JPS6346451A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a high sensitivity and less tendency for generating coloring fog and color turbidity by incorporating a highly reactive yellow coupler and a silver halide particle having a high silver chloride content to a silver halide emulsion layer, and a specific compd. to a non- photosensitive layer respectively. CONSTITUTION:The highly reactive yellow coupler having a relative coupling reaction rate RM/RN of >=0.5 is incorporated to the silver halide emulsion layer. And, the silver halide particle having >=80mol% silver chloride content is incorporated to said layer. The compd. shown by the formula is incorporated to a non-photosensitive layer as a stain inhibitor. In the formula, R1 and R2 are each 1-5C alkyl group, (n) is 1-20, (k) is 1 or 2, A is -CO-X-R3 or -OY, -NR4R5 group, etc., (wherein X is -O-, -NR4-, Y is R3, or -CO-R3, R3-R5 are each H, alkyl or aryl group, etc.). Thus, as the titled material contains the highly reactive yellow coupler, the silver halide particle having the high silver chloride content, and the compd. shown by the formula, the titled material having the high developing speed and capable of reducing color turbidity is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
The present invention relates to a silver halide photographic light-sensitive material that has excellent photographic performance such as sensitivity and maximum density, has little occurrence of strong color fogging and color turbidity, and is suitable for rapid processing.

[Background of the invention]

In general, silver halide color photographic light-sensitive materials have three types of silver halide photographic emulsion layers coated on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. has been done. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side.1, and between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light that passes through the blue-sensitive emulsion layer. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. Furthermore, for example, in exposed materials for color photographic paper, the layers are generally coated in the order of the red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer from the side to be exposed, and each layer has a special coating, similar to the exposed material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, an M retaining layer, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by the reaction of the dye with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanoacetyl couplers are used to form cyan, magenta and yellow dye images, respectively. A magenta coupler and a pacylacetamide-based or benzoylmethane-based yellow coupler are used. These dye-forming couplers are present in light-sensitive color photographic emulsion layers or in developer solutions.
The present invention relates to a silver halide photographic material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, various measures have been taken to speed up color development. As one method, it is known to use a development accelerator when developing an exposed silver halide color photographic light-sensitive material using an aromatic primary amine color developing agent. Among such development accelerators, compounds with relatively high activity often have the disadvantage of forming fog. However, among these compounds, certain black-and-white developing agents exhibiting superadditive properties in color development can provide a development accelerating effect with relatively low fog generation compared to other development accelerators. An example of such a black and white developing agent is British Patent Tube 81.
1-phenyl-3-pyrazolidone described in No. 1,185,
N-methyl-p described in U.S. Pat. No. 2,417,514
-aminephenol, N,N,N',N'-tetramethyl-p-phenylenediamine described in JP-A-50-15554, and the like.

Regarding the mechanism of superadditive development in this color development, see G.
Journal by Van Veelen, F.
Of the Photographic Science, No. 20,
Reported on page 94 (1972). There are two ways to obtain the effect of promoting color development using such a black and white developing agent as an auxiliary developer: one is to include it in advance in a silver halide color photographic light-sensitive material, and the other is to include it in a color developer. There is.

Among these, 1-aryl-3-pyrazolidones are particularly preferably used when the black-and-white developing agent is included in a silver halide photographic material to promote color development. For example, JP-A-58-89739 discloses that a silver halide color photographic light-sensitive material having a silver halide emulsion layer on a support in which the grain size ratio of silver halide grains differs by 50% or more has a 1-aryl- The addition with 3-pyrazolidone is disclosed. However, the silver halide color photographic light-sensitive material containing 1-aryl-3-pyrazolidone shown as IM in this publication can be subjected to intensification treatment in the presence of an intensifier such as Kobal I complex salt. However, when processed as a normal color development process, its development promotion effect is extremely insufficient, especially when a normal color development process is performed using a silver halide emulsion with a large average grain size. It was found that almost no effect of promoting color development could be obtained.

Furthermore, JP-A-56-64339 describes a method of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-64339 describes
No. 144547, No. 58-50532, No. 58-50
No. 533, No. 58-50534, No. 58-50535
No. 58-50532, 1-aryl-
It has been disclosed that 3-pyrazolidones are added to a silver halide color photographic light-sensitive material and processed within an extremely short development time.

However, although the techniques described in these publications may be satisfactory in terms of simply obtaining the effect of accelerating development, they are not necessarily satisfactory when photographic performance such as sensitivity, gradation, and maximum density are comprehensively taken into consideration. It's hard to say that there was.

Furthermore, when color development is performed using such a development acceleration technique, there is another problem in that color fogging and color turbidity are likely to occur. Conventionally, it has been well known that certain hydroquinone derivatives are used to prevent color fogging and color turbidity.

However, when large amounts of these hydroquinone derivatives are added to prevent color development, although they are effective against color fog, they may cause deterioration of photographic performance such as deterioration of sensitivity and maximum density.
Furthermore, combinations with certain color couplers may have an adverse effect on image storage stability.

As described above, conventional techniques have not yet produced silver halide photographic materials with satisfactory rapid processing suitability.
At present, its development is strongly desired.

[Purpose of the invention]

The purpose of the present invention is to provide a silver halide sensitizer that has good photographic performance such as sensitivity and maximum density, has very little color fog and color turbidity during color development, and also promotes color development and is suitable for rapid color development processing. The purpose is to provide materials.

Further objects will become apparent from the description below.

[Structure of the invention]

The above object of the present invention is to provide a silver halide emulsion layer containing a yellow coupler having a relative coupling reaction rate ratio RM/RN value of 0.5 or more, a silver halide emulsion layer containing a magenta coupler, and a cyan coupler on a support. In a silver halide photographic light-sensitive material having a photographic constituent layer composed of a silver halide emulsion layer and a non-photosensitive layer, each of the silver halide emulsion layers has a silver chloride content of 80 mol% or more. and at least one of the non-photosensitive layers contains silver halide grains having the following -f1
This is achieved by including at least one compound represented by formula [1].

