JPS62168145A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity, superior graininess and superior shelf stability at high temp. by reducing the total thickness of layers and using a coupler releasing a fogging agent. CONSTITUTION:The total thickness of all of hydrophilic colloidal layers on one side of a support having photosensitive silver halide emulsion layers on the side is restricted to 18mum on the dry basis and a compound (FR compound) releasing a fogging agent, a development accelerator or a precursor thereof by a reaction with the oxidized product of a developing agent is incorporated into at least one of the silver halide emulsion layers. A compound represented by the formula is preferably used as the FR coupler. By the combination of the reduced thickness with the FR coupler, a remarkably graininess improving effect is produced and the shelf stability at high temp. is improved. Since the color developability is improved, a sharpness improving effect is also produced by the reduced thickness.

Description

[Detailed description of the invention]

(Industrial Application Field 1) In recent years, color photographic materials for silver halide films with an ISO sensitivity of 1600 have been released, and
A photosensitive material having a sensitivity of 0.00 or higher is desired. Moreover, consumers are eagerly awaiting photosensitive materials with visually high image quality. The present invention relates to a color photographic material to meet such social needs.

PRIOR ART It is well known that after exposure of a silver halide photographic material, an oxidized aromatic 1ta amine developer and a dye-forming coupler react to form a color image. In this method, a subtractive color reproduction method is usually applied to form cyan, magenta, and yellow color images, which are complementary colors to red, green, and blue, respectively. The reaction between the coupler and the oxidation product of the color developing agent takes place at the active site of the coupler, and couplers with hydrogen atoms at this active site have 4
It is an equivalent coupler, ie, one in which stoichiometrically 4 moles of silver halide with development nuclei are required as an oxidizing agent to form 1 mole of dye. On the other hand, those having a group capable of leaving as an anion at the active site are 2-equivalent couplers, that is, couplers that require only 2 moles of silver halide having a development nucleus to form 1 mole of dye; Depending on the nature of the group, it is possible to vary the camping activity with the color developing agent over a wide range. Furthermore, two-equivalent couplers whose separation products have the effect of inhibiting development are development inhibitor-releasing couplers (
This is called a DIR coupler (DIR coupler), and because it suppresses development in proportion to the amount of developed silver, it has effects such as making the image finer, adjusting gradation, and improving color reproducibility. It can also be used in a diffusion transfer method by utilizing the effect on adjacent layers. It is also possible to use this type of coupler in a diffusion transfer method in which the leaving group contains a diffusible dye moiety and the leaving group is used to form a dye image of the diffusible dye on the image-receiving layer. It is called a dye-releasing coupler. Furthermore, certain colored two-equivalent couplers have a masking effect for color correction of dye images1, and this type of couplers are called colored couplers. In this way, various functions can be imparted to the 2-equivalent coupler by selecting the leaving group. The present invention provides couplers that release a fogging agent as a leaving group.
(fogging agent-releasing coupler; FoBantRel
EasingCoupler (abbreviated as Fl't coupler). Hereinafter, the compounds of the present invention will be referred to as F
It is called R coupler. In recent years, two major trends can be seen in silver halide photographic materials, particularly in photographic materials. One is IS
Could it be high sensitivity as typified by O1600 film? The first step is to improve image quality in response to smaller film sizes. Regarding the former, various methods have been studied, including increasing the size of silver halide grains, increasing coupler activation, and accelerating development. Regarding increasing the size of silver halide, see r and c. Farnell, J.B., Chanter+J., Pho.
As reported in Togr, Sci., 9.75 (1961), there is already a tendency for the sensitivity to reach a plateau, and even if the size is increased, no significant increase in sensitivity can be expected. Furthermore, increasing the size of silver halide grains is accompanied by various side effects such as deterioration of graininess. Many studies have been conducted on increasing the activation of couplers, but their contribution to sensitivity has not been sufficient.
