arbitrarily selected, or dissolved in an arbitrary multi-component mixture of two or more, and then represented by the general formula (I) of the present invention. In the presence of the compound, it is dispersed in water or a hydrophilic colloid aqueous solution. In this case, the compound of the present invention is allowed to coexist in a solution containing a photographically useful substance, water, and / or a hydrophilic colloid aqueous solution.

The oily liquid containing a photographically useful substance and the aqueous liquid may be mixed by a so-called forward mixing method in which the oily liquid is added to the aqueous liquid under stirring, or a reverse mixing method of the reverse.
In particular, the phase inversion method, which is one of the back mixing methods, is preferable in that it gives a finer aqueous dispersion. The amount of the compound used in the present invention is, for example, the type and amount of the photographically useful substance, the high-boiling point organic substance, the low-boiling point organic solvent or the water-miscible organic solvent used, and the type and amount of the surfactant used in combination. The optimum amount varies depending on the amount, but the usable range is 0.1 to 300% by weight based on the total amount of the substances to be dispersed, that is, photographically useful substances, high-boiling point organic substances and water-immiscible organic solvents. Is 0.2 to 50% by weight.

In the present invention, the oil-soluble photographically useful substance can be stably dispersed in either water or the hydrophilic colloid composition, but it is preferably dispersed in the hydrophilic colloid composition. As the hydrophilic colloid in the hydrophilic colloid composition used in the present invention, a binder or a protective colloid usually used in silver halide photographic light-sensitive materials is used. Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Use various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme dispersion may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used. The present invention can be applied to various color and black and white light-sensitive materials. As the light-sensitive material, a color negative film for general use or movies, a color reversal film for slides or televisions, a color positive film, a color paper, a color reversal paper, a color diffusion transfer type light-sensitive material, a heat development type color light-sensitive material, a general For black and white film,
Black-and-white paper, black-and-white sensitive material for X-ray photography, black-and-white sensitive material for printing,
Examples thereof include black-and-white diffusion transfer type light-sensitive materials, heat-development type black-and-white light-sensitive materials, infrared light-sensitive materials for laser scanners, and COM or ordinary microfilm.

The type of silver halide used in the silver halide emulsion layer, intermediate layer, surface protective layer, subbing layer, back layer and the like of the photographic light-sensitive material of the present invention, the production method, the chemical sensitization method, the antifoggant, There are no particular restrictions on stabilizers, hardeners, antistatic agents, couplers, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizers, dyes, ultraviolet absorbers, etc.
For example, Product Licensing Magazine
g) 92, pp. 107-110 (December 1971) and Research Disclosure.
176, 22-31 (December 1978), 238
The description on pages 44 to 46 (1984) can be referred to.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material produced by using the present invention may include coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development). Various surfactants other than the compound represented by the general formula (I) of the present invention may be additionally contained for various purposes such as acceleration, contrast enhancement, and sensitization. these,
Examples of the surfactant which may be used in combination with the compound (I) of the present invention are Ryohei Oda et al., “Surfactants and Their Applications” (Maki Shoten,
1964), Hiroshi Horiguchi's "New Surfactant" (Sankyo Publishing Co., Ltd., 1975) or "Mac Cation's Detergent and Emulsion Fires" (Mc Cation Divisions, MC Publishing Company 1985) (" Mc Cutcheon's Dete
rgents & Emulsifiers "(Mc Cutcheon Divisions, MC Pu
blishing Co. 1985)), JP-A-60-76741.
No. 61-16056, Japanese Patent Application No. 61-13398
No. 61-32462.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. It may consist of a mixture of particles of various crystal forms. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm.
The monodisperse emulsions described in 4,628, 3,655,394 and British Patent 1,413,748 may be used. The silver halide photographic emulsion that can be used in the present invention is
For example, Research Disclosure (RD) No. 17
643 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", and ibid.
No. 18716 (November 1979), p.648, ibid.
o. 307105 (November 1989), 863-86.
Page 5, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et Phisique Pho
tographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Pho
tographic Emulsion Chemistry (Focal Press, 196
6)), "Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al., Making and
CoatingPhotographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4) or the like.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and En
gineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
A method for producing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion is 3 to 4 depending on development processing and the like.
0 nm is preferable, and 5 to 20 nm is particularly preferable.