General formula [IcoN [In the formula, R1 and R2 each represent an alkyl group having 1 to 5 carbon atoms, each represents an integer of 1 to 20, and k represents 1 or 2. A represents a hydrogen atom, R5 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, R4 represents a hydrogen atom, an alkyl group, or an aryl group),
-〇Y〈Here, Y represents R1 or CR3, R1 has the same meaning as above), hydrogen atom, alkyl group, aryl group or CRy, and R1 has the same meaning as above. 〉, R1 has the same meaning as above, R6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group) or a cyano group, B represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, Heterocyclic group or R6 -b-CnH2n++- represents a group represented by -(A)k (,,:, where R, R2, n, and A each have the same meanings as above)] [Invention Specific Structure] The silver halide photographic light-sensitive material of the present invention includes a silver halide emulsion layer containing a yellow coupler having a relative coupling reaction rate ratio RM/RN value of 0.5 or more, and a silver halide emulsion layer containing a magenta coupler. A support has photographic constituent layers composed of an emulsion layer, a silver halide emulsion layer containing a cyan coupler, and a non-light-sensitive layer.

In each of the silver halide emulsion layers containing the above couplers, silver halide grains having a silver halide composition having a silver chloride content of 80 mol % or more (hereinafter referred to as silver halide grains according to the present invention) However, silver halide grains having a silver chloride content of 90 mol % or more are preferred.

Further, the content of silver iodide is 1 mol % or less, preferably 0.
It is 5 mol% or less. More preferred are silver chlorobromide grains or silver chloride grains having a silver bromide content of 10% or less.

The silver halide grains according to the present invention may be used alone or mixed with other silver halide grains having a different composition, and the silver halide grains have a silver chloride content of less than 80 mol%. It may be used in combination with particles.

Further, the silver halide grains having a silver chloride content of 80 mol% or more are all silver halide grains contained in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 80 mol% or more. It accounts for at least 50% by weight, preferably at least 75% by weight.

The composition of the silver halide grains according to the present invention may be uniform from the inside to the outside of the grain, or the composition between the inside and outside of the grain may be different, or the composition between the inside and outside of the grain may be different. When the compositions are different, the compositions may change continuously or discontinuously.

The grain size of the silver halide grains according to the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6μ, more preferably 0.2μ to 1.6μ. It ranges from 25 to 1.2 μ-. The above particle size can be measured by various methods commonly used in the technical field; a representative method is Loveland's "Particle Size Analysis Method JA, S
, T., M., Symposium on Light Microscopy 1955.

pp. 94-122 or [Theory of the Photographic Process] by Mies and James, 3rd edition, published by Macmillan (19
It is described in Chapter 2 of 1966). This particle size can be measured using either the projected area of the particle or an approximation to the diameter.If the particles are of substantially uniform shape, the particle size distribution can be measured fairly accurately as either the diameter or the projected area. can be expressed.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse. Preferably, the grain size distribution of the silver halide grains has a coefficient of variation of 0. Monodisperse silver halide grains with a particle size of 22 or less, more preferably 0.15 or less.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Σn1ri Average particle size (bottom) -X. i Here, ri represents the particle size on each side of the particle, and ni represents the number.
The grain size here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted to a circular image of the same area in the case of grains with shapes other than cubic or spherical. .

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having +100+ planes as crystal surfaces.

Also, U.S. Patent Nos. 4,183,756 and 4,22
No. 5,666, JP-A-55-28589, JP-A-55
Specifications such as -42737, The Journal of
Photographic Science (J, Photg
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared and used by the method described in the literature such as R.R., Sei), 21.39 (1973). Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape, or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The grains may be grown all at once, or they may be grown after forming seed grains. The method for producing and growing the 0-species particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a form of simultaneous mixing method,
1lh-con 1- described in No. 4-48521 etc.
A rolled-double jet method can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains according to the present invention can be prepared by adding cadmium salt, zinc salt,
Adding metal ions using lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts,
It can be included inside the particle and/or on the particle surface,
Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

The silver halide grains according to the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

The silver halide emulsion containing the silver halide grains according to the present invention (hereinafter referred to as the silver halide emulsion of the present invention) may be processed by removing unnecessary soluble salts after the growth of the silver halide grains is completed, or In the case of removing the salts, which may remain contained, the method described in Research Disclosure No. 17643 can be used.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
The sulfur sensitization method using activated gelatin, the selenium sensitization method using selenium compounds, the reduction sensitization method using reducing substances, the noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. I can do it.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening and/or for the purpose of preventing fog during storage or photographic processing and/or maintaining stable photographic performance.
or at the end of chemical ripening and/or after the end of chemical ripening,
Compounds known in the photographic industry as antifoggants or stabilizers can be added before coating the silver halide emulsion.

A yellow coupler having a relative coupling reaction rate ratio RM/RN value of 0.5 or more (hereinafter referred to as a fast-reactive yellow coupler according to the invention) is used in one of the silver halide emulsion layers of the invention.

The fast-reacting yellow coupler according to the present invention is a yellow coupler having a relative coupling reaction rate of 0.5 or more.

The coupling reaction rate of the couplers is determined by the rate of the coupling reaction of the two couplers M and N, which give different dyes that can be clearly separated from each other, in the color image obtained by mixing the mixture and adding it to a silver halide emulsion for color development. It can be determined as a relative value by measuring the amount of pigment.