It also has the disadvantage of worsening graininess. In order to accelerate development, the addition of various development accelerators such as hydrazine compounds to the emulsion layer or developer has been considered, mainly for black-and-white photosensitive materials, but all of these methods are accompanied by increased fog and deterioration of graininess. Many are not practical. As a method for improving this, a method is disclosed in JP-A-57-150845, in which the undeveloped silver halide grains in the vicinity of the silver halide grains where development has started are dabbed by emitting gabbling shavings imagewise, thereby starting development. 59-50439.59-
15763.59-170840.59-172640
．． 60-37556.60-154245.60-15
6059.60-128429.60-128430゜60-128431.60-153039.60-19
1241. The concept of such development accelerator-releasing couplers is based on the US-
3214377, IJs-3253924, Japanese Patent Application Publication No. 1973
-17437, and all of them aim to release thiocyanate ions and promote development through their dissolution physical development action. However, most commonly used emulsions are of the surface latent image type, and the rate at which the number of development starts increases due to dissolution physical development is small; rather, development is accelerated by increasing the number of development start points for each emulsion. As a result, graininess deteriorates. On the other hand, the coupler of the present invention releases the sulfur compound, which is thought to be caused by a reductive fogging effect due to an electron injection reaction into the silver halide during the polishing process, or by forming developable silver sulfide nuclei. It accelerates development by increasing the number of development starting points through the hanging action, and its mechanism of action is different from that of the above-mentioned dissolution physical development, and the development promotion action is also very large. In conventional conventional silver halide photographic materials, only the silver halide particles on which a latent image has been formed after being exposed to light are developed, but in the present invention, the fogging agent generated from the starting point of development 1ii1 is diffused, and the fogging agent in the vicinity is The undeveloped silver halide grains are deflected, one development starts, "!, multiple grains from ζ or 1 g
This enables the development of a plurality of I14 silver halide grains at the same time. In the present invention, the shavings are released imagewise. In other words, the emission from the capri part is small, and the higher the exposure, the more the release, and the higher the exposure, the greater the effect. On the other hand, it also enables development of silver halide grains with low exposure, which are hardly developed by normal exposure and development. As described above, the FR coupler was found to have an effect of not only increasing sensitivity but also improving graininess. In addition, in recent years, with the trend toward higher sensitivity and higher image quality, it has become important to reduce the thickness of the dried sample after coating. If the film is thin, the distance from the outermost surface (the surface furthest from the support side) will be shortened, which will improve developability and reduce light scattering, so theoretically graininess and sharpness will be improved. The trend is towards improving the sensitivity. However, in reality, when the film is made thinner, the graininess worsens. OBJECTS OF THE INVENTION A first object of the present invention is to provide a color photographic material that is highly sensitive and has excellent graininess. A second object of the present invention is to provide a color photographic material that has excellent storage stability under high humidity conditions. A third object of the present invention is to provide a color photographic material with excellent sharpness. As a result of extensive research, the present inventors have found that a red-sensitive 10-densified plate emulsion layer containing a cyan color-forming coupler is formed on a support, a green-sensitive silver lodenide emulsion scrap containing a magenta color-forming coupler, and a blue emulsion layer containing a yellow color-forming coupler. In a silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer, the total dry film thickness of all the hydrophilic colloid layers on the side having the photosensitive silver halide emulsion layer is 18 μm or less, and at least A silver halide color photograph characterized in that one photosensitive silver halide emulsion layer contains a compound that reacts with an oxidized herbal drug to release a deflecting agent, a development accelerator, or a precursor thereof. The object of the present invention could be achieved by means of a photosensitive material.

[Effects of the present invention]

As a result of intensive research by the present inventors, surprisingly, when a thin film was formed and an FR coupler was used in combination, not only no deterioration of graininess was observed, but also a noticeable effect of improving graininess was observed. Normally, when stored at high temperatures, an atmosphere becomes more easily oxidized by water, oxygen, etc., resulting in a situation where photosensitive nuclei and latent images are more likely to be bleached. This tendency becomes more obvious when thinning the film, but FR
The improvement in high-temperature storage stability with the combined use of Cicaplar is a surprising result. In addition, the effect of improving sharpness was also observed due to the improvement in color development when used in combination with FR coupler, which enabled the film to be made thinner. The present invention will be specifically described below. [Structure of the present invention] Fogging agent or development accelerator sound 11 used in the present invention
Alternatively, a compound that releases these precursors through a coupling reaction with an oxidized form of a developing agent (hereinafter referred to as a fogging agent-releasing compound of the present invention) is preferably represented by the following general formula (1). CI] Coup-(TIME')++1 D
^In the formula, Coup represents a coupler residue that can cause a coupling reaction with the oxidized product of an aromatic primary amine developer, and TIME' represents C through a force/bring reaction. After being separated from ul+, there is a timing group that releases D8, n is 0 or 1, D^ is a group that can be separated from Coup in the coupling reaction when nl is O, When nl is 1, it is a group that is released from TIME', has an adsorption property to silver halide grains, and has a substantially dabbing effect on silver halide grains. . Here, the term "group having a substantial fogging effect" refers to a group (compound) that produces a measurable fog when developed in the presence of the compound. The coupler residues represented by Coup include the following. Cyan coupler residues include 7E7-kabrar, naphthol coupler, and the like. 5 as a magenta coupler
- pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, ingenolone couplers, and the like. Yellow coupler residues include benzoylacetanilide couplers, bihaloylacetanilide couplers, malonoanilide couplers, and the like. Non-coloring coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid noester, imidazolinone, oxazolidine, thiazolinone, etc.). Furthermore, among the coupler residues represented by Coup''t', those preferably used in the present invention are of the general formula %.
