JPH01186938A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity and granular characteristic by using silver halide particles of a specific size to constitute at least one layer of emulsion layers and allowing silver iodobromide contg. a specific ratio of silver iodide to exist in a distinct laminar structure in the silver halide particles and specifying the content of the silver iodide over the entire part of the particles. CONSTITUTION:The emulsion in at least one layer of the emulsion layers consists of the chemically sensitized silver halide particles having <=1.7mum average particle size and the silver iodobromide contg. 30-45mol.% silver iodide exists in the silver halide particles by having the distinct laminar structure; in addition, the content of the silver iodide over the entire particles is specified to <=15mol.% The preferable total content of the silver iodide is 15-25%, more particularly preferably 15-20mol.%. The high sensitivity, decreased fogging and excellent granular characteristic are thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material, and particularly to a color photographic material with excellent sensitivity and graininess.

(Prior Art) The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, fine grains, and high development activity. Particles with a clear layered structure consisting of parts with different halogen compositions improve light absorption, improve quantum sensitivity by preventing recombination, improve development progress, and prevent development from proceeding too much. Contributed to improving basic performance through improvements in grain quality, etc. (
Particles with a clear layered structure have been shown to be useful in the case of dog-sized particles or in the case of more isotropic particles with a low aspect ratio; He has contributed to the development of sensitive materials. However, insufficient attention has been paid to the demands for higher sensitivity and higher image quality, and further efforts have been made to develop emulsion grains with high silver iodide content, fine-grained grains with a clear layered structure, and tabular grains with a high asquick ratio. In the case of particles having a layered structure, the conventional techniques were also unsatisfactory.

(Objectives of the Invention) Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material that is highly sensitive, has little capri, and has excellent graininess.

An object of the present invention is to provide a silver halide emulsion with high light absorption efficiency and high development activity, and a color photographic light-sensitive material using the same.

DISCLOSURE OF THE INVENTION These objects of the present invention are to provide on a support at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer. In a silver halide color photographic material having a metal layer, at least 15 emulsions in the emulsion layer have an average grain size of l.

It consists of chemically sensitized silver halide grains of 7 μm or less, in which silver iodobromide containing silver iodide of 3O-4Cj molar ratio exists in a clear layered structure, and The silver iodide content in the entire grain is 1. One of the reasons for the high sensitivity of the silver halide emulsion used in the present invention, which is achieved by the silver halide color photographic light-sensitive material which is characterized by having a molar ratio of at least t molar ratio, is that it reduces the development activity. This is partly due to the increase in light absorption due to the high iodine content, but an even greater effect is due to the fact that the core of the particle has a clear layered structure containing a high iodine layer and the outermost layer contains a low iodine layer, which reduces the amount of latent image. This is thought to be due to improved formation efficiency.

The clear layered structure mentioned here can be determined by the method of X-ray diffraction. An example of the application of the X-ray diffraction method to silver halide grains is described in H. Hirsch's Journal of Photographic Science, Volume 10, page 12 onwards. If the lattice constant is determined by the halogen composition, Black's condition (2dsinθ=nλ)
A diffraction peak occurs at a diffraction angle that satisfies .

Regarding the measurement method of X-ray diffraction, please refer to the Basic Analytical Chemistry Course λu "X
It is described in detail in ``X-ray Analysis'' (Kyoritsu Shuppan) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.). The standard measurement method uses a cut as a target and uses β-rays as a radiation source (tube voltage 4!).

(kV, tube current: OmA) This is a method for determining the diffraction curve of the (C20) plane of silver halide. To increase the resolution of the measuring machine, slits (divergent slit, light receiving slit, etc.)
It is necessary to appropriately select the width of the goniometer, the time constant of the device, the scanning speed of the goniometer, and the recording speed, and to confirm the measurement accuracy using a standard sample such as silicon.

A clear layered structure in the present invention means that the curve of diffraction intensity versus diffraction angle of the (-220) plane of silver halide is determined using Cu (DKβ ray) with a diffraction angle (λθ) in the range of 3r0 to 4c2°. When obtained, at least two diffraction peaks, one corresponding to a high iodine layer containing 30-≠j mol of silver iodide, and the other diffraction peak corresponding to a low iodine layer containing less than t mol of silver iodide. There is a maximum and one minimum between them, and the diffraction intensity corresponding to the high iodine layer is 10 to 3/l compared to the peak diffraction intensity corresponding to the low iodine layer. More preferably, the diffraction intensity ratio is //j~3
/1. This is especially the case for I/J~3//.

In the present invention, the emulsion having substantially two distinct layered structures is more preferably a diffraction maximum (peak) with a minimum diffraction intensity between two peaks, which has a weaker intensity. It is preferable that the ratio is 20 or less.

More preferably r0 or less, particularly preferably 4
04 or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 1/Lattice Defects (Kyoritsu Publishing).

This book is useful for analyzing curves using a Du Pont curve analyzer, assuming that the curve is a function such as a Gaussian function or a Lorentzian function.

Even in the case of an emulsion in which two types of grains having different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction.

As described above, emulsions cannot exhibit the excellent photographic performance obtained by the present invention.

In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the EPMA method (E
Electron-Probe Micro.

This becomes possible by using the Analyzer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and the sample is then irradiated with electron beam gold. [X-ray analysis using electron beam excitation] Elemental analysis of extremely small parts can be performed.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

By confirming the halogen composition of at least 30 grains by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention.

In the emulsion of the present invention, it is preferable that the iodine content among the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is preferably to4 or less, more preferably 31% or less.

Another preferred interparticle iodine distribution is one in which particle size and iodine content exhibit a positive correlation. In other words, the iodine content of large size particles is high and the iodine content of small size particles is low.

Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is ≠0 or more, and furthermore, roI
It is preferable that it is S or more.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

The composition of the outermost layer is silver halide containing silver iodide with a molar coefficient below r, and more preferably! It is a silver halide containing silver iodide below the molar coefficient.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

Regarding the total halogen composition, the silver iodide content is 13'
The effect of the present invention is remarkable when the amount is more than 1 molar.

A more preferable total silver iodide content is l! ~Ko! It is particularly preferable to use l! ~20 moles or more.