The silver halide grains are cadmium salt, zinc salt,
A metal ion is added using at least one selected from a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt) and an iron salt (including a complex salt), and / or inside the particle. These metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere. In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. The removal of the salts can be carried out according to the method described in Research Disclosure 17643II.

The silver halide emulsion is usually prepared by physical ripening,
The one that has been chemically aged and spectrally sensitized is used. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and N
o. No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used. Silver halide grains having a fogged grain surface described in U.S. Pat. No. 4,082,553, and halogens having fogged grains described in U.S. Pat. No. 4,626,498 and JP-A-59-214852. Silver halide grains and colloidal silver can be preferably used in the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm, particularly 0.05.
˜0.6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40 of the average grain size). %) Is preferable).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average grain size (average value of circle-equivalent diameter of projected area) of 0.01 to 0.5 μm, and 0.02 to
0.2 μm is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. The coating amount of silver of the light-sensitive material of the present invention is 6.
It is preferably 0 g / m ² or less, and most preferably 4.5 g / m ² or less.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23 to 24 page 648 right column to 866 to 868 page strong color increase Sensitizer page 649 right column 4 whitening agent page 24 647 right column 868 page 5 antifoggant, pages 24 to 25 page 649 right column 868 to 870 stabilizer 6 light absorber, page 25 to 26 page 649 right Column to page 873 Filter dye, page 650 Left column UV absorber 7 Anti-stain agent Page 25 Right column page 650 Left column to page 872 Right column 8 Dye image stabilizer page 25 650 page left column 872 page 9 Hardener page 26 Page 651 Left column 874 to 875 Page 10 Binder page 26 Page 651 Left column 873 to 874 page 11 Plasticizer and lubricant page 27 650 Page right column 876 Page 12 Coating aid, Page 26 to page 650 Right column 875 to 876 Page Surfactant 13 Antistatic agent page 27 page 650 page right column 876 to 877 page 14 matting agent page 878 to 879 pages

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound which can be immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat. Nos. 4,740,454 and 4,788,132.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, international publication WO88 / 04
No. 794, a dye dispersed by the method described in JP-A-1-502912 or a dye described in EP317,308A, US Pat. No. 4,420,555, and JP-A-1-259358. preferable. In the light-sensitive material of the present invention, phenethyl alcohol or JP-A-63-2 is used.
No. 57747, No. 62-272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethyl described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as phenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

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

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. US Patent No. 2 as required
No. 681294, No. 2761791, No. 3526
Multiple layers may be coated at the same time by the coating methods described in No. 528 and No. 3508947. The present invention can be applied to various color and black and white light-sensitive materials. Color photographic light-sensitive materials include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type light-sensitive materials and heat-development type color light-sensitive materials. Can be mentioned as a representative example.

Examples of the black and white photographic light-sensitive material include plate-making films such as lith film and scanner film, X-ray films for direct and indirect medical treatment or industrial use,
The present invention is also applicable to negative black and white films for photography, black and white photographic papers, COM or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.
When the photographic element of the present invention is applied to a color diffusion transfer photographic method, it is a peel-apart type or JP-B-46.
-16356, 48-33697, JP-A-50-
13040 and an integrated type as described in British Patent 1,330,524 and a peel-free type film unit as described in JP-A-57-119345. You can
The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is advantageous for broadening the processing temperature latitude. When used in the color diffusion transfer photographic method, it may be added to any layer in the light-sensitive material, or may be contained as a developing solution component in a processing solution container before use. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, 23
It is more preferably not more than μm, further preferably not more than 18 μm, particularly preferably not more than 16 μm. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art.
For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, No. 2, p. ) Is used, T _1/2 can be measured with a developing solution at 30 ° C. for 3 minutes 15
90% of the maximum swollen film thickness reached when the second treatment is performed is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 on the side opposite to the side having the emulsion layer.
Hydrophilic colloid layer of μm to 20 μm (referred to as back layer)
Is preferably provided. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the light-sensitive material can be used as the proof light source or the writing light source. Flashlight sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. Gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a fluorescent image (CRT or the like) emitted from a fluorescent body excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The photographic light-sensitive material according to the present invention has the above-mentioned R content.
D. No. 17643, pages 28-29, same No. 18716
651 left column to right column, and the same No. 307105 88.
The development can be carried out by a usual method described on pages 0 to 881. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p- Examples thereof include toluene sulfonate. Among these, especially 3-methyl-
4-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a p-type developer such as an alkali metal carbonate, borate or phosphate.
It is common to include a development inhibitor such as an H buffer, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N
Hydrazines such as biscarboxymethylhydrazine, phenylsemicarbazides, various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines Development accelerators, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids. Various chelating agents represented by acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1. Representative examples are 1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. Can be mentioned as.