), [■], CIX ], or (X). l1l R1° In the formula, R1 represents a 7-sylamide group, anilino group or a ureido group, and Ls represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups. (1) j: ■) [■] In the formula, R2゜ represents a halogen atom, a 7-sylamide group, or an aliphatic residue, R21 and R22 each represent an aliphatic residue,
Represents an aromatic residue or a heterocyclic residue. Further, one of R21 and R22 may be a hydrogen atom. a represents an integer of 1 to 4, b represents an integer of θ to 3, and C represents an integer of θ to 5. [■] In the formula, R23 represents a tertiary alkyl group or an aromatic residue, and R24 represents a hydrogen atom, a halogen atom, or an alkoxy group. 825 represents an acylamide group, an aliphatic residue, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom, or a sulfonamide group. In the formula, R26 is an aliphatic residue, an alkoxy group, a mercapto group, an alkylthio group, a 7-sylamide group, a flufkidicarbonyl group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, an acyl group, a noraflamino group. group, alkylsulfonyl group or 7-arylsulfonyl group, R2
7 represents a hydrogen atom, a halogen atom, an alkoxy group, a 7-syl group, a nitro group, an alkylsulfonyl group or an arylsulfonyl group, and enol esters of indanone can also be used in the present invention. (IXI R,ll In the formula, R28 represents an aliphatic residue or an aromatic residue, and
represents an oxygen atom, a sulfur atom or a nitrogen atom. (X) R2, -C-R,. ■ In the formula, R21 and R ◇ are each a blank space. However, R31, R32, and R33 each represent a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocycle, and W represents a nitrogen atom and 5 or 6 shell rings. Represents a group of nonmetallic atoms necessary for formation. R211 and R1° may form a 5- to 6-shell ring together with a necessary group of nonmetallic atoms. As described in US Pat. No. 4,248,962, JP-A No. 57-56837, etc., the timing group represented by TIME' can be separated from Coup by a coupling reaction, and then I)D by an intramolecular substitution reaction. Those who leave ＾,
British Patent No. 2,072,363A, Japanese Unexamined Patent Publication No. 154-1987
No. 234, No. 57-188035, etc., which leave D^ by electron transfer via a conjugated system, JP-A-5
No. 7-111536, which is a coupling component capable of decoupling D8 through a coupling reaction with an oxidized product of an aromatic primary amine developer. These reactions may occur in one step or in multiple steps. In the general formula (1) of the present invention, D^ is 111. When %Ill is 1, it is a group that can be separated from Coup in the coupling reaction, and when %Ill is 1, it is a group that can be released from TIME', and (i) has adsorption property to silver halide grains. , (ii) a group having a substantially distracting effect on silver halide grains. D^ is, for example, a group represented by ^BS (Q) + e1X3, or a group having both the effects or structures of ^BS and X in one group. Here, ^8S represents a group that can be adsorbed to silver halide grains, and Q is 2.
represents a valent linking group, X is a reducing group or a group capable of forming silver sulfide during development, and 1III is 0 or 1. When D^ is a group represented by ^BS-(Q)m+ -X3, the bonding position with TIME' is ^BS-(
Q) Any position in ml-X- is acceptable. Of course, as D^, a group having both the functions and effects of ^BS and X3 in one group is also preferably used. Further, 80S may be directly bonded to the carbon atom at the coupling position, or Q or X may be bonded to the coupling carbon as long as they can be separated by the coupling reaction. Also coupling carbon and 8B
What is known as a so-called 2-equivalent leaving group may be present between S. These groups include alkoxy groups (e.g. methoxy), aryloxy groups (e.g. ), a heterocyclic group (eg, pyridylthio), a heterocyclic group (eg, a higntoynyl group, a pyrazolyl group, a triazolyl group, a benzotriazolyl group, etc.). The pond described in British Patent Publication No. 2,011,391 can be used as D^. Examples of groups capable of adsorbing to halogenated atoms represented by ABS''C include nitrogen heterocycles having a dissociable hydrogen atom (
Virol, imidazole, pyrazole, triazole,
(tetrazole, benraimiguzole, benzopyrazole, benzotriazole, uracil, tetraazaindine, imigzotetrazole, pyrazolotriazole, pentaazainthin, etc.), with at least one nitrogen atom in the ring and a pond hetero Heterocycles (oxazole, thiazole,
thiazoline, thiazolidine, thianoazole, benzothiazole, benzoxazole, etc.), with 6 mercapto groups
two heterocycles (2-mercaptobenzothiazole, 2-mercaptobiriminone, 2-mercaptobenzothiazole, 1-phenyl-5-mercaptotetrazole, etc.), 4
salts (tertiary amines, birinone, quinoline, benzothiazole, benzimidazole, benzoxazole, etc.)