The size of the silver halide grains having a clear layered structure of the present invention is preferably 1.7 μm or less, and furthermore, i3
It is preferably 1.2 μm or less, particularly 1.2 μm or less.

The silver halide grains having a clear layered structure of the present invention may have regular crystal shapes (normal crystal grains) such as hexahedron, octahedron, dodecahedron, and dodecahedron. , or may have an irregular crystal shape such as spherical, potato-shaped, or tabular.

In the case of normal crystal particles, particles having (///) planes '1jO4 or more are particularly preferred. Even in the case of irregular crystal forms (///
) Particles having a coefficient of 30 or more are particularly preferred. (//
/) surface ratio can be determined by the Kubelka-Munk dye adsorption method. This is (///) face or (ioo)
A dye is selected that preferentially adsorbs to one of the planes and the association state of the dye on the (/l/) plane is different from the association state of the dye on the (100) plane in terms of the spectral spectrum. The area ratio of the (//l) plane can be determined by adding such a dye to an emulsion and closely examining the spectral spectral spectral spectral response to the amount of dye added.

Although the emulsion of the present invention can have a wide grain size distribution, a sandwiched emulsion with a grain size distribution is preferred. In particular, in the case of regular crystal grains, the size of the grains occupying 204f of the total of each emulsion in terms of the weight or number of silver halide grains is within ±≠oL4 of the average grain size, and further ±30 (4
Monodisperse emulsions such as those listed below can also be used.

The effect of the present invention can be best seen in twin grains. It is preferable that tabular grains having λ or more parallel twin planes are contained in a projected area of 30 or more, preferably j0 or more, more preferably 70% or more.

The emulsion of the present invention having a clearly layered structure can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble silver salt and soluble halogen salt can be selected from one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method of keeping pAgt constant in the liquid phase in which silver halide is produced, that is, a controlled double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (eg, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.

Silver halide solvents such as ammonia, rhodan salts, thioureas, thioethers, and amines may be selected and used during core preparation. It is desirable that the emulsion has a narrow grain size distribution of core grains. The monodisperse core emulsion mentioned above is preferred. It is desirable to have an emulsion in which the halogen composition and iodine content of individual grains are more uniform at the core stage.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particles is more uniform, the diffraction width of X-ray diffraction becomes narrower and sharper peaks are obtained.

After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
A method of accelerating the addition rate over time is disclosed in Irie and Suzuki's Special Publication μR-Styli No. 0, or by Saito in US Patent No. ≠.

2442, $4! Uniform silver iodobromide can also be obtained by the method disclosed in No. J, in which silver iodobromide grains are grown by increasing the additive concentration over time.

These methods give particularly favorable results. Irie et al.'s method involves the production of poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid. , be added at an addition rate Q that is above a certain temperature acceleration and below an addition rate that is proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, at a rate not less than Q = r and not more than Q = αt + βt + r. It is something.

On the other hand, Saito's method is a method for producing silver halide crystals in which two or more types of inorganic salt aqueous solutions are simultaneously added in the presence of a purulent colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. It increases the level of purity that never occurs. The real deal! In preparing silver halide grains having a clear layered structure, shelling may be carried out directly after the formation of fur grains, but it is preferable to carry out shelling after washing the core emulsion with water for desalting.

Shelling can also be prepared by various methods known in the field of silver halide photographic materials, but a simultaneous mixing method is preferred. The aforementioned methods of Irie et al. and Saito's method are preferred as methods for producing emulsions having a clear layered structure.

In the case of fine-grain emulsions, conventional tools are useful for preparing grains with a well-defined layered structure, but they alone are not sufficient to increase the degree of completeness of the layered structure. First, it is necessary to carefully determine the halogen composition of the high iodine layer. Silver iodide and silver bromide each have different thermodynamically stable crystal structures, and it is known that mixed crystals are not formed at all composition ratios. The mixed crystal composition ratio depends on the temperature during particle preparation, but 30
It is important to select the optimum one from within the range of ~lj molar range. Although the stable mixed crystal composition ratio depends on the atmosphere, J
It is estimated that it exists in O-4J-mol. When growing a low iodine layer outside the high iodine layer, it is of course important to select the temperature, pY, pAg, stirring conditions, etc., but it is also important to select the amount of protective colloid when growing the low iodine layer. and a spectral sensitizing dye,
It is preferable to take measures such as growing a low iodine layer in the presence of a compound adsorbed on the surface of silver halide, such as an antifoggant or a stabilizer. It is also effective to add fine grain silver halide instead of adding water-soluble silver salt and water-soluble alkali metal halide when growing a low iodine layer.

As mentioned above, in the present invention, silver halide grains having a clear layered structure mean that the grains contain λ of different halogen compositions.
It has been explained that there are essentially three or more regions, and the center side of the particle is the core part, and the surface side is the shell part.

Substantially λ means a third region (in addition to the core and shell).
For example, the presence of a layer (intermediate between the central core and the outermost shell) also means mellowness.

However, even if such a third region exists, when the X-ray diffraction nomiturn is determined as described above, two peaks (
This means that it may exist within a range that does not substantially affect the shape of the peaks (λ peaks corresponding to the high iodine portion and the low iodine portion).

That is, there are a core region with high iodine content, a middle region, and a shell region with low iodine content, and the X-ray diffraction pattern has λ peaks and λ peaks.
One minimum portion exists between the two peaks, and the diffraction intensity corresponding to the high iodine portion is ±10 to that of the low iodine portion.
3/l, preferably l/evening to 3/1. Especially //3~j/
/, and when the minimum part of the smaller of the λ peaks is below the coefficient O, preferably below the ROM, particularly below the coefficient 70, such silver halide grains have substantially two distinct layered structures. It is a particle having

The same applies when the third region exists inside the core portion.

It is essential that the color light-sensitive material of the present invention has at least 15 emulsion layers containing silver halide grains according to the present invention, and in the emulsion layer, the grains according to the present invention are present in the core layer. The sum of projected areas of all silver halide grains is preferably 3704 or more, more preferably 704 or more, particularly preferably 20 or more.