Maximum concentration (DM) wax of coupler M, D in the middle stage
If the color development of M and the color development of coupler N are (D N )wax and D N, respectively, then the ratio RM/RN of the reaction activity of the double force puller is expressed by the following formula.

That is, in a silver halide emulsion containing mixed couplers,
The value of the coupling activity ratio RM/RN can be determined from the line shape obtained by plotting several pairs of DM and DN obtained by applying various stages of exposure and color development as two orthogonal axes. .

By using a fixed coupler N and determining the value of RM/RN for various couplers as described above, a relative value of the coupling reaction rate, that is, a relative coupling reaction rate value can be determined.

In the present invention, it refers to the RM/RN value when the following coupler is used as the above coupler N.

The color developing solution used in the color development is as follows. Developed at 38°C for 3 minutes and 30 seconds.

(Color developer composition) Benzyl alcohol 15++1 ethylene glycol 15% potassium sulfite 2.0g potassium bromide
0. Sodium chloride
0.29 potassium carbonate
30.0g hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.5゜3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (
4,4'-diaminostilbenzsulfone derivative)
1,oy potassium hydroxide
Add 2.0° water to bring the total volume to 11 and adjust the pH to 1.
Adjust to 0.20.

The fast-reactive yellow coupler according to the present invention can have any structure as long as the above-mentioned relative coupling reaction rate value is 0.5 or more, but couplers represented by the maximum (A) below can be preferably used. .

^ In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction.

R3 is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially t-butyl group), and R2 is an aryl group (preferably phenyl group)
The alkyl group represented by these RI and R2 includes ``ζ'' and ``aryl'' which are profanities, and the aryl group of R is preferably substituted with a halogen atom, an alkyl group, or the like.

As X, a group represented by -maximum (B) or (C) below is preferable, and a group shown by (B) among -maximum (B) is particularly preferable.

General Formula (B) In the formula, zl represents a group of nonmetallic atoms that can form a 4- to 7-membered ring.

General formula (C) -O-R,.

In the formula, R1 represents an aryl group, a heterocyclic group or an acyl group, with an aryl group being preferred.

-maximum (B') represents the nonmetallic atomic group obtained.

The yellow coupler according to the present invention, which is preferred in the above-mentioned maximum (A), is represented by the following general formula (A').

-Maximum (A') In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and 9 or R14 is preferably a halogen atom.
+s, R, and R1? each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamide group, a ureido group, or an amine group 3 RI5 and RSS are each a hydrogen atom, R17 is preferably an alkoxycarbonyl group, an acylamide group or an alkylsulfonamide group, and X represents a group having the same meaning as that shown in the maximum (A) above. , preferably said - maximum (B) or (C)
and, among (B), the above-mentioned -a is more preferable.
Examples include a group represented by formula (B').

The yellow coupler used in the present invention and having a relative coupling rate value RM/RN of 0.5 or more (hereinafter simply referred to as the yellow coupler according to the present invention) may be added in any desired silver halide emulsion layer, but preferably blue It is a photosensitive silver halide emulsion layer, and the amount added is 2 x 1 per mole of silver.
It is preferably from 0-' to 5 X 10-' mol, more preferably from 1xlO-2 to 5 X 10-1 mol. Specific examples of the yellow coupler according to the present invention are listed below, but the invention is not limited thereto.

[Exemplary compounds]

(Y-1> (Y-2) (Y-3) (Y-4) (Y-5> (Y-6) (Y-7) (Y-8) (RM/RN=0.65) ( Y-9) (RM/RN=0.92> (Y-10) (Y-11) (Y-12) (Y-13) (RM/RN = 1, 27) (Y-14> (Y- 15) (Y-16) (Y-17) (Y-18) (Y-19) (Y-20) (R14/RN=0.88) (Y-21) (Y-23) (Y-24 ) (Y-25) (Y-26) (RM/RN=0.94) In addition, yellow couplers other than the yellow coupler according to the present invention may be further added as necessary, but in that case, The molar ratio of the yellow coupler of the invention to the yellow coupler of the invention is less than 0.5, preferably less than 0.3.

The yellow coupler according to the present invention can be produced using various methods such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the coupler. The oil-in-water emulsion dispersion method can be applied to a method of dispersing hydrophobic additives such as couplers. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low-boiling point and/or water-soluble organic solvent is added. After dissolving it in combination with a solvent and emulsifying and dispersing it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, and ultrasonic device, It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

In the present invention, among the above-mentioned high-boiling point organic solvents, high-boiling point organic solvents having a dielectric constant of 6.0 or less are particularly preferably used. Examples include phthalic acid esters, phosphoric acid esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably, the dielectric constant is 6.0 or less and 1.9 or more and 100
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less at °C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent, and even more preferred are phthalic esters. Note that the organic solvent may be a mixture of two or more types, and in this case, it is sufficient that the dielectric constant of the mixture is 6.0 or less.

Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

The phthalate esters which are high boiling point organic solvents with a dielectric constant of 6.0 or less that are most advantageously used in the present invention include:
Examples include those represented by the following formula [I[].

General formula [II] In the formula, R++1 and R34 are each an alkyl group,
Represents an alkenyl group or an aryl group. However, R33
The total number of carbon atoms in the groups represented by and R34 is 9 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, R33 and R of the above-mentioned formula [11]
The alkyl group represented by 34 is a linear or branched one, such as a butyl group, a pentyl group, a hexyl group,
heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
These include a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by Ro and R14 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have multiple substituents, such as halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. Examples of substituents on the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

In the case of a phosphoric acid ester having a dielectric constant of 6.0 or less, which is advantageously used in the present invention, and 1-, the general formula [II[] O RI90 F OR+ is traversed by the following formula [1] I].

In the formula, R3S I R3G and R1, are each
6 representing an alkyl group, alkenyl group or aryl group
However, R35, R) @ and R)? The total number of carbon atoms represented by is 24 to 54.