class salts), thio7er/-ols, alkylthiol compounds (
Examples include those consisting of thiourea, dithiocarbamate, thioamide, logenine, thiazolinonethione, thiohydantoin, thiobarbital acid, etc.). The divalent linking group represented by Q in Kennaka is commonly used alkylene, alkenylene, phenylene, naphthylene, -〇-1-S-1-SO-1-3O3-1N =N
-, carbonylamide, thio7mide, sulfonamide,
It is composed of a ring selected from ureido, thioureido, heterocycle, etc. The group represented by , polyamine, acetylene, ami/borane, tetrazolium salt, quaternary salt carbamic acid represented by ethylene bisbilinonium salt, etc.) or compounds that can form silver sulfide during development (thiourea, thio7mide, dithiocarbamate, rhodanine, thiohydantoin, thiazo compounds, etc.). Among the groups represented by X3, some of those capable of forming silver sulfide during development have adsorption properties to silver halide grains and can also serve as adsorption groups. D^ may be bonded to TIME or Coup at an adsorption site on the silver halide grain (for example, nitrogen atom of benzotriazole, sulfur atom of 1-722-5-mercaptotetrazole, etc.), but this is not necessarily the case. . In this case, a hydrogen atom is bonded to the adsorption site, or a group that can be hydrolyzed in the developer solution (
(e.g. acetyl group, benzoyl group, methanesulfonyl group) or a removable group (e.g. 2cyanoethyl group, 2
-notanesulfonylethyl group) is preferable, and examples of ^DS are shown below in the margins. Here is an example of how Q. u
b-CH2--Cil. C12--Ql:1i2
-OCH2CH25CH2- Examples of X are shown below. -NHN)IcHO-NHNHCOCH, -NHNHS
O2CII. -NHNHCOCF3 0OCJs Preferred examples of D^ are shown below. C1l□CH2CHO CH2C=CH NHCNIICH3 Preferred specific examples of the compound represented by the general formula (ff) are as follows. Below are the margins (F-1) (F-2) (F-7). H3 (F-10) (F-11) (F-12) CI. (F-13) CI! (F-14
) (F-15) (F-16) (F-17) 0 ■ (F-18) H (F-23) (F-24) u (F-25) (F-26) (F-27) n-C+ 5H3tOcOcHcOOc+ J3t-n
(F-28) CH
3. The fogging release compound of the present invention is disclosed in, for example, JP-A-57-
It is synthesized according to the synthetic route described in No. 150845. The JQ agent-releasing compounds of the present invention can be introduced into silver halide emulsion layers by known methods, such as U.S. Pat.
The method described in No. 27 is used. For example, furkyl 7 ether (di-tert)yl 7 ether, ditertiary amylphenol, 7 tar acid alkyl esters (dibutyl 7 thalate, dioctyl 7 talate, etc.), phosphoric acid esters (diphenyl 7 male 7 2- to,
Tori 7 Enil 7t Sufu! -),) Likurenol sulfate, nooctylbutyl sulfate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide) , fatty acid esters (e.g. dibutoxyethyl succinate,
octyl 7 gelate), trimesate ester M (e.g. tributyl trimesate), or a boiling point of about 3
After dissolving in an organic solvent at 0°C to 150°C, for example, lower alkyl acetate such as ethyl acetate or butyl acetate, 70 ethyl pionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Also, Japanese Patent Publication No. 51-39,853, Japanese Patent Publication No. 51-59,
The polymer dispersion method described in No. 943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. In the present invention, the fogging agent releasing compound is
It is preferable that 1X10-" to 1X10-" mol is added, and more preferably 1X10-3 to 1X10-' mol, per 1 mol. The dry film thickness according to the present invention is measured under conditions where the humidity is controlled to 23° C. and 55%. The lower limit of the total dry film thickness of all the hydrophilic colloid layers on the side having the emulsion layer (hereinafter referred to as "film thickness on the emulsion side") includes /10 Silver denide emulsion, oil M such as coupler, additives There is a limit depending on the volume occupied by gelatin and other pigments, and the preferred film thickness on the emulsion surface is 5 to 18 microns, more preferably 8 to 17 microns. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14μ or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is different from the emulsion layer in photosensitivity and closest to the support is 1
Preferably 0μ or less. The silver halide emulsion used in the present invention includes silver 10-dendide such as silver bromide, silver iodine, silver iodochloride, silver chlorobromide, and silver chloride. Any compound commonly used in silver lodenide emulsions, such as silver chloride and silver chloride, can be used, but silver bromide, silver iodobromide, and silver chloride iodobromide are preferred. Is silver lodenide grains used in silver halide emulsions are
It may be obtained by any of the acidic method, neutral method and 7-ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, 10denide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. In addition, while increasing the critical growth rate of 7% silver lodenide crystals to IfIM, /10 denride ions and silver ions were generated by sequentially and simultaneously adding l)H+l)Ag in a mixing pot while controlling the concentration of l)H+l)Ag. good. By this method, silver denide grains having a regular crystal shape and a nearly uniform grain size of % Iff can be obtained. Conversion methods may be used at any step of the Ag formation to change the halogen composition of the particles. Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains. Silver halide grains are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), ronium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. The silver halide emulsion may be freed of poorly soluble salts after the growth of silver halide grains is completed, or may be left containing them. When removing the salts, Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17463, Section (2) may be used. The silver halide grains may have a uniform silver denide MLr& distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of 11001 planes to 1llll1 planes can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used. Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. The monodisperse emulsion referred to here refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less, where the grain size is spherical) 10 In the case of silver denide, the diameter is shown, and in the case of particles with shapes other than spherical, the diameter is shown when the projected image is converted into a circular image of the same area. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used. Pigments useful for marking include cyanine dyes, merocyanine dyes,
It is a complex merocyanine pigment. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention are coated with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength.
Hardening can be achieved by using n or two or more types. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylo/lenomethyl-hydantoin, etc.), oxane derivatives (2,3-dihydroquinnooxane, etc.), Active vinyl compound (1,3,
5-) lyacryloylhexahydro-5-) riazine, 1,3. -vinylsulfonyl-2-propanol, etc.), active nos-lodene compounds (2,4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids
(mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in layer top A of RD 17643. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycytyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or these and acrylic acid, Polymers containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (°meth)7 acrylate, styrene sulfonic acid, etc. as monomer components can be used. The emulsion layer of the light-sensitive material contains a dye that forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenenoamine derivative, aminophenol derivative, etc.) during color development processing. Forming couplers are used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, a /10 silver denide color photographic light-sensitive material may be produced using a method different from the above combination. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. , hardener, capri agent, capri prevention J
Compounds that release photographically useful 7-ragments such as '111, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release development inhibitors during development and improve image sharpness and image graininess are D.