Dyes used when growing the low iodine layer include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, -monothiooxazolidine-,
2. A j-A member heteroartic ring nucleus such as a bituric acid nucleus can be applied to the ≠-dione nucleus, thiazolidine-x, 4A-dione nucleus, rhodanine nucleus, and thiopa.

For example, Re5earch Disclosure, I
Compounds described in tem/74413, page 3, section 2 (IYYR/J month) or the compounds described in the cited literature can be used.

A typical example is Tokugansho, 4-2-IA722!
Examples include the compounds described in No.

Antifoggants and stabilizers are also very useful compounds when growing low iodine layers. Re5search D described above
It is possible to use a compound selected from among the compounds shown in isclosure. However, there are some compounds, such as the tetrazaindene compounds shown in Examples, that do not exhibit desirable effects.

Preference is given to the invention to add mercapto compounds.

The mercapto compound preferably used in the present invention is a compound represented by the following general formula.

In the general formula, %Ml represents a hydrogen atom, a cation or an alkali-cleavable mercapto group, and 2 is! Represents a group of atoms required to form a negative or t-negative heterocycle. This heterocycle may contain a substituent or be fused. To explain in more detail, Ml is a hydrogen atom,
Cations (e.g. sodium ions, potassium ions,
(e.g. ammonium ion) or alkali-cleavable mercapto group protecting groups (e.g. -COR', -COOH')
, -CH2CHz COR', etc. However, B' represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, etc.

2 is! Represents a group of atoms necessary to form a negative to 6-membered heterocycle.・This heterocycle may contain a sulfur atom, selenium atom, nitrogen atom, oxygen atom, etc. as a heteroatom, and may be fused, or may have a substituent on the heterocycle or wire ring. You can leave it there.

20 Examples include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene, benztriazole, benzimidazole, benzoxazole, dnzteazo. -, benzselenazole, and naphthoimidazole. ti Substituents for these rings include alkyl groups (e.g., methyl group, ethyl group, n-hexyl group, hydroxyethyl group, carboxyethyl group, etc.), alkenyl groups (e.g., allyl group, etc.), aralkyl groups (e.g., benzyl group, etc.). , 7enethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, p-7 cetamidophenyl group, p-carboxyphenyl group, m-hydroxyphenyl group, p-sulfamoylphenyl group, p-7 cetyl phenyl group) group, o-methoxyphenyl group, co, ≠-diethylaminophenyl group,
-zt4A-dichlorophenyl group, etc.], alkylthio groups (e.g., methylthio group, etherthio group, n-butylthio group, etc.), arylthio group (e.g., phenylthio group, naphthylthio group, etc.), aralkylthio group (e.g., benzylthio group, etc.), mercapto group, etc. may be replaced with . Furthermore, in addition to the above-mentioned substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group, etc. may be substituted particularly on the mesh ring.

The amount of these mercapto-containing compounds used is preferably at most B,io moles per mole of silver halide.

Specific examples of preferable titso-containing heterocyclic compounds having a mercapto group are disclosed in Japanese Patent Application Shobuko 4t7λjJ%IIC
Are listed.

The emulsion of the present invention may be further bonded with silver halide having a different composition by epitaxial bonding, or may be bonded with a compound other than silver halide, such as rotane silver or lead oxide.

It is also possible to use mixtures of particles of various crystalline forms.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure & 17
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type 411 RD17643 RD18
7161 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity increasing agent Same as above 4 Brightening agent page 24 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 Page 650 right column Various color couplers can be used in the present invention,
A specific example of this is the aforementioned Research Disclosure (R
D) It is described in the patent described in 17643, ■-〇-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26.024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425. ．． No. 020, No. 1. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 10.619, No. 4.351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
Same 3rd. ．． No. 725,067, Research Disclosure & 24220 (June 1984), JP-A-6
No. 0-33552, Research Disclosure N1
24230 (June 1984), JP-A-60-4365
No. 9, U.S. Patent No. 4,500,630, U.S. Patent No. 4.54
Particularly preferred are those described in No. 0.654.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4.146,396, No. 4.228,23
No. 3, No. 4. 296. No. 200, No. 2,369
．． No. 929, No. 2,801.171, No. 2.77
No. 2,162, No. 2.895.826, No. 3.
772. No. 002, No. 3.758.308, No. 4,334.011, No. 4.327.173, West German Patent Publication No. 3.329.729, European Patent No. 121
．． 365A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999, U.S. Patent No. 4,451.559, U.S. Patent No. 4.427.767, European Patent No. 161.626A
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146,
The one described in No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-451944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
2.131 No. 188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the fluorescent material of the present invention include the competitive couplers described in U.S. Patent No. 4,130,427, and U.S. Pat. JP-A-60-185950;
DIR redox compound or DIR coupler releasing coupler or DIR coupler releasing coupler or redox described in JP-A-62-24252 etc., European Patent No. 1
73,302A, a coupler that releases a dye that recolors after separation, R, D, No. 11449, No. 24241, a bleaching accelerator releasing coupler described in JP-A No. 6L-201247, etc., U.S. Pat. No. 4,553. Examples include the ligand-releasing couplers described in No. 477 and the like.

Specific examples of color couplers that can be used in the present invention are listed below, but the invention is not limited thereto.

C-(1) C-wei) C-(j) C-(≠) H3 C-(51 C-(61 °′　　　Oh, Fffiゎ. ,oo.