- R3s + Rz s and R37 of maximum [I11]
The alkyl group represented by is, for example, a butyl group, a pendel group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl group, 1-lysoyl group, tetradecyl group, pentadecyl group, hexadecyl group,
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl, alkenyl and aryl groups may contain single or multiple π substituents, preferably R3,, R, and R,? is an alkyl group, for example, 2-ethylhexyl group, n-octyl group, 3
．． 5.5-T-limethylhexyl group, n-nonyl group,
Examples include n-decyl group, 8cc-decyl group, 5ee-dodecyl group, and octyl group.

Examples of preferred high boiling point organic solvents with a dielectric constant of 6.0 or less are shown below.

Mu H5 12 C, H.

■ o-CHzCH (C1lz) scI130 CJ+5
(i) ■ 0”P OCJ1*(1) 0 Cs1Ls(i) o-CJ, 5(n) 0=P-0-C,)11.(n) 0 C5tL*(n) 0-01°H2 , (i) Jin0=P-0-CI.11.1(i) 0-C7゜Ll(i) 0 C+oL+(n) 0=P OC+2Hzs (n) oc,, nt+(n) 0 C88230 ) ■ O-C1□o2s(i) 0-P OC+2Hzs(i) O-C,□++25(i) In order to enhance the effect of the present invention, the weight ratio of the yellow coupler/high boiling point organic solvent according to the present invention is 3.5/1 or less, 1
．． It is particularly preferable to set it to 5 or more.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

Further, in the silver halide photographic light-sensitive material of the present invention, a magenta coupler and a cyan coupler are each contained in the silver halide emulsion layer of the present invention having a silver chloride content of 80 mol % or more.

As magenta dye-forming couplers, azole couplers, 5-pyrazolone couplers, open-chain acylacetonitrile couplers, etc. can be used, and as cyan dye-forming couplers, naphthol couplers, phenol couplers, etc. can be used.

In the silver halide photographic light-sensitive material of the present invention, the following general formula [
Couplers represented by [a] and [al] can be preferably used.

General formula [,] R.A.

^r [In formula 1. Ar represents an aryl group, Ra represents a hydrogen atom or a substituent, Ra2 represents a substituent, Y
is a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent, and W is -Nll-.

-NIICO- (the N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N II CON H-, where the integer is an integer of 1 or 2. ] Specific example of [,] II il shil 13 14 shi! l In the magenta coupler represented by the above general formula [a1] and general formula [a I ], Za represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Za is It may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyan group,
Spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group Heteroeroxy: J certain Shilokire acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group,
ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

19 Kasumi-12 116 Nabe-17 Magenta couplers represented by the general formulas [,L] and [,1] used in the present invention are disclosed in, for example, U.S. Pat.
No. 0.788, No. 3,061,432, No. 3.0
No. 62,653, No. 3,127,269, No. 3,
No. 311,476, No. 3,152゜896, No. 3
, No. 419,391, No. 3,519,429, No. 3,555,318, No. 3,684,514, No. 3,888,680, No. 3,907,571 ,
Same No. 3,928,044, Same No. 3930.861, Same No. 3,930,866, Same No. 3,933,500
Specifications such as No. 49-29639, JP-A No. 49-1
No. 11631, No. 49-129538, No. 50-13
No. 041, No. 52-58922, No. 55-62454
No. 55-118034, No. 56-38043,
Publications No. 57-35858 and No. 60-23855, British Patent No. 1,247,493, Belgian Patent No. 7
No. 69,116, No. 792.525, West German Patent No. 2,
No. 156, 111 of each Mei #II damage, Special Publication Showa 46-604
No. 79, JP-A-59-125732, JP-A No. 59-228
No. 252, No. 59-162548, No. 59-1719
No. 56, No. 60-33552, No. 60-43659, West German Patent No. 1,070,030, and US Pat. No. 3,725,067.

As the cyan image-forming coupler used in the present invention, couplers represented by the following maximum [E] and [F] can be preferably used.

-Maximum [E] 0■ In the formula, R3 represents an aryl group, a cycloalkyl group, or a heterocyclic group, R2 represents an alkyl group or a phenyl group, and R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. .

Z2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [F] H In the formula, R4 is an alkyl group (e.g. methyl group, ethyl group,
(propyl group, butyl group, nonyl group, etc.), Rs represents an alkyl group (e.g. methyl group, ethyl group, etc.),
R6 is a hydrogen atom, a halogen atom (e.g. fluorine, chlorine,
(bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

Z2 represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

Typical examples of cyan image forming couplers used in the present invention are described below, but the present invention is not limited thereto.

- I C-9 I I I 2 The cyan couplers of the present invention represented by maximum [E] and [F] are, for example, JP-A-59-146050, JP-A No. 60-117249, JP-A No. 59- No. 31953.

Examples of cyan couplers used in the Ikemi invention include, for example, U.S. Pat. No. 2,306,410, U.S. Pat.
, 367.531, 2,369,929, 2,423,730, 2,474°293, 2,476.008, 2,498,466 ,
No. 2,545,687, No. 2,728,660, No. 2,772,162, No. 2,895,828
No. 2,976.146, No. 3゜002.83
No. 6, No. 3,419,390, No. 3,446,6
No. 22, No. 3,476.563, No. 3,737,
No. 316, No. 3,758゜308, No. 3,839
,044, British Patent No. 478,991, British Patent No. 945
, No. 542, No. 1,084. ．． No. 480, Nos. 1 and 3
No. 77.233, No. 1,388,024 and No. 1
, 543,040, and JP-A-47-
No. 37425, No. 50-10135, No. 50-252
No. 28, No. 50-112038, No. 50-11742
No. 2, No. 50-130441, No. 51-6551,
No. 51-37647, No. 51-52828, No. 51
-108841, 53-109630, 54-
No. 48237, No. 54-66129, No. 54-131
Examples include those described in publications such as No. 931 and No. 55-32071.