It is called an IR coupler. Instead of the DIR coupler, an old R compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. The DIR couplers and DIR compounds used include those in which an inhibitor is directly bonded to the coupling position, and those in which 1 before suppression is bonded to the coupling position via a divalent group, and the group is separated by the coupling reaction. Intramolecular nucleophilic reaction,
Included are compounds in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as timing Drll couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
5.057, 3.265,506, 3.4
No. 08,194, No. 3,551,155, No. 3,
No. 582.322, No. 3,725.072, No. 3
．． No. 891,445, West German Patent No. 1,547,868,
West German Application No. 2,219,917, No. 2,261,3
No. 61, No. 2,414,006, British Patent No. 1.42
No. 5,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 51-21827,
No. 51-102636, No. 52-82424, No. 5
No. 2415219, No. 58-95346, etc. As magenta dye-forming couplers, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, IIIirt
Acylacetonitrile-based caprajyl indasilone-based couplers and the like can be used. Specific examples of magenta color forming couplers that can be used include, for example, U.S. Pat. Nos. 2,600,788 and 2,983,608
No. 3,062,653, No. 3,127,26
9, f13,311.476, f13,311.476, f13,311.419,
No. 391, No. 3,519,429, No. 3.558
．． 319, 3.582.322, 3.61
No. 5,506, @3.834,908, No. 3.8
91,445, West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2,408.665, West German Patent No. 2,4
No. 17,945, No. 2,418.959, No. 2.42
No. 4,467, Special Publication No. 40-6031, 'Vj Kaisho 4
No. 9-74027, No. 49-74023, No. 49-1
No. 29538, No. 50-60233, No. 50-159
No. 336, No. 51-20826, No. 51-26541
Examples include those described in Japanese Patent Application No. 52-42121, No. 52-58922, No. 53-55122, and Japanese Patent Application No. 55-110943. As cyan dye-forming couplers, phenol or 7-tole couplers are generally used. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat.
No. 23.730, @ No. 2,474,293, No. 2
t801,171, 2,895,826, 3.476.563, 3,737,326, 3,758,308, 3,893,044 , JP-A-47-37425, JP-A-50-10135, JP-A-50-25228, JP-A-50-112038, JP-A-50-117422, JP-A-50-130441, etc.; Couplers described in Japanese Patent No. 58-98731 are preferred. Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, stir in a hydrophilic binder such as gelatin aqueous solution using a surfactant,
After emulsifying and dispersing using a dispersion means such as a homonizer, colloid mill, 7o-knot mixer, or ultrasonic device,
It may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion. The following high boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, alkyl heptatarates, distyl phosphates, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. An organic solvent having a temperature of 150°C or higher is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Low boiling point substantially water-insoluble organic solvents include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, VA
Examples include tn-jXZ, nitromethane, nitroethane, and benzene. When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. Hydrophilic colloids can also be introduced. A hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent, and fi? Anionic surfactants, /ionic surfactants, cationic W-surface active agents, and amphoteric surfactants can be used as dispersion aids when dispersing in water using high-speed or high-frequency sound waves. . The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable. The color antifoggant may be contained in the emulsion layer itself, or
An intermediate m layer may be provided between adjacent emulsion layers and contained in the intermediate layer. An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of RD17643. Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain an ultraviolet absorber to prevent capri from discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. A development delay resistant agent or bleach accelerator can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material. Compounds that can be preferably used as development retardation waste are the compounds described in Section XXI, Section E of No. 17643. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section V of RD 17843. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. These dyes and/or emulsion layers may contain dyes that flow out from the light-sensitive material during development or are bleached. Such dyes include oxonol dyes, hemioxol dyes, hemioxol dyes, Examples include styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. A matting agent can be added to the silver halide emulsion layer and/or its underlying hydrophilic colloid layer for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers and esters of acrylic acid and methacrylic acid, polyvinyl resin, Examples include polycarbonate and styrene polymers and their copolymerization rates. The particle size of the matting agent is 0.05μ to lOμ
Norano is preferred. The amount to be added is 1 to 3ooI11bi/
162 is preferred. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and/or the emulsion layer on the side where the Vt layer is attached to the support. It may also be used in colloid layers. Preferably used antistatic agents are the compounds described in RD 17643 Xff [. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (promotion of development, hardening, sensitization, etc.). The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymerization rate), synthetic paper, semi-synthetic materials such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of molecules, flexible supports on which these films are provided with reflective layers, glass, metals, ceramics, etc. After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be coated through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which are so reactive that if added to the coating solution in advance will cause gelation of the coating, it is recommended to mix them using a static mixer or the like immediately before coating. preferable. As coating methods, extrusive polish coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, 7-ion surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamines, quaternary ammonium salts, pyridine, and others. heterocycles, cationic surfactants such as phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric esters, and phosphoric esters; amphoteric surfactants such as amino acids, amine/sulfonic acids, and sulfuric or phosphoric esters of amino alcohols may also be added. Moreover, it is also possible to use a fluorine-based surfactant for the same purpose. To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, it is also possible to perform a bleach-fixing process using a 1-bath bleach-fix solution, and the 1-bath bleach-fix process J! It is also possible to carry out a monobath treatment process using a liquid. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, a color developing agent or its precursor may be contained in the material and the development process may be performed with a 7 activator solution, or a 7 activator solution may be used for the monobath treatment. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Process/Pre-shelf film processing process - Color development process - Stop fixed stone process - Water washing process - Bleaching process Constant fixation process - Water washing process - Post hardening process/color development process - Water washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process / Activator process - Bleach-fix process - 7 Activator process - Bleach process Constant fixation process / Monobath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C. A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes amino 7-ether derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of developing acids and inorganic acids, such as chloride acids, sulfates, p-)luenesulfonates, sulfites, oxalates, benzenesulfonates, etc. I can do it. These compounds generally have a color developer IQ of about 0.