C-(71 C-(81 C-α forceCjI C-beatOf( Shih3 C-(2) H C-α^ H C-αH C-a・CH3 C-αη H ■ 5CHtCHzCOJ C-( 2) CJ+t(t) C-(To) H ≧υ30a C-(24) C-(25) C-(26) Peep I C-(27) C-(28) OH C-(29) OH C- (3O) C-(J/ ) C-(32) 0CHzCHiCONHCHzCHzOCH3C-(3
3) C-(34) OH OH C-(35) C-(38) CIJt+ C-(39) I C-(40) )I Cjl C-(41) H C-(44) C-(45) ■ jl C-(46) HC-(47) I C-(48) HC-(49) C-(50) C-(51) C-(53) C-(57) r σ c-( 58) r σ し113 C-(59) 1'M C! H The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Acid esters (trifel phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-° ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenshade, etc.), amide MCN, N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-diptyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat. No. 4.199.363, West German Pat. etc. are listed.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Fish 17643, page 28, and Questionnaire 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The color photographic material according to the present invention is described in the above-mentioned RD, pages 28-29 of 17643, and 6 of 18716.
51. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-fuynylenediamine compounds are preferably used, typical examples of which include 3-methyl-4-amino-N,N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, penzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2゜2.2〕octane)), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and fogging agents such as sodium poron hydride. , auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids;゛Tylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N,N,N-)+J
Me5-lenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N''-tetramethylenephosphonic acid, ethylene glycol (O-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains 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. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic material to be processed, but is generally less than 31 per square meter of photosensitive material, and by reducing the bromide ion concentration in the replenishing solution! 7!
It can also be set to 00 rpm or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Further, by using means for suppressing the significant accumulation of bromide ions in the developer, the total amount of replenishment can be reduced.

Color development processing time is usually λ~! The processing time can be further shortened by using a high temperature, a high pH, and a high concentration of a color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As a bleaching agent, for example, iron (■), copal) (II)
I), compounds of polyvalent metals such as chromium (■), steel (■), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or iron (m);
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(I[I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(II[) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. I[[) complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, No. 2,059°988, JP-A No. 53-32.736, No. 53-57.831, No. 5
No. 3-37.418, No. 53-72.623, No. 5
No. 3-95.630, No. 53-95.631, No. 53
-10.4232, 53-124.424, 5
3-141.623, 53-28.426, Research Disclosure No. 117.129 (1978
Compounds having a mercapto group or disulfide group as described in JP-A-50-140.129; Japanese Patent Publication No. 45-8.506;
Thiourea derivatives described in JP-A-52-20.832, JP-A-53-32.735 and US Pat. No. 3.706.561; West German Patent No. 1.127.715, JP-A-58-
Iodide salts described in West German Patent No. 16゜235; polyoxyethylene compounds described in West German Patent No. 966゜410 and West German Patent No. 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; No. 49-42.434, No. 49-59,644, No. 53-94.927, No. 5
No. 4-35.727, No. 55-26.506 No. 58-
Compounds described in No. 163.940; bromide ions, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are more similar in terms of their greater promoting effect, and in particular, U.S. Patent No. 3.893.858 and Western Patent No. 1.290.8.
No. 12, JP-A No. 53-95,630 are preferable, and compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as intermediate flow or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on1! ngineers Vol. 64, P, 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microorganisms" written by Hiroshi Horiguchi, It is also possible to use the fungicides described in "Area Reduction, Sterilization, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8.543 and 58-14.8
All known methods described in No. 34 and No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144.547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226.770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, Jikai @ No. 60-133449, No. 5
It can also be applied to close-up a photosensitive materials described in Patent No. 9-218443, No. 61-238056, European Patent No. 210.660A2, etc.

The present invention will be further explained below with reference to Examples.

Example 7 (Preparation of emulsion) An aqueous solution of inert gelatin 2Of, potassium bromide, ≠2, potassium iodide, 0rff, dissolved in distilled water r00yd, was stirred at 1e7j°C, and silver nitrate was added thereto! ,0
An aqueous solution of ISO 2 was added instantly, excess potassium bromide was added, and physical ripening was performed for 20 minutes. Furthermore, U.S. Patent No. ≠.

24t2,4141! According to the method described in (1) were added at a flow rate of 1 Occ per minute to allow total growth of silver iodobromide grains of ≠λ moles. Emulsion A was prepared by washing with water for desalting.

What is the finished amount of emulsion A? It was OO2. The grain size of emulsion A is Oorμm. 1. Same as emulsion A. //Am
All silver iodobromide grains of 7.03 μm in diameter were prepared,
Each was designated as emulsion B%C. Further, silver iodobromide grains with a core molar predominance of 1.22 μm were prepared and used as an emulsion.

Emulsion A, JOOf, distilled water rzocc, 1014 potassium bromidej 0CCYf: Added 7roCK, heated and stirred, an aqueous solution in which silver nitrate Jiff was dissolved JOOOOc, potassium bromide cojft-dissolved aqueous solution J20CK:.

was added at the same time over 30 minutes, and further 1002 tons of silver nitrate
By simultaneously adding for 10 minutes an aqueous solution roocc dissolved in potassium bromide and an aqueous solution rtocz'gH dissolved in potassium bromide 71f, a silver iodide content of 744 mol width 1. ≠ μm silver iodobromide emulsion/ was prepared. (For comparison) Emulsion 1 has an aspect ratio of 2.
6 twin crystals, and its (/// ) plane ratio was rz. A silver iodobromide emulsion with a silver siliodide content of 1 mol was prepared by taking emulsion B as a rotary rotary emulsion and shelling it in a total amount of silver nitrate of 1 mol in the same process as in the preparation of emulsion I.

(For comparison) Emulsion Bt-4AIOf and 9 distilled water tracC
After adding 7 and 3 parts of potassium bromide and heating to 7J0C to adsorb the spectral sensitizing dye with the following structure + 11Th, silver nitrate! Aqueous solution of t dissolved in 2101 and potassium bromide/7°!
f''Ik dissolved aqueous solution 270CX::'@: Added at the same time, further silver nitrate 71ft-dissolved aqueous solution to
ocx:, and potassium bromide! A silver iodobromide emulsion 3 having a silver iodide content of 21 moles was prepared by simultaneously adding 6jOcct to an aqueous solution in which λ, jff were dissolved.

Compound (1) t Emulsion (:'i760 F) A silver iodobromide emulsion with a silver iodide content of 77 moles was prepared by shelling the total amount of silver nitrate in the same manner as in Emulsion 3. However, after the antifoggant (2) having the following structural formula was completely adsorbed onto the spectral sensitizing dye (1), the shell was attached.