Two or more of the above magenta and cyan couplers may be contained in the same layer of the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, respectively.
It may be included in more than one layer.

These magenta and cyan couplers are generally used in amounts ranging from 2.times.10@-" moles to 1 mole, preferably from 1.times.10@-2 moles to 8.times.10@-3 moles per mole of silver in the emulsion layer.

In order to incorporate the magenta coupler and cyan coupler used in the present invention into the emulsion, for example, phthalate ester (
dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, triphenyl phosphate, trioctyl phosphate, etc.) or N,N-dialkyl-converted amides M<N, N-diethyllaurinamide, etc. ) and low-boiling organic solvents such as ethyl acetate, butyl acetate or butyl propionate, or optionally in mixtures of these solvents. Or after mixing and dissolving, mix with gelatin aqueous solution containing surfactant, then high speed rotation mixer,
After emulsifying and dispersing using a colloid mill or an ultrasonic disperser, a silver halide emulsion can be prepared by adding silver halide.

In the present invention, at least one of the non-photosensitive layers contains a compound represented by the general formula [1].

-Formula [1] In the general formula [1], examples of the alkyl group having 1 to 5 carbon atoms represented by R1 and R2 include methyl group, ethyl group, n-propyl group, i-propyl group, and n-butyl group. group, S-butyl group, n-pentyl group, neopentyl group, etc. n represents an integer of 1 to 2o, preferably an integer of 2 to 15, k represents 1 or 2, A
represents a hydrogen atom, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, R6 represents a hydrogen atom, an alkyl group, or an aryl group),
-〇Y (here, Y represents R3 or CR), R1
) represents a hydrogen atom, an alkyl group, an aryl group or CR3, and R1 has the same meaning as above. ), R1 has the same meaning as above, R6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group) or a cyano group.

B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a group represented by R9 -C・R2・+, - to -(A)k<
Here, R,, R2, n, and A have the same meanings as above. ), an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group represented by R3, an alkyl group, an aryl group represented by R1, an alkyl group, an aryl group represented by R9, an alkyl group represented by R6, Cycloalkyl group, alkenyl group, aryl group, and B
The alkyl group, alkenyl group, cycloalkyl group, aryl group, and heterocyclic group represented by include those each having a substituent, and examples of the substituent of the above alkyl group include a halogen atom, a cycloalkyl group, an alkenyl group, Examples include aryl groups, alkoxy groups, aryloxy groups, acyl groups, heterocyclic groups, cyano groups, etc. Substituents for the above alkenyl groups, cycloalkyl groups, aryl groups, and heterocyclic groups include, for example, halogen atoms, alkyl groups, etc. , cycloalkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acyl group, heterocyclic group, cyano group, and the like.

Examples of the alkyl group represented by R), R4, Rs, Rs and B include methyl group, ethyl group, 1-propyl group, n-butyl group, S-butyl group, n-hexyl group, 2-ethyl-hexyl group. Examples of alkenyl groups represented by R3, R* and B include aryl groups, and examples of alkenyl groups represented by R, R* and B include Examples of the cycloalkyl group include a cycloalkyl group.

Examples of the aryl group represented by Rx, R4, Rs, Rs and B include a phenyl group and a naphthyl group.

The compound represented by the above-mentioned maximum [1] may further be a compound represented by the following maximum [1-11] or the compound represented by the maximum [1] below.
-1] [wherein R, , R2, R3+X and n are general formula [1]
has the same meaning as R8, R2, Rs, X and n. ]
Specific examples of the compound represented by the general formula [1] used in the present invention are shown below, but the present invention is not limited thereto.

H(1) H(2) H(3) H(5) Ul+! -1(6) H(7) H(8) H(9) H(10) H(11) H(12) )+ (13) H(14) H(15) i H(16) H(17 ) Regarding the compound represented by the maximum formula [1] above (hereinafter referred to as the compound represented by the formula [1] according to the present invention),
The compounds described in JP-A No. 58-24141 are basically included, and the synthesis methods described therein can be referred to.

The compound represented by the general formula [i] according to the present invention is contained in at least one layer selected from non-photosensitive layers (for example, an intermediate layer, a protective layer, an undercoat layer, a filter layer, etc.) of a silver halide photographic light-sensitive material. The amount added is not particularly limited, but preferably lXl0-' to 1 x 1o-2
The compound represented by the general formula [11] according to the present invention may be used alone or in combination of two or more.

In the silver halide photographic light-sensitive material of the present invention, each of the silver halide emulsions of the present invention containing silver halide grains of the present invention having a silver chloride content of 80 mol % or more is coated with the silver halide emulsion of the present invention on a support. It has a silver halide emulsion layer containing the fast-reacting yellow coupler, magenta coupler and cyan coupler according to the invention, and further has a non-photosensitive layer,
At least one of the non-photosensitive layers contains a compound represented by the general formula [I].

The silver halide photographic material having the structure of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but especially when applied to color photographic paper for direct viewing. The effects of the present invention are effectively exhibited.

The silver halide emulsion layer of the present invention containing yellow, magenta, and cyan couplers and the non-light-sensitive layer have a structure in which M layers are formed on a support in an appropriate number and order of layers. It is within the scope of the present invention to appropriately change the number of layers and the order of layers depending on the important performance and purpose of use.

In the silver halide photographic light-sensitive material of the present invention, as a specific preferred layer structure, a yellow dye image forming layer, a first intermediate layer, a magenta dye image forming layer, and an ultraviolet absorber are sequentially formed on the support from the support side. A second intermediate layer containing a cyan dye image forming layer, an intermediate layer containing an ultraviolet absorber, and a protective layer are arranged.