When the reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature and high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927, and 54-35, 727, 5
Compounds described in JP-A Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains p for adjusting the pH.
It is preferable to add a compound having a Ka of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, Japanese Patent Laid-Open No.
No. 183460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using the rotating means of JP-A No. 62-183461, and a wiper blade provided in the solution. Examples include a method of moving the light-sensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is
JP-A-60-191257 and 60-191258.
No. 60-191259. The above-mentioned JP-A-60-19
As described in No. 1257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture.
and Television Engineers Volume 64, P. 248-2
53 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Published by Hygiene Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986). The pH of washing water in the processing of the light-sensitive material of the present invention is
It is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected.
Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14 have been used.
All known methods described in No. 834 and No. 60-220345 can be used. In addition, following the water washing treatment, there is a case where a further stabilization treatment is performed, and as an example,
A stabilizing bath containing a dye stabilizer and a surfactant, which is used as the final bath of a color light-sensitive material for photographing, can be mentioned. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14,850 and the same.
Schiff base type compounds described in Nos. 15 and 159, 1
Aldol compounds described in US Pat. No. 3,924, US Pat.
Metal salt complexes described in 719, 492, JP-A-53-13.
The urethane type compound described in No. 5628 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-144547.
No. 58-115438 and the like. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449 and JP-A-59-218443,
61-238056, European Patent 210,660A2.
It can also be applied to the photothermographic material described in No.

[0093]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of Samples 101 to 112) 22 g of the oil-soluble photographically useful compound PUC-1 having the following structural formula and the amount of the compound used as the emulsifier shown in Table 1 also shown in Table 1 were tricresyl phosphate 11 g and 60 g in 80 g of ethyl acetate
It was heated and dissolved in. To this solution, 630 g of a 16% gelatin aqueous solution heated and dissolved at 50 ° C. was added with stirring,
Then, the mixture was stirred with a high-speed stirring impeller for 30 minutes under the condition of keeping the temperature at 50 ° C. Then add 370g of water and add 50
After stirring for 10 minutes, emulsion samples 101 to 107 (invention) and 108 to 112 (comparative example) were obtained.

[0094]

[Chemical formula 23]

[0095]

[Table 1]

Comparative compounds W-1 to W-4 used in Table 1
Is a surfactant having the following structure.

[0097]

[Chemical formula 24]

[0098]

[Chemical 25]

[0099]

[Chemical formula 26]

[0100]

[Chemical 27]

(Evaluation of Emulsion Dispersion Stabilizing Effect) The obtained fine emulsified dispersion samples 101 to 111 were kept at 40 ° C. for a while and the change in particle size was measured using a Coulter N4 particle size measuring device. Also, after storing in a refrigerator (6 ° C) for 2 days, 4
The sample was dissolved at 0 ° C. and allowed to stand at 40 ° C. for 2 days as it was, and a sample after aging was taken on a preparation and examined for crystallization by observing with a polarizing microscope. These results are summarized in Table-1.

Emulsion samples 101 to 107 prepared by using the compound of the present invention and emulsion samples 108 to 110 prepared by using the comparative compound were obtained as extremely finely dispersed emulsions immediately after emulsification. Was given. However, in the emulsion samples 108 to 110 (comparative examples), after keeping the temperature at 40 ° C., coalescence of fine particles proceeded, and the particle size was remarkably increased. On the other hand, in all of the emulsion samples 101 to 107 prepared using the compound of the present invention, the particle size remained extremely fine after being kept warm at 40 ° C. for 2 days. In addition, in the emulsion dispersion using the compound of the present invention, no precipitation of crystals was observed with refrigeration. From these results, it can be seen that the compound of the present invention is excellent in the stability of the extremely fine emulsion during heat retention.