Compound (λ) Emulsion A silver iodobromide emulsion ji having a silver iodide content of it molar was prepared in the same manner as in Emulsion Hiroshi. However, 1 molar silver iodobromide was used for shelling. A silver iodobromide emulsion tt with a silver iodide content of 17 molar width was prepared by completely adsorbing the compound (3) having the following structural formula in place of the compound (2) in the same process as Emulsion Hiro, and then adding a shell.
-I made it. (For comparison) Compound (3) Emulsion Dt-40Of and Copper ingot silver 6 in the same process as Emulsion 3
Shelling corresponding to 7f was carried out to prepare silver iodobromide emulsion 7 having a molar silver iodide content. Emulsion tt- was prepared in the same manner as emulsion j. In this case, an emulsion with a picomolar diameter of 1.5 μm was used as the core grain. The final size is λ-Or
It was μm. The structures of emulsions l to r are summarized in Table 1.

A clear layered structure refers to a layered structure in which the presence of a silver iodobromide layer containing silver iodide with a molar ratio of 30-≠j as defined in this patent can be confirmed by X-ray diffraction.

Emulsion 1. After desalting f and adding gelatin, p at ≠ O0C
H' was 4,4&, pAgkl, IKXIII.

The emulsions were optimally chemically sensitized using sodium thiosulfate, chloroauric acid and potassium thiocyanate, and the following spectral sensitizing dyes were added to all emulsions except emulsions 3 and 7 in optimal amounts. r was created from sample/.

Undercoat layer The emulsion and protective layer were coated on a triacetylcellulose film support coated with gold at the coating weights shown in Table 2.

Table 2 fil Emulsion layer 0 Emulsion...W, emulsion shown in Table 7-) ~ 7 (2./x 70-2 mol/m2 of silver) 0 Coupler E x C-/ (1.jx 10-3 mol/m2) o Tricresyl phosphate (/, /O97m2) 0 Gelatin (2,3017m2) (2)
Protective layer o2,4t-dichlorotriazine-6-hydroxy-s
- Triazine sodium salt (0.0r 97m2) 0 Gelatin (1.tO97m2) These light-sensitive materials were sensitometrically exposed through a red filter and subjected to the following color development process 2.

The concentration of all treated samples was measured using a red filter.

RMS indicates the granularity of the photographic performance results obtained.

The third value along with the value (≠value at the anomieture of tμ diameter)
Shown in the table.

The development treatment used here was carried out at 3°C under the following conditions.

1. Color development・・・・・・・・・・・・2 minutes 4
T! Bleach for 30 seconds and wash with water for 30 seconds.
3 minutes/j seconds≠, constant wear・・・・・・・・・6
Minutes and 30 seconds! , Washing with water・・・・・・・・・・・・
3 minutes/6 seconds, stable...
・3 minutes 75 seconds The composition of the processing liquid used for each type of work is as follows.

Color developer sodium nitrilotriacetate 1. Ofsodium sulfite sodium carbonate
30. Of potassium bromide
1. μ? hydroxylamine sulfate
2. Hiro? Hiro-(N-Ethyl-N-β-hydroxyethylamino)-coatacyl-aniline sulfate Hiro, jf Add water lt bleach solution ammonium bromide /1,0. Of ammonia water (ur%) coj, 0 goethylenediamine-tetraacetic acid sodium salt /3Of glacial acetic acid
l≠ Add water resistance
IT fixer sodium tetrapolyphosphate 2. Of sodium sulfite, oy ammonium thiosulfate (70%) / 7! , Otd Sodium Bisulfite
≠31 Add water
It was found that the emulsion of the present invention was excellent in terms of sensitivity and graininess.

Example: On a subbed cellulose triacetate film support,
Samples ioi to 1llt, which are multilayer color photosensitive materials having each layer having the composition shown below, were prepared.

(Composition of photosensitive layer) For silver halide, colloidal silver, and coupler, the coating amount is expressed in units of 1!7m2 of scissors, and for sensitizing dye, the coating amount is expressed in units of 1!7 m2 of scissors, and for sensitizing dye, the amount is Expressed in moles. See you again, Hirohiro! ,r,to%14! and 1
Table 4 shows a 6-layer emulsion! The emulsion sound shown was used.

@1 layer: antihalation layer black colloidal silver Silver coating amount 06-2 gelatin ko, ko UV-1o, tUV-J o, kocpct-/0-01S
olv-/
o , o /5olv −
J 01018o
1v-J O,O
rth λ layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount o, is Gelatin 1.0Cpd-1 〇,co 3rd layer: 7th red-sensitive emulsion layer Silver iodobromide emulsion ( AgI looQ molar range, internal high AgI type, equivalent sphere diameter 0゜7μ, coefficient of variation of equivalent sphere diameter 744%, l tanhedral grains) Silver coating amount O, K is silver iodobromide emulsion (AgI≠, θ molar ratio , internal high AgI type, equivalent sphere diameter Q, ≠ μ, coefficient of variation of equivalent sphere diameter -2, /4c-hedral particle) Silver coating amount O, cogelatin
/-0Ex8-/
44. jX/ 0-'MokExa-x
1. ! Xl0-4=LeExS-3o, a×i
o-'MoleExS-IA O0J×IO-'Mok
ExC-10.33 ExC-,j O,009E
xC-3o, o23 ExC-+0. /1 4th tN: 2nd red-sensitive emulsion layer Silver iodobromide emulsion Silver coating amount 0.13 Gelatin 0.7Ex8-/
3X/(7-'ExS-2/x10-
' ExS-j O, 3×10′″″4
ExS-11O,jXlo-4 ExC-60,01 ExC-30,01 ExC-u O, 10th! Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion Silver coating amount θ, tazelatin
0. BuExS-/
2×to-'ExS-ko
O0≦X1o-'ExS-J
O, A×10-'ExC-≠
0.07ExC-r
O,01s8o1v-/
0. /28o1v-20
,/J.

Layer 1: Middle layer Gelatin i.