The compound represented by the above general formula [11] contained in at least one layer of the non-photosensitive layer is preferably added in the first intermediate layer in the layer structure preferable for the present invention. gelatin is used as the binder (or protective colloid) in the silver halide emulsion of the present invention, and more preferably in the first intermediate layer and the second intermediate layer containing the ultraviolet absorber. It is advantageous to
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer is contained in the photographic emulsion layer or other hydrophilic colloid layer of a photosensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. I can do things.

In the light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention contain 11J! It may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging due to rubbing, etc., and to prevent deterioration of images due to ultraviolet light.

A light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, increases the ease of writing, and prevents photosensitive materials from sticking together. A matting agent can be added to achieve this goal.

Slip R1 of photosensitive material using silver halide emulsion of the present invention
6. A lubricant can be added to reduce scratches.An antistatic agent can be added to the light-sensitive material using the silver halide emulsion of the present invention for the purpose of preventing static electricity.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in colloid layers.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

□The photosensitive material using the silver halide emulsion of the present invention is a photographic emulsion, and the other layers are a baryta layer or a visible reflective support such as paper laminated with an α-olefin polymer, synthetic paper, cellulose acetate, cellulose nitrate, It can be applied to films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be prepared directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
It may be applied via one or more subbing layers to improve wear resistance, hardness, antihalation, friction properties, and/or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Lusion coatings and curtain coatings are particularly useful.

The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region in which the emulsion layer constituting the light-sensitive material of the present invention has a negative effect. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by subjecting it to a color development treatment known in the art.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than in the free state. Additionally, these compounds generally have a content of about 0.1. ,~about 30. concentration, preferably from about 1 g to about 15 g for color developer 11
Use at a concentration of g.

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, the alkyl group and phenyl group may be substituted with any substituent.Among them, particularly useful examples include N,N'-diethyl-p-phenylenediamine. Dilenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N
, N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl 4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate.

The pH value of the color developer is usually greater than 7, most commonly from 10 to about 13.

The silver halide photographic light-sensitive material of the present invention contains these color developing agents in the hydrophilic colloid layer as the color developing agent itself or as its precursor, and can be used for zero color development which can be treated with an alkaline activation bath. The active ingredient precursor is a compound that can generate a color developing agent under alkaline conditions, such as a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, and a sugar amine. Examples include reactant glecursers and urethane-type precursors. The precursors of these aromatic primary amine color developing agents are:
For example, U.S. Patent No. 3,342.599, U.S. Pat.
No. 7,114, No. 2,695,234, No. 3,7
No. 19,492, specifications of British Patent No. 803,783, Japanese Patent Application Publication Nos. 53-185628 and 54-79035
Issues of publications, Research Disclosure Magazine 1515
No. 9, No. 12146, and No. 13924.

These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient color development can be obtained upon activation treatment. The amount varies depending on the type of photosensitive material, but is generally in the range of 0.1 to 5 moles, preferably 0.5 to 3 moles, per mole of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc.
It can be added as an emulsified dispersion using a high-boiling organic solvent such as dioctyl phthalate or tricresyl phosphate, or it can be added by impregnating a latex polymer as described in Research Disclosure No. 14850. can.

It is preferable that the color developing solution contains a hydroxylamine compound as a preservative.

The hydroxylamine compound is not particularly limited, and includes, for example, hydroxylamine itself, N-monoalkylhydroxylamine such as N-methylhydroxylamine hydrochloride, or N.

N-diethylhydroxylamine, aminoalkylhydroxylamine as described in U.S. Pat. No. 3,287.125, alkoxyhydroxylamine as described in U.S. Pat. No. 3,293,034, sulfone as described in U.S. Pat. No. 3,287,124. N,N-dialkylhydroxylamines such as hydroxylamine, or heterocyclic N-hydroxylamines such as N-hydroxypiperidine are used as such or in the form of salts, but usually cost,
Hydroxylamine sulfate, hydroxylamine hydrochloride, and oxalic acid N from commercial viewpoints such as stability, water solubility, supplyability, and suitability for use.

The concentration of the hydroxylamine compound used depends on the type and concentration of the color developing agent, and the pH and temperature of the color developer, but the preferred concentration of the hydroxylamine compound is preferably 0, O1 to 0.0 per 11 of the color developer. 2 mol, more preferably in the range of o, oio to 1.10 mol. The color developing solution of the present invention contains sodium hydroxide, hydroxide (hypotassium, ammonium hydroxide, sodium carbonate, potassium carbonate) as a common alkaline agent. , sodium sulfate, sodium metaborate, tertiary sodium phosphate, tertiary potassium phosphate, etc. In addition, in order to provide alkaline buffering capacity, dibasic phosphate, dipotassium hydrogen phosphate, and sodium dihydrogen phosphate are added. , potassium dihydrogen phosphate, potassium heavy carbon, sl/lium heavy carbon, and other salts are used.

In addition, the color developing solution contains sulfites (e.g. sodium sulfite, potassium sulfite), various additives such as benzyl alcohol, halogenated alkali such as potassium bromide or potassium chloride, and various antifoaming agents. or a surfactant, and an organic solvent such as methanol, dimethylformamide or dimethyl sulfoxide.

However, benzyl alcohol is not necessarily necessary in the color developing solution of the present invention, and is preferably reduced or removed from the viewpoint of low pollution.

In addition, the bromide ion concentration is 0.4 to 2.0 g, preferably 0.6 to 2.0 g per 11 color developing solution, in terms of potassium bromide.
It is 1.5g.