Example 2 (Preparation of Samples 201 to 211) 2.5 g of an oil-soluble photographically useful material (yellow coupler) PUC-2 having the following structure was dissolved in 4 ml of ethyl acetate, and the emulsifier 0 shown in Table 2 was added to this solution. 25 g of an aqueous gelatin solution having a concentration shown in Table 2 containing .25 g, which was heated to 50 ° C., was added with stirring,
Then, the emulsion samples 201 to 206 (invention), 20
7-211 (comparative example) was obtained. (Preparation of Samples 212 to 215)

[0104]

[Chemical 28]

2.5 g of the above oil-soluble photographically useful material (yellow coupler) PUC-2 was added to n-propanol 12.5.
A solution of the surfactant W having the following structure is dissolved in 50 ml at 50 ° C.
-52.5 g was gradually added to 50 ml of the dissolved aqueous solution,
A dispersion was prepared. At this time, the n-propanol solution was 1
The entire amount was added dropwise in minutes, and the aqueous solution was stirred at 800 RPM.
25 g of a 10 weight percent solution of this dispersion and gelatin
And were mixed and stirred for 30 minutes under a temperature keeping condition of 50 ° C. to obtain an emulsion sample 212. Emulsion sample 212 except that the concentration of the gelatin aqueous solution to be mixed was set to 5% by weight.
An emulsion sample 213 was obtained by the same method as described above. Further, the emulsion sample 212 prepared above is heated to 65 ° C. under reduced pressure,
Emulsion sample 214 was removed by removing n-propanol, and n-propanol was removed by performing pressure dialysis using an ultrafiltration membrane to obtain emulsion sample 215, respectively.

[0106]

[Chemical 29]

[0107]

[Table 2]

(Evaluation of Stabilizing Effect of Emulsified Dispersion) The obtained fine emulsified dispersion samples 201 to 215 were kept warm at 40 ° C. for a while, and then the change in particle size was measured using a Coulter N4 particle size measuring device. . Emulsion samples 201 to 206 using the compound of the present invention, emulsion sample 20 using the comparative compound
Emulsion samples 212, 213 and 215 prepared by a dispersion method using 7-210 and a water-miscible organic solvent all gave very finely dispersed emulsions immediately after emulsification. However, the emulsion samples 207 to 210 (comparative example) had 4
The coalescence of the fine particles proceeded as the temperature was kept at 0 ° C, and the particle size was remarkably increased. On the other hand, emulsion sample 2
In all of 01 to 206, 212, 213 and 215 (the above comparative examples), the particle size remains extremely fine even after the temperature is kept at 40 ° C. for 2 days, and it is very effective in stabilizing an extremely fine emulsion. Recognize. However, among these, the emulsion sample 215 has an extremely high filtration pressure when performing pressure dialysis using an ultrafiltration membrane, and thus the recovery rate after de-n-propanol is extremely low at 45%, Further, since it takes a long time for filtration, the productivity is poor and it is inconvenient as a fine emulsion for a silver halide photographic light-sensitive material.

(Evaluation as an emulsion for silver halide photographic light-sensitive material) The total amount of the fine emulsion samples 201 to 206 (invention), 212 and 213 (above comparative example) was replaced with 40 g of silver chlorobromide emulsion (silver). 73 g / kg emulsion Gelatin 90 g / kg emulsion, silver bromide 80 mol%) and mixed and held at 50 ° C. for 24 hours with stirring. When this solution was filtered while being pressurized with a 3 μ filter, an increase in filtration pressure and precipitation were observed in emulsions 212 and 213. On the other hand, in the silver halide emulsion mixture of a fine emulsion sample prepared using the compound of the present invention, no increase in filtration pressure or precipitation of aggregates was observed, and the fine emulsion prepared using the compound of the present invention was , It has been found that it has extremely excellent dispersion stability for silver halide photographic materials.

Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 301 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 301) First layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40

Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.070 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-10 .060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.04

Third Layer (First Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing Dye I 6.9 × 10 ⁻⁵ Sensitizing Dye II 1.8 × 10 ⁻⁵ Sensitizing Pigment III 3.1 × 10 ⁻⁴ EX-2 0.34 EX-10 0.020 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth layer (second red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ^-4 EX-2 0.40 EX-3 0.050 EX-10 0.015 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.30

Fifth Layer (Third Red Sensitive Emulsion Layer) Emulsion D Silver 1.60 Sensitizing Dye I 5.4 × 10 ⁻⁵ Sensitizing Dye II 1.4 × 10 ⁻⁵ Sensitizing Dye III 2.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

Sixth Layer (Intermediate Layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 Seventh Layer (First Green Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing dye IV 3.0 × 10 ⁻⁵ Sensitizing dye V 1.0 × 10 ⁻⁴ Sensitizing dye VI 3.8 × 10 ⁻⁴ EX-1 0.021 EX-6 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth Layer (Second Green Sensitive Emulsion Layer) Emulsion C Silver 0.45 Sensitizing Dye IV 2.1 × 10 ⁻⁵ Sensitizing Dye V 7.0 × 10 ⁻⁵ Sensitizing Dye VI 2.6 × 10 ⁻⁴ EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ⁻³ Gelatin 0.50

Ninth Layer (Third Green Sensitive Emulsion Layer) Emulsion E Silver 1.20 Sensitizing Dye IV 3.5 × 10 ⁻⁵ Sensitizing Dye V 8.0 × 10 ⁻⁵ Sensitizing Dye VI 3.0 × 10 ^-4 EX-1 0.025 EX-11 0.10 EX-13 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54

Layer 10 (yellow filter layer) Yellow colloidal silver Silver 0.050 Yellow 5 0.080 HBS-1 0.030 Gelatin 0.95 Layer 11 (first blue-sensitive emulsion layer) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 Sensitizing dye VII 3.5 × 10 ⁻⁴ EX-8 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Second Blue Sensitive Emulsion Layer) Emulsion G Silver 0.45 Sensitizing Dye VII 2.1 × 10 ⁻⁴ EX-9 0.15 EX-10 7.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78 Thirteenth layer (third blue-sensitive emulsion layer) Emulsion H Silver 0.77 Sensitizing dye VII 2.2 × 10 ⁻⁴ EX-9 0.20 HBS-1 0.070 Gelatin 0. 69

14th Layer (First Protective Layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 15th Layer (2nd Layer) Protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 gelatin 1.20

Further, all layers have preservability, processability, pressure resistance,
PW-1, PW-2, PW-3, B-4, B-5, in order to improve antifungal / antibacterial properties, antistatic properties and coating properties,
F-1, F-2, F-3, F-4, F-5, F-6, F
-7, F-8, F-9, F-10, F-11, F-1
2, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

[0122] 11th Layer HBS-1,0.28g / m ² and the removal of, the amount of EX-8 in 0.021 g / m ^2, except that further reduce the amount of gelatin 0.7 g / m ² Sample 302 was prepared in exactly the same manner as 301. At this time EX-8,
As a surfactant for dispersing EX-9, PW-3 was added to 0.0
8 g / m ^{2 was} used. Sample 5 except that Compound 10 of the present invention was used in place of PW-3 of Sample 302 at 0.24 g / m ^2.
A sample 303 was prepared in the same manner as 02, but a sample 304 was prepared in the same manner except that the compound 11 of the present invention was used at 0.24 g / m ² instead of PW-3.

[0123]

[Chemical 30]

[0124]

[Chemical 31]

[0125]

[Chemical 32]

[0126]

[Chemical 33]

[0127]

[Chemical 34]

[0128]

[Chemical 35]

[0129]

[Chemical 36]

[0130]

[Chemical 37]

[0131]

[Chemical 38]

[0132]

[Chemical Formula 39]

[0133]

[Chemical 40]

[0134]

[Chemical 41]

[0135]

[Chemical 42]

The sample produced as described above was cut into a piece having a width of 35 mm, imagewise exposed, and processed by an automatic processor. The treatment was performed continuously for a sample of 35 mm width for 500 m. The treatment process and the treatment liquid composition are shown below.