Cpd-G Q・' 15th: First green-sensitive emulsion layer Silver iodobromide emulsion (AgIlo, O-molti, internal high AgI type, equivalent sphere diameter 0°7μ, coefficient of variation of equivalent sphere diameter 74L%, /≠hedron Grain) Silver coating amount 0.2 silver iodobromide emulsion (AgI ≠, θ molar ratio, internal high AgI type, equivalent sphere diameter 0
．． (gμ, coefficient of variation of equivalent sphere diameter 22 mm, l prohedral particle) Silver coating amount 0.7 gelatin
1.2ExS-r
t×io-'ExS-Δ
koX10-'ExS-7/×10-' ExM-10,≠/ ExM-20,IO ExM-j 0103So
lv-/ (), 2nd r layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion Silver coating amount O0U gelatin
0.35Exa-s
3. r×to-4ExS-+
1. IAXlo”-4ExS-70, 7×1
010 -4Ex/ o, ori ExM
−30,0/ S o I v −/ θ
,/! Second layer: Intermediate gelatin o3 First O layer: Third green-sensitive emulsion layer Silver iodobromide emulsion Trowel coating 'Ikl, 0 gelatin o, rExS-j
x×10-'ExS-1O,l
? ×10-' E x S -70, ♂×10-' ExM-Hiroshi θ
40≠ExM−j
O,0/ExC-440,006 Solv-10-Co 11th layer: Yellow filter layer Cpd-JO・0' Gelatin 0. j8o1v-
/ 0. /12th layer: Intermediate layer gelatin 0. jCpd-
20, / 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI/θ molar ratio, internal high iodine type, equivalent sphere diameter 0°7 μ, coefficient of variation of equivalent sphere diameter / Hiroki, /≠hedron Grains) Silver coating t O, /Silver iodobromide emulsion (AgI Hiroshi, Q mole superior, internal high iodine type, equivalent sphere diameter O1 μμ, coefficient of variation of equivalent sphere diameter Ko2, 7 μhedral grains) Silver coating amount o , or gelatin
i.

ExS-43×10"-' ExY-/0.13E
xY-20,0ko5olv-/0. /! 1st
μ layer: 21st sensitive emulsion layer Silver iodobromide emulsion Silver coating amount O1/Tagelatin 0.3ExS-I
2×1o-4ExY-10, λλ 5olv-/o, o77 No. 11: Intermediate layer fine grain silver iodobromide (AgI-mole ratio, uniform type, equivalent sphere diameter 0.1Jμ) Silver coating amount Ol, 2 Gelatin 0. 36 1st A layer: 3rd blue-sensitive emulsion layer silver iodobromide emulsion Silver coating amount 1. O gelatin
03Ex8-r
t, r×to-4ExY-/
0.28o1v-/
0-07 No. 115: First protective layer gelatin 1. tUV-7
0,/UV-λ 0.28o1v
-/0.0/5olv-2
0,0/ It layer: @-6 layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Trowel coating 4J: 0. /♂ Gelatin 0.7 Polymethyl methacrylate particles (diameter 1.jμ) 0.2 W-70,02) 1-70. ≠ cpa-j 1.0 As shown in the table≠, the emulsion r-/J of the present invention and the comparative emulsion l≠
I prepared ~/ri. Sample 101 using a comparative emulsion in each photosensitive layer. Samples ioλ~107, in which each layer of No. ≠, j%t, 101/Hiro, /A was replaced with the emulsion of the present invention;
Sample 10 in which the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each replaced with the emulsion of the present invention! r, /10. In addition, samples 1/lt were prepared in which all the layers in the table were replaced with the emulsion of the present invention.

The photographic element was exposed to light using a tungsten light source with a color temperature adjusted to ≠r00'KK using a filter, and then developed at jf'c according to the processing steps described below.

Color development 3 minutes/j seconds bleaching 6 minutes 30 seconds washing with water 2 minutes 10 seconds fixing μ minutes - 20 seconds washing with water
Stable for 3 minutes/j' seconds 7 minutes 02 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1. Of/-hydroxyethylidene-7゜l-diphosphonic acid, -2.01 sodium sulfite Hiroshi, Of potassium carbonate
Jo, 0? potassium bromide
1. Hiro? potassium iodide
1. J■Hydroxylamine sulfate sulfate Coco≠2 ≠-(N-ethyl-N-β-hydroxyethylamine)-2 -methylaniline sulfate Hiroshi, j? Add water 1.02 pH 10.0 Bleach solution Ethylene diamine Nishi acetate ferric ammonium salt ioo, oy Ethylene diamine Nishi acetate disodium salt IO+ OP Ammonium bromide ijo, oy Ammonium nitrate 10. Add water
1.02pH+, O Fixer Ethylenediaminetetraacetic acid disodium salt 1.0? Sodium sulfite Hiroshi or ammonium thiosulfate aqueous solution (70'4) /73.0td Sodium bisulfite μ, 6f Add water
1. 0tpH+, g Stabilizing liquid formalin (μθ coefficient) λ, Oyd polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3f Add water 1. It was found that the effects of improving sensitivity and graininess as shown in Example 1 can be obtained whether the O4 emulsion of the present invention is used alone or in combination in each photosensitive layer.

Example 3 Undercoat 1i? Each layer having the composition shown below was coated on a cellulose triacetate film support to prepare sample 30/f, which is a multilayer color light-sensitive material.

(WIA optical layer composition) What is the number corresponding to each component? The coating amount is expressed in /m2, and for silver halogenide, the coating amount is expressed in terms of silver.
It shows. However, for sensitizing dyes, the coating amount is expressed in units of total mole based on 1 mole of silver halide in the same layer.

(Sample 30/) 1st layer: Antihalation agent black colloidal silver・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Silver 0. #gelatin·····
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. HiroO 2nd layer; Intermediate layer 2, j-di-t-interdecylhydroquinone ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・o、itExM-A ・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.07ExC-J ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
Oko cpct-+ ・1 Old・・・・・・・・・・・・
...Old...0.002U-/ ......
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・o、atU-2・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・o、orU−J ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.10S o l v -/ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
10Solv-2・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.02 gelatin
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・1. 017 Third layer (7th red-sensitive emulsion layer) Emulsion A ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Silver O, Ko! Emulsion B ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・Silver 0.2! E x S -/・・
・・・・・・・・・・・・・・・・・・・・・t,y
xio-sExS-Hiroshi・・・・・・・・・・・・・・・
・・・・・・・・・1. AXlo-6ExS-2...
・・・・・・・・・・・・・・・・・・・・・1. rX
lo-5Exa-J・・・・・・・・・・・・・・・
・・・・・・・・・3. /X10-'E x C-t
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.331ExC-7・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.0λO gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.17 μth layer (second red-sensitive emulsion layer) Emulsion C・・・・・・・・・・・・・・・・・・・・・・・・
...1 Old...Silver 1. OE x 8-/・Old・
...1 old...z, 1xio-sEx
S-λ・1 Old... Old... 1. u×
10”-5EX8-j・・・・・・・・・・・・・・・
・Old...-03xio-'E x C-/ ・
...Old...Dan...Old...o,
io.