The color development treatment of the silver halide photographic light-sensitive material according to the present invention can be carried out under any conditions, but it is carried out at a temperature of 25°C or higher, preferably 30°C or higher and 45°C or lower, and the development time is 40 seconds or more and 120 seconds or less. It is preferable that

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be carried out simultaneously with fixing treatment.Many compounds are used as bleaching agents, among them iron (Iff), cobalt (I[[), 1
polyvalent metal compounds such as (II), in particular complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid , metal complex salts such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and 1,000-onythyl.

After the fixing process, a washing process is usually performed.

In addition, as an alternative to washing with water, stabilization treatment may be performed, or both may be used in combination. can be done. These specific conditions are described in Japanese Unexamined Patent Publication No. 5
8-134636 etc. can be referred to.

[Specific effects of the invention]

As explained above, it is an object of the present invention to provide a highly sensitive silver halide photographic material that is outstanding not only in high development speed but also in high color development speed, and in which the occurrence of brown turbidity is suppressed to a minimum. was completed.

〔Example〕

The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to these embodiments.

[Example 1] A multilayer silver halide photographic material was prepared with the configuration shown in Table 1. The stain inhibitors contained in the second, fourth and sixth layers and the yellow coupler contained in the first layer were changed as shown in Table 2.

<Preparation of silver halide emulsion> (EM-A) (Silver chloride) A silver nitrate solution and a sodium chloride solution were added to an inert gelatin aqueous solution for 60 minutes by a double jet method.

At this time, the temperature was maintained at 50° C. and pA g = 7.0.

Next, desalting and washing with water were performed in a conventional manner to obtain EM-A.

EM-A consists of cubic silver chloride grains with an average grain size of 0.8 μm.

(EM-B) (Silver chlorobromide) A silver nitrate solution and an aqueous solution containing sodium chloride and potassium bromide were added to an inert gelatin aqueous solution by a double jet method. At this time, the temperature was maintained at 60''C1pA9=5.5.

Next, desalting and washing with water were performed in a conventional manner to obtain EM-B.

EM-B is cubic silver chlorobromide particles (
Silver chloride content: 20 mol%).

The EM-A and EM-B obtained here were sensitized with sulfur by adding sodium thiosulfate, and the sensitizing dye [5D-
1] was spectrally sensitized.

The following emulsions were prepared in the same manner as EM-A and EM-B.

Spectral sensitizing dye used [5D-1] [5D-2] [5D-3] Table-1-1 The numbers in parentheses indicate the coating type or amount added.

* is shown in Table-2 Table-1-2 The structures of the compounds used in the table are shown below.

Yellow coupler (Y-1> Ultraviolet absorber (UV-1> Ultraviolet absorber (UV-2> Anti-stain agent (AS-1) l Cyan coupler (CC-1) Shi! Cyan coupler (c c -2) Magenta Coupler (MC-1) The obtained samples 1 to 14 were subjected to optical wedge exposure with white light using a sensitometer (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Here, the following tests were conducted to examine the effects of the present invention.

■Photoelectric densitometer (Konishi Roku Photo Industry Co., Ltd.) for each sensitometry-treated sample
The relative sensitivity and maximum reflection density were determined using a PDA-65 model manufactured by Co., Ltd., and the results are shown in Table 3.

0 Color turbidity test After obtaining a yellow colored sample using blue exposure instead of the white exposure, the blue density (D It) of the sample was 1.
The green density component (DG) when giving a value of 0 was used as a representative characteristic of color turbidity from the third layer to the first layer.

Similarly, green exposure is performed to obtain a magenta colored sample, and when the green density (DG) is 1.0, the representative characteristic of color turbidity from the fifth layer to the third layer is determined by the red density component (D R). Toshina.

The lower these values, the better the color turbidity.

[Processing process] Temperature
Time development color development 34.7±0.3℃ 5
0 seconds bleach fixing 34.7±0.5℃ 5
Stabilization for 0 seconds 30-34℃ 90 seconds Drying 60-80℃ 60
Seconds [Color developer] Pure water
800m&'ethylene glycol
10mfN, N-diethylhydroxylamine 1
0y Potassium chloride 29N-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add water to bring the total volume to 11 and adjust to +9810.08 (:a white fixer) ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 31? Ammonium thiosulfate (70% solution) 100mj + ammonium sulfite (40% solution) 27.5me Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to make the entire wall 1e.

(Stabilizing liquid) 5-di-4-2-methyl-4-inthiazolin-3-one 131-hydroxyethylidene-1,1-diphosphonic acid Add 2 g of water to make 11, and adjust to pH 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

From the results in Table 3, we first compare Samples 1 to 4 using silver halide emulsions with low silver chloride content ratios. It is clear that even if yellow couplers are used alone or in combination, the sensitivity and maximum density will not be as good as those obtained when rapid processing is performed as shown in this example.

On the other hand, in Sample 5, which used a silver halide emulsion with a higher silver chloride content than Sample 1, although the sensitivity and maximum density were slightly improved, the color turbidity was significantly deteriorated, which greatly affected color reproduction. Put it away.

Moreover, compared to sample 5, sample 6 using the stain inhibitor according to the present invention and sample 8 using the yellow coupler according to the present invention do not show a significant improvement in color turbidity. Even if the amount of anti-staining agent other than the invention is increased, the color turbidity is hardly improved and desensitization increases.

7, 10 to 1 according to the present invention compared to these comparative samples.
3, the color turbidity has been improved to a level where there is no problem at all,
Moreover, the sensitivity and maximum concentration in rapid processing were also sufficient.

Further, when a silver halide emulsion having a low silver chloride ratio is used, as in Sample 14, deterioration occurs in relative sensitivity, maximum density, or color turbidity.