Treatment process Treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 05 seconds 38.0 ° C 600ml 5l Bleaching 50 seconds 38.0 ° C 140ml 3l Bleaching fixing 50 seconds 38.0 ° C ── 3l Fixed 50 seconds 38.0 ° C 420ml 3l Washing with water 30 seconds 38.0 ℃ 980ml 2l stable (1) 20 seconds 38.0 ℃ ── 2l stable (2) 20 seconds 38.0 ℃ 560ml 2l dry 1 minute 60 ℃ ＊ Replenishment amount per 1m ² of photosensitive material

A countercurrent system of rinsing water (2) to (1),
The overflow of washing water was introduced into the fixing bath. To replenish the bleach-fixing bath, connect the top of the bleaching tank of the automatic processor and the bottom of the bleach-fixing tank and the top of the fixing tank to the bottom of the bleach-fixing tank with a pipe, and supply the replenisher to the bleaching tank and the fixing tank. All the overflow solution generated was allowed to flow into the bleach-fix bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process and the amount of fixing solution brought into the rinsing process were each 1 m ² 65 ml, 50 m
l, 50 ml, 50 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.2 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 l 1.0 l pH 10.05 10.15

(Bleach) Mother liquor (g) Replenisher (g) 1,3-Propylenediaminetetraacetic acid Ammonium ferric monohydrate 144.0 206.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Hydroxyacetic acid 63.0 90.0 Acetic acid 54.2 80.0 Water In addition 1.0l 1.0l pH [adjusted with ammonia water] 3.80 3.60

(Bleaching Fixing Solution Mother Liquor) 15:85 mixture of the above bleaching liquor mother liquor and the following fixing liquor mother liquor (fixing liquor) mother liquor (g) replenisher (g) ammonium sulfite 19.0 57.0 ammonium thiosulfate aqueous solution (700 g / l) 280ml 840ml Imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12.5 37.5 Add water to 1.0l 1.0l pH [adjust with ammonia water and acetic acid] 7.40 7.45

(Washing water) Common to mother liquor and replenisher tap water was prepared by using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-). Four
(00) was passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate dichloride and 150 mg / l of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5. (Stabilizer) Mother liquor, replenisher common (unit g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid Disodium salt 0.05 Water was added to 1.0 l pH 7.2

Samples 301-304 were imagewise exposed and then passed through the treatments described above. Samples 301-304 all gave almost similar images. 80 samples of this processed
When stored for 3 days under the conditions of ℃ and 70% RH, sample 30
Only in No. 2, yellow oily bleeding was observed on the surface.
This yellow oily matter was not observed in Samples 301, 303, and 304. From this, thinning (reduction of gelatin and HBS-1) as seen in Sample 302 is accompanied by deterioration of film quality, whereas when the compound of the present invention is used, thinning of film is accompanied by deterioration of film quality. It turns out that there is no such thing. Also, in the sample 302, the amount of W-3 used is changed to the samples 303 and 304.
Even if the amount was changed to 0.24 g / m ² similar to the above, exudation of the above oily matter was not improved.

[0144]

INDUSTRIAL APPLICABILITY The present invention uses the compound represented by the general formula (I) to agglomerate during the production of a photographic light-sensitive material.
A silver halide photographic light-sensitive material containing a hydrophobic photographically useful substance, which is emulsified and dispersed extremely finely without causing coalescence and extremely stable even after storage, without using a water-miscible organic solvent. It is a technology that can be supplied.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideki Naito 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, which contains a compound represented by the following general formula (I). . General formula (I) In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group or an α-furyl group, and may be the same as or different from each other. R ₁ and R ₂ may be linked to each other to form a ring. R ₃ , R ₅ , R ₈ and R ₁₀
Represents an alkyl group, an aryl group, an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. Also, R ₃ and R
₄ , R ₅ and R ₆ , R ₇ and R ₈ or R ₉ and R ₁₀ may be linked to each other to form a ring. R ₃ , R ₅ , R ₈ and R ₁₀ may be the same or different from each other.
R ⁴ , R ⁶ , R ⁷ and R ⁹ are hydrogen atoms or alkyl groups,
Aryl group, alkoxy group, halogen atom, acyl group,
It represents an amide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group. L ¹ and L ² each represent a chemical bond or a divalent linking group, and may be the same as or different from each other. M ¹ and M ² each represent a hydrogen ion, an ammonium ion or a metal ion,
They may be the same as or different from each other.