．． Concentration of 1 to 30 g, more preferably color developer 11
It is used at a concentration of about 1 to 15 g. If the amount added is less than 0.1 g, sufficient color density cannot be obtained. Examples of the above-mentioned Ami/7 el/-based developer include 0-7
Minophenol, p-7 mi/7 er/-, 5-7 mi/-
Included are 2-oxy-toluene, 2-7 minnow-3-oxy-toluene, 2-oxy-3-7 minnow-1,4-methyl-benzene, and the like. Particularly useful primary aromatic amine-based color development abrasions include N, N
-difurkyl-1)-phenycyamine M compound, in which the furkyl group and the phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N-tmethyl-1)-phenylenediamine salt fi[, N-methyl-
p-phenylenediamine ml, N,N-tumethyl-
p-7 2-diamine hydrochloride, 2-ami/-5-(N
-ethyl-N-dodecyl7mi/)-)luene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate, N-ethyl-N-β-hydroxyethylamino 7-niline, 4-amino-3-methyl-N, N-noethylaniline, 4-7 minnow N-(2
-nodoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfone), and the like. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. In this case, it is also possible to treat the silver halide color photographic material with an alkaline solution (7 activator solution) instead of a color developing solution, and immediately after the alkaline solution treatment, the material is bleached and fixed. The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. and also various additives, such as benol alcohol, alkali metal herodides, such as potassium bromide. Alternatively, it may contain potassium chloride, etc., or a development regulator such as anthranonic acid, and a preservative such as hydroxylamine or sulfite. In addition, various antifoaming agents and
A surfactant and an organic solvent such as methanol, dimethylformamide or dimethyl sulfoxide may be appropriately contained. The color developer used in the present invention usually has a PU of 7 or more,
Preferably it is about 9-13. In addition, the color developing solution used in the present invention may optionally contain antioxidants such as noethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, Pentose or hexose, pyro7ycol-1
, 3-dimethyl ether, etc. may be contained. In the color developing solution used in the present invention, various chelate compounds can be used as metal ion sequestering agents.
For example, ethylenenoaminetetraacetic acid as the chelate,
Diethylenetriamine five vinegar l! ! 7-minobolycarboxylic acid, 1-hydroxyethylidene-1,1'-7 phosphonic acid, etc. ! Phosphonic acids, amino/polyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenenoaminetitralinic acid, citric acid, oxycarboxylic acids such as gluconic acid, 2-phospho/butane (1.2.4-)
Examples include phosphonocarboxylic acids such as recarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid such as hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be carried out simultaneously with the fixing process, or may be carried out separately. As bleaching agents, complex salts of the ft group of organic acids are used, such as polycarboxylic acids, amino/polycarboxylic acids, or organic acids such as oxalic acid and citric acid, coordinated with metal ions such as iron, cobalt, and copper. used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and amide/polycarboxylic acids. Specific examples of these include ethylenenoaminetitraacetic acid, noethylenetriaminebentaacetic acid, and ethylenenoamine-N-(β-oxyethyl).