[Example 2] In sample 7 in Example 1, the yellow coupler was changed to Y.
-3, Y-8, Y-12 and Y-23 to create samples 15, 16, 17 and 18. Similarly, stain inhibitors were added to H-2, H-4, H-10 and H-1.
Samples 19, 20, 21 and 22 were prepared by changing the sample to 1.

Example 1 regarding these samples 15 to 22 according to the present invention
When a similar test was conducted, almost the same results as in Example 1 were obtained.

[Example 3] Preparation of silver halide emulsion> A silver nitrate aqueous solution and an aqueous solution containing sodium chloride and potassium bromide were added to an inert gelatin aqueous solution by the Gubrunoet method. At this time, the temperature is 45°C11) ε is 7.0
I tried to keep it at .

Subsequently, the emulsion was desalted and washed with water in a conventional manner to obtain a cubic silver chlorobromide emulsion EM-G to EH-L shown in Table 4.

Table-4 Addition time Average particle size Silver chloride content Spectral sensitizing dye EM
G 150 minutes 0.70μta 99,3
Mol% SD-IEM-H60 minutes 0.35μ theory
99.5 mol% SD-2EM-I 80 minutes 0.40 μm 99.7 mol% SD-3E
M-J 150 minutes 0.70 μm 85 mol%
SD-IEM-K 60 minutes 0.35μ 85 mol% SD-2EM-L 80 minutes 0.40μ 85 mol% 5D-3 Add sodium thiosulfate and gold chloride from the EM-G obtained here to EH-L. Chemical sensitization was performed by adding an acid, and further spectral sensitization was performed using the spectral sensitizing dyes shown in Table 4.

A multilayer silver helodenide photographic material was prepared in the same manner as in Example 1. Furthermore, the stain inhibitor of the present invention,
The yellow coupler and silver halide emulsion were changed as shown in Table 5. Furthermore, magenta couplers and cyan couplers are also shown in Table 5.

In addition, in Table 5, the silver risk of the three-layer foil coating for sample 37 was set at 0.2 g/2 mackerels.

The obtained samples 30 to 38 were exposed to light in the same manner as in Example 1, and subjected to sensitometry and a color turbidity test. The results obtained are shown in Table-6.

However, here, the following treatment was performed.

[Development process] Temperature ("C) Time (seconds) Color development 35.0+0.3 45 Bleach-fixing 35.0±0.5 45 Stabilization
30-3490 Dry 60-80
60 The composition of the treatment liquid used in each treatment step is as follows.

"Color developer" Pure water 800ml Trieta/-luamine 10gN, N-noethylhydroxyamine 5g Potassium chloride
2g potassium bromide
0.010゜Potassium sulfite
0.3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenecyaminetetraacetic acid a 1. Tefur-3,5-nosulfonic acid disodium salt 1.0gN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7mino7niline sulfate
4.5g potassium carbonate
27g 7g Fluorescent brightener -4'-diaminostylpentsulfonic acid derivative J(k) 1.0g Add water to bring the total volume to 11, and adjust to pH = 10.10.

"Bleach constant' = 6.2, and add water to bring the total volume to 11.

"Stabilizing liquid" 5-chloro-2-methyl-isothiazolin-3-one
1.0 g ethylene glyfur 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 20 g ethylenequamine tetraacetic acid g t,o.

Ammonium hydroxide (20% aqueous solution) 3.0g
Ammonium sulfite 3.0g Fluorescent brightener (4-4'-diaminostilpentesulfonic acid derivative) 1.5° Water was added to make the solution 11, and from the results of sulfuric acid or potassium hydroxide fi-6, the structure of the present invention was determined. Samples 32 to 38 are comparative samples 30 and 3.
It can be seen that, compared to Example 1, color turbidity has been improved to a completely non-problematic level, and sensitivity and maximum density in rapid processing are also sufficient.

[Example 41 Samples 41, 42, 43 and 44 were prepared by changing the Yea-a coupler in Sample 32 in Example 3 to Y-3, Y-8, Y-12 and Y-23. Similarly, stain inhibitors were added to H-2, H-4, H-10 and V.
H-IN=Change, TeE! 445.46.4'l I made 48 pieces.

When the same tests as in Example 3 were carried out on these samples 41 to 48 according to the present invention, the same results as in Example 3 were obtained.

Applicant Konishi Roku Photography Co., Ltd. Procedures - How to write the city official ヱ0 1. Description of the case 1985 Patent Application No. 102435 2 Name of the invention Silver halide photographic photophobic material 3 Person making the amendment Relationship to the case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 191, Japan (tel: 0425-83-1521) Patent Department.

5. Subject of correction Full statement.

6. Contents of amendment Engraving of the statement (no changes to the contents).

As per attached sheet.

Claims (1)

[Claims] The relative coupling reaction rate ratio RM/RN value is 0 on the support.
．． A photographic constituent layer composed of a silver halide emulsion layer containing a yellow coupler of 5 or more, a silver halide emulsion layer containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and a non-photosensitive layer. In the silver halide photographic light-sensitive material, each of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 80 mol% or more, and at least one of the non-photosensitive layers has the following general formula: A silver halide photographic material comprising at least one compound represented by [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.
represents 1 or 2. A includes ▲mathematical formulas, chemical formulas, tables, etc.▼(Here, X represents -O- or -N-, and R
_3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and R_4 represents a hydrogen atom, an alkyl group, or an aryl group. ), -OY(
Here, Y represents R_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_3 has the same meaning as above. ), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R_4 has the same meaning as above, R_5 is a hydrogen atom, alkyl group, aryl group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Representation, R
_3 has the same meaning as above. ), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (Here, l represents 0 or 1, R_3 has the same meaning as above, and R_6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. ) or a cyano group. B is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a group represented by ▲ which has a numerical formula, chemical formula, table, etc. (here, R_1, R_2, n,
k and A have the same meanings as above. ). ]