ExC-J...Old...Old old old old...o, oz.

E x C-7... Old... Old...
・Dan...0.01! Ceratin ・1 Old・・・・Dan・・・・・Dan・Dan・・・・1. 30th!
Layer (third red-sensitive emulsion layer) Emulsion-D ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Silver 1. 40E x S
-／・・・・・・Old and old・l1・t, ≠xio-5E
xa-J... Old... Old... 1
．． lfi×IO-5ExS-j・・・・・・・・・・・・
・・・・・・Dan-・・-2, 4<X/0-4E
xa-μ...Φold old old old old...1. ．． 2Xlo-5
ExC-J・・・・・・・・・Old Old Old Old Old・Dan・
o,oi.

ExC-/・・・・・・・・・・・・1 Old...
Old...o, o♂QExC-6...1 Old...
......Old...0.097801v-
4!・Old old old old old...1 old...o, λλ8
o1v-t・・・old old old・・・・・・old・
・・・・・・0.10 Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・1
．． 63rd layer (middle layer) Cpd-7・・・・・・・・・・・・・・・・・・ Old・・・・・・・・・0.0μ08olv-J・Old old old old old・Dan・・・・・・・・・o、oλ0gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・o, t.

15th (7th green-sensitive emulsion layer) Emulsion A... River... Old......
Old...Silver o, /j emulsion B...
・・・・・・・・・・・・1 Old・・・・・・Silver o, 1sE
xS-j...old old old old...3. oxi
o-sExa-6・・・・・・・・・・・・・・・・・・
Group...1.0X10-'E x 8-7...
...... Old... Old... 3. rxio-<Ex
M-／ ・・・・・・・・・・・・・・・ Old・Dan・
...dan o, ag.

B x M -6・・・・・・・1 Old・・・・・・・・・・
・・・・・・・o, oilExM-j ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
．． 030ExY-2・Use・・・・・・Old・・・・・・
・Dan...0.02! S o l v -/・・・・
・River...River...Old and old・-0,100Cpd-
4・・・・・・・・・・・・・・・・・・ Old・・・Old・・・・・・0.010 Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
．． 63th r layer (second green-sensitive emulsion layer) Emulsion C・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Silver 00atE x
S-!・Old・・・・・・Old Old Old・2. /×
10-”ExS-6・・・・・・・・・・・・・・・
・・・・・・・・・7.0X10-5E x 8-7・・
・・・・・・・・・・・・・・・・・・・・・2.6
×10-'E x M-/ ・・・・・・・・・・・・
・・・・・・River・・・・・・・・・・・・0.09≠Ex
Y-J ・Old・・・・・・・・・・・・・・・・・・
Old...0.011ExM-j...
・・・・・・・・・・・・・・・・・・・・・・・・O0
Okoro5olv-2-・・・・・・・・・・・・・・・
...River...o, it.

cpa-r ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o, oor gelatin ・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.10th layer (third green-sensitive emulsion layer) Emulsion D ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Silver 1. jE x S
-!・・・・・・・・・・・・・・・・・・・・・・・・
・3. jxlo-”E x 8-4・・・・・・・・・
・・・・・・・・・・・・・・・r、oxio-5E
x 8-7・・・・・・・・・・・・・・・・・・
...3,0X10-4E x M -/ ...
·················river·······
o, oizE x M -7・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・o, io.

E x M −J ・・・・・・・・・・・・・・・
・Old...Old...0.02J-8olv-/...
・・・・・・・・・・・・・・・・・・・・・1 Old...
・・0.2j8o1v−μ・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.10 Gelatin・・・・・・Mountain・・・・・・・・・・・・・・・
・・・・・・・・・・・・1. Hiro 10th layer (yellow filter layer) Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・Silver o, orcpct-7・・・・・・・・・
・・・・・・・・・1 Old・・・・・・・・・o, orS
olv-≠river・old・・・・・・・・・・・・・・・old・
・・Old・0.03 gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.1.0 Layer II (7th blue-sensitive emulsion layer) Emulsion A ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Silver o, or emulsion B ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・1 Old・・Silver 0007 Emulsion F ・・・・・・・・・
・・・・・・・・・・・・Old old old・・・・・・Silver 0.0
7ExS-Jr---, old and old... old...
J...! rX10-4E x Y −/・・・・・・
・・Old・・・・Old・dan・・・・0.7λlE
X C-70,,,0,,,,,,,,,,,,,,
, , , , , , , , 0, OJ 0ExY-J ・
・・・Old・・・・・・・・・・・・Old・・・・・・
o, oijS o 1 y -/river...
・・・・・・Old・・・・・・・・・・・・o、-2i Seratin ・Kawa・・・・Old・Yamakawa・・Dan・
・・・・・・1. 10 12th layer (7th blue-sensitive emulsion layer) Emulsion G ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ Silver 0. II-jExS-
1r... Old... Old... Old... P, jX/
Q-'E x Y -/ ・・・・・・・・・・・・
・River...1 Old...0. /! 4AExC-7...
・・・Group・・・・・・・・・1 group・・・0-0
07ExY-2... Old... Group...
・・・・・・・・・0.010Solv-J ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・・・0
．． Oj gelatin・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.71 7th
3 layers (@3 blue-sensitive emulsion layer) Emulsion H・・・・・・・・・・・・・・・・・・・・・
,・・・・・・・・・・・・ Silver 0゜77E x 8
- r ・・・・・・・・・Myself・・Group・・・・・・・
ko, 2×l0−4E x Y −/ ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0,20ExC-7・・・・・・・・・・・・River・
・・・・・・・・・・・・0.001S o 1v
-／ ・1 Old・・・・・・・・・・・・ Old・・・Old・0.07 Gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・O0≦
2 1st t/L layer (1!/protection layer) Emulsion process ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Silver O0 yo UV-/ ・・
・・・・・・・・・・・・・・・・・・ Old... Old...
・・・・・・0.1/UV-1 ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Mountain・・・0.
/7Solv-Hiroshi・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.0! gelatin
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・1. 00 1st layer (second protective layer) Polymethyl acrylate particles (1.5 μm in diameter)・・・・・・・・・・・・・・・
・・・o, r≠Cpd-yo ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・o, i.

cpct-y ………・Old・・・・・・・・・・e・
...0.10 gelatin
1. In addition to the above ingredients, a gelatin hardening agent H-/ and a surfactant are added to each layer.