-N. N',N'-) diacetic acid, pro- and di-7minetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, imi7noacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ethernoamine titraacetic acid,
Glycol ether diamine tetraacetic acid, ethylene? )
Examples include aminetetrapropionic acid and phenylenediaminetetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches contain 5 to 450 g/l, more preferably 2
Use at 0 to 250 fI/f. In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron(I[I) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． 0 to 9.5, preferably 4.5 to 8.0, and most preferably 5.0 to 7.0. A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiosulfate, and thiocyanine, which are used in ordinary fixing processing, are used. Typical examples include thiocyanates such as potassium acid, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 70 to 250 g/I or more, but is generally within the range of soluble. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.1) H loose lj
m can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, and surfactants can be contained. In addition, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as amide/polycarboxylic acids, stable M such as nitro alcohols and nitrates, and hardening agents such as water-soluble aluminum salts. , methanol, dimethylsulfamide, dimethylsulfoxide, and other organic solvents may be contained as appropriate. The fixer is used at a pH-r of 3.0 or higher, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9. The bleaching agents used in the bleach-fix solution include those listed in the bleaching process above. Mention may be made of metal complex salts of acids, and the preferred compounds and concentrations in the treatment solution are also the same as in the above bleaching treatment step. The bleach-fix solution contains a silver heronide fixer in addition to the above bleaching agent, and if necessary, a solution containing sulfite as a preservative is applied. In addition, iron ethylenediaminetetraacetate (IT[) complex salt bleach and halogenated f
i. Bleach-fix solutions containing small amounts of halides such as ammonium bromide in the fixer pond, or conversely bleach-fix solutions containing large amounts of halides such as ammonium bromide; A special bleach-fix solution having a composition consisting of a combination of an iron acetate (■) complex salt bleach and a large amount of a halide such as ammonium bromide may also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above. The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5. [Example-1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. In all the examples below, the amount of oil added in the silver halide photographic light-sensitive material is 1 m2, unless otherwise specified. In addition, silver halide and Floyd silver are shown in terms of silver. Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetylcellulose film support from the support side. Sample-1 (comparison) First layer; antihalation layer (IC-1) Gelatin layer containing black colloidal silver. Intermediate layer (1,L,) in the second MI: a gelatin layer containing an emulsified dispersion of 2.5-not-t-octylhydroquinone. 3rd N: Low sensitivity red-sensitive silver halide emulsion layer (RL-1
) Average grain 4 (r) Monodisperse emulsion (milk El) consisting of 8 g Brl containing 0.30 μm + 16 mol % of silver...Amount of silver coated 1.89/m2 Sensitizing dye I... Silver 1 6 x 10-' moles per mole of sensitizing dye ■... 1 per mole of silver. OX 10-5 Morcian coupler (C-1)...0.06 per mole of silver
Molar colored cyan coupler (CC-1)...0.003 mol per mol of silver DJII compound (D-1)...0.0015 mol per ml DI11 compound ( D-2)...0.002 mol 47th ffl per 1 mol of silver; Highly sensitive red-sensitive silver halide emulsion layer (I
IH-1) Average particle size (7) 0.5 μm11. Heg17
, 0 mol% of ΔgDr l (emulsion ■)...silver coating amount 1.3 g/l11
2 Sensitizing dye I... 3 x 10-' mol per 1 mol sensitizing dye ■... ff 1. OX 10 Morun Uncoupler (C-1)...0.0 per mole
2 mol colored cyan coupler (CC-1) 0.0015 mol DIR compound (D-2) f! i 0.001 mol per 1 mol No. 5M; Intermediate layer (1, L,) Same as No. 2N, gelatin layer. 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1
) Emulsion-I... Coating silver jt1.5g/l1
12 Sensitizing dye ■・・・・・・ 2,5× 10−’ mol per mole of ff Sensitizing dye ■・・・・・・ 1,2× 10−5 mol magenta coupler (M -1)...0.0 per ii mole
50 mole colored magenta coupler (CM-1)...
0.009 mol DIR compound (D-1) per 11 mol ff 0.0010 mol DIR compound (D-1) per 11 mol ff
D-3)... ff11 mol 1 mol larger size 0,
00:30 mol 7th WI; Highly sensitive green-sensitive silver halide emulsion layer ([1; I+-1) Emulsion - ■... Coated silver amount 1,4y/m" Sensitizing dye ■...・・1.5X 10-' mol sensitizing dye per ml mol■・
... t, ox to s moles per mole of silver Magenta coupler (M-1) ... o, o per mole of silver
zomol colored magenta coupler (CM-1)...
@0.002 mol DIR compound per 1 mol (
D-3)...0.0010 per mole of silver
Mole 8th layer; Yellow filter single layer (VC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-not-t-octylhydroquinone. 9th layer; low sensitivity blue-sensitive silver halide milk layer (BL-1)
Average particle size 0.48μ-, 8gBr containing 16mol% Heg
Monodispersed emulsion (emulsion ■) consisting of 1 silver coated amount: 0.9 y/m2 Sensitizing dye ■... 1.3X 10-S mol yellow coupler (Y -1) per 1 mol of silver )...0.0% per mole of silver.
29 mol 10th layer: Highly sensitive blue-sensitive emulsion layer ([1+1-1) Monodispersed emulsion (emulsion ■) consisting of 88 BrI with an average grain size of 0.84 m and containing 115 mol % of Ag...silver coating amount 0. 5g/m2 Sensitizing dye V...1. OX 10-' mol Yellow coupler (Y-1)...O per 1 mol of silver,
OS mol DIR compound (D-2)...0.0015 mol per mol of silver 11th layer; 1st protection N (Pro-1) Silver iodobromide (8 g [1 mol% average Particle size: 0.07μ1m) Silver coating amount: 0.5
47 Yagi 2 12th gelatin layer containing ultraviolet absorbers UV-1 and UV-2; 2nd protective layer (Pro 2) polymethyl methacrylate particles (diameter 1°, 5 μff1) and formalin scavenger (Its-1> In addition to the above composition, each layer contains a gelatin hardening agent (H-1).