(Samples 302 to 316) Samples 302 to 3it were prepared by replacing the emulsions of the !th layer, the second layer, and the 73rd layer of sample JOI as shown in Table B.

Note that emulsions A and P used in these samples were prepared according to the above-mentioned preparation method. Table of characteristics of emulsion A-P! summarized in.

These samples were subjected to imagewise exposure and subjected to the following development process.
The relative sensitivity of each color-sensitive layer was determined. Relative sensitivity The logarithm of the reciprocal of the exposure amount that gives a density of fog + 0.2 for each density of hasian, magenta, and yellow was expressed as a relative value as sample J O/fO.

In addition, exposure was performed using a wedge for measuring the grain size of the MS grain size, and each density of cyan (几), magenta (G), and yellow (B) was
RMS of the aperture diameter rμ at 0.2 [′t
- Measured.

All the following treatments were carried out at 3♂0C using an automatic developing machine.

Color development 3 minutes/j seconds bleaching 7 minutes bleach fixing 3 minutes is seconds water washing ■ μO seconds water washing ■ 7 minutes stable 30 seconds drying (jQ'c)/minutes/! Sec. In the above treatment steps, water washing (1) and (2) were performed using a countercurrent water washing method from (1) to (2). Next, the composition of each treatment liquid will be described.

The replenishment amount of each processing solution is /200 ttl for color development per 1 m2 of color photosensitive material, and for everything else including washing! 00 yards
And so. Also, the amount of pre-bath carried into the washing process is different from color photosensitive materials/
It was 0d per m2.

Color developer> Mother solution Replenisher diethylenetriaminepentaacetic acid i, or i, 1tl-hydroxyethyridan-1,/-diphosphonic acid co, Of 2.29 Sodium sulfite ≠, Of ≠, 4! f Potassium carbonate JO0Of3, Ot Potassium bromide
1. Reference t O, 7f Potassium iodide
1. ! ! Iv-Hydroxylamine sulfate ≠? 2.6f≠-(
N-Ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate Hiroshi! f j, Ot
Add water 1. Ot 1.0tpH1
0,010,0! Bleaching solution> Common to mother liquor and replenisher ethylenediaminetetraacetic acid ferric ammonium salt /λo, or disodium ethylenediaminetetraacetate io, or ammonium nitrate io, or ammonium bromide
100. Of bleach accelerator
Add zxio-3 mole ammonia water and pi
(4. Add water 1. O
Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium salt common to mother liquor and brightening solution 10. Of ethylene diamine acetic acid disodium salt!・Of sodium sulfite, Ov ammonium thiosulfate aqueous solution (70%), add ammonia water, and add H7, J water.
/l (washing water) Calcium ion 32■/l, Magnesium ion 7.
Tap water containing 3 η/l was passed through a column filled with a 1 kHz strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin, and treated to calcium ions of 1.2 η/l and magnesium ions of 0/l. It was used by adding 20 ml of sodium isocyanurate dichloride per tit to water.

(Stabilizing solution) Mother solution/replenisher common formalin (J7% w/v) 2.Of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.Jf ethylenediaminetetraacetic acid di-sodium salt o, ozy water Add 1tp)i
r, r (Drying) The drying temperature was IO″'c.

Table 6 shows that the sample using an emulsion having a clear layered structure with an average silver iodide content of less than the molar ratio (JO Co., 304.J
lo) has high sensitivity but poor graininess l! A sample using an emulsion with a molar mass or higher and no clear layered structure (
It is clear that JO4A, JOI, jl, 2) is inferior in sensitivity and graininess, while the sample of the present invention has high sensitivity and excellent graininess.

The structures of the compounds used in Examples 1 to 3 are shown below.

EχS-60! H8 xS-8 olv-1 olv-3 olv-4 pd-3 Cpd-4 cp d-5 CI F+tSO*NHCkh CHz CHt 0C
Hz CHtN (CHJ3CHx -CH5Ot
CHx C0NH-CH! CH! ■CH30I CHx
C0NHCHxυ-1 L1r'+3 υ-2 Shir- t/-3 xM-6 ``d-7(, aH+s xM-7 L CPd-'1 Procedural amendment 1. Display of the case Showa 13 Prison Petition No. 1/ 214A
No. 2, Name of the invention Silver halide color photographic light-sensitive material 36 Relationship with the person making the amendment Applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment ``Detailed description of the invention'' in the specification Column 5, the description in the "Detailed Description of the Invention" section of the description of contents of the amendment is amended as follows.

1) 3rd line of page 1 rpYJt= pHJ and correct it.

2) Page 70, line 3 "Emulsion Man" "Emulsion A" and correct it.

3) Number 7! page 13th line "/~7" "/-rJ and correct it.

s) 1st line of page ty "Emulsion l~/3" "Emulsion 2~/4AJ and correct it.

6) Co-row of page ty ``Emulsion l reference~/PJ "Emulsion/J-co-O" and correct it.

7) Correct "Emulsion-IJt-"Ultrafine grain emulsion (grain size 0.0jμ)" on the 1st page//line.

Claims (1)

[Claims] A silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on a support, The emulsion in at least one of the emulsion layers is composed of chemically sensitized silver halide grains having an average grain size of 1.7 μm or less, and the silver halide grains contain 30 to 45 mol % of silver iodide. 1. A silver halide color photographic light-sensitive material, characterized in that silver iodobromide containing silver iodobromide is present with a clear layered structure, and the silver iodide content in the entire grain is 15 mol % or more.