and surfactants were added. The compounds contained in each layer of Sample 1 are as follows. Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl 3,3'-no (3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl 3,3'-no (
3-sulfopropyl) 4+5+4', 5''-
Dibenzothi7carpocyanine hydroxide sensitizing dye ■; Anhydro 5,5'-nophenyl-9-ethyl 3,3''-no (3-sulfopropyl)oxacarposi7ine hydroxide sensitizing dye ■; Anhydro 9-ethyl- 3,3′-no(
3-sulfopropyl)5,6゜5',6'-nobenzoxacarbocyanine hydrokind sensitizing dye Margin below methoxythiacyanine C-t H H H M-1 rσ I 1V-1 0■ C4119(L) V-2 In the same manner as Sample 1, type and amount of FR coupler added to the 7th layer. Samples with varying sums of the dried film j7 of the wood-philic colloid layer were prepared from No. 2 to No. 12, and the results are shown in Table 1. The amount was adjusted by changing the amount. Samples Nos. 1 to 12 prepared in this way were exposed to sea urchin light using white light, and then subjected to the following development treatment. Processing step (38°C) Color development 3 minutes 15 Sec) White paper 65 ml, 30 seconds wash
3 minutes 15 seconds constant '4 a minute:; 0 seconds washing with water
Stabilization for 3 minutes and 15 seconds and drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows. [Color development liquid] 4-7mi/-3-methyl-N-ethyl-N-(β-hydroxylethyl)-7niline sulfate 4.75g Anhydrous sodium sulfite 4.25g hydroxylamine 1/2 Sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid.
Trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.03 Add water to make 11. [) White liquid] Ethylenediaminetetraacetic acid iron ammonium salt 100. . Ethylenediaminetetraacetic acid diammonium salt 10.0. 7mmonicum bromide 150.0 g Glacial acetic acid 10.0 t Add water to make 11, and use rum water to make 1]11=6
．． Adjust to 0. [Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.52 Sodium metasulfite 2.3 g Add water to 11
Then, add acetic acid to adjust pl+ to 6.0. [Stabilizer] Formalin (37% aqueous solution) 1,5z
1 Funig Nkusu (Konishi Roku Photo Industry 5i!> 7
, 5xl water to make 11. 5-U, below margin: / Book 1 - Amount of water added per mole of silver 2 ----
The relative value of the reciprocal of the exposure amount that gives the fog density of the magenta image +0.1 is the RMS value of the minimum density of the magenta image +1.
The concentration of No. 2 is expressed as a value 1000 times the standard deviation of the variation in concentration value that occurs when scanning with a microdecimometer having an aperture scanning area of 250 μl 112 times. Tree 4 - After applying the sample, the density of the magenta image is changing at the same exposure amount for a sample that was conditioned to 55% humidity at 23℃ and a sample that was further conditioned to 60% humidity at 50℃. is expressed as a percentage. As is clear from the results in Table 1, the total dry film thickness is 18
μ or less and that when used in combination with a suitable mF coupler, sensitization is achieved and graininess and high-temperature storage stability are significantly improved. Incidentally, the results of visual evaluation of samples Nos. 1 to 12, which were actually printed on photographic paper, were also the same. [Example-2] Sample No. 1 of Example-1 A sample identical to 1 was prepared, and the type and amount of FR coupler added to the fourth layer and the total dry film thickness of all hydrophilic colloid layers were determined. Changed sample N
No. 2 to 12 were prepared, and the results are shown in Table 2. The following margins are 1------Amount added per mole of the group 2------~
The relative value of the reciprocal of the exposure amount that gives the fog density of the cyan image +0.1 *3-11~-RMS value is the minimum density of the cyan image +1.2
The density is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning with a microdecimometer having an aperture scanning surface Mt of 250 μm 2 . Wood 4 - After applying the sample, the sample was kept humid at 23°C 55%: A and the sample was further conditioned to 50°C 60%.
The difference in cyan image density at the exposure point is shown. As is clear from the results in Table 2, the total force of dry film thickness '1
811710 or less and when used in combination with an appropriate uF coupler, it is sensitized and graininess and high-humidity storage stability are significantly improved! I understand the basics. Incidentally, the results of visual evaluation of the printing of samples Nos. 1 to 12 on photographic paper were also the same. 1. Permission: Roku Konishi Roku Photography Industrial Company Procedural Amendment (Method) 5 April 23, 1986 6゜1985 Patent Application No. 11742 2 Name of Invention Silver Halide Color Photographic Light-sensitive Material 3 , Relationship with the case of the person making the amendment Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact address: Konishiroku Photo Industry Co., Ltd., 1-Sakura-cho, Hino-shi, Tokyo, 191 Japan (0425-83-1521)
Target of amendment by the Patent Department, content of amendment to the specification

Claims (1)

[Claims] A silver halide color having a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, and a blue-sensitive silver halide emulsion layer containing a yellow color-forming coupler on a support. In the photographic light-sensitive material, the total dry film thickness of all the hydrophilic colloid layers on the side having the photosensitive silver halide emulsion layer is 18 μm or less, and at least one photosensitive silver halide emulsion layer contains a developing agent. A silver halide color photographic material containing a compound that reacts with an oxidant to release a fogging agent, a development accelerator, or a precursor thereof.