JPH01292335A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sharpness and the color reproducibility of an image by incorporating a jointly a layer contg. a cationic polymer having a guanidyl ketimine residual group and a dyestuff in the photosensitive material. CONSTITUTION:Silver chlorobromide or silver chloride contd. in a total silver halide particle having a mean silver chloride content of >=90mol.% is incorporated in at least one layer of photosensitive emulsion layers. The layer contg. a polymer compd. having the guanidyl ketimine residual group is mounted on the photosensitive material adjacent to the emulsion layer thereof. A mercaptozole compd. is incorporated in anyone layer selected from the emulsion layer, its adjacent layer and an intermediate layer between them. Thus, the generation of a fog is prevented. The polymer compd. is selected from a polymer having a repeating unit structure. The dyestuff having a light absorption at a spectral sensitive wavelength region is incorporated in the photosensitive layer mounted on the layer contg. the cationic polymer to prevent the halation of the photosensitive material, and the dyestuff having the light absorption at a wavelength region of the sensitivity to be corrected is incorporated in the photosensitive layer to correct the spectral sensitive distribution of the photosensitive material.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photographic material provided with a silver halide emulsion layer, and in particular, a mordant layer is provided to improve sharpness, color reproducibility, and whiteness of a reflective support. This invention relates to a color print photosensitive material that has been improved.

(Prior art) Color photosensitive materials for general photography have a multilayer structure including a photosensitive layer containing a color coupler, and a layer containing a polymer that provides cation sites is provided as an antihalation layer or filter layer to improve image quality. It is known to use an adsorption layer of a development-inhibiting substance to improve sharpness and color reproducibility, and to speed up the development process and improve stabilization. This is true, for example, in U.S. Pat.
No. ゜057, No. 2,882,156, No. 2゜97
2.535, 3,125,550, 3,7
No. 40,228, No. 2,839.401, No. 3,
625,691, Japanese Patent Publication No. 49-15820, Japanese Patent Application Laid-open No. 55-33172, and Japanese Patent Application Laid-open No. 50-65230.

In recent years, there has been an increasing demand for improvements in image sharpness, color reproducibility, and gradation in color photosensitive materials for general photography, and in particular color negative photosensitive materials, as well as improvements in image sharpness and color reproducibility in color photosensitive materials for printing.

As a method for improving the sharpness of images of color print sensitive materials, previously disclosed in JP-A-62-32448, at least 50% or more of the total projected area of silver halide grains are plate-shaped with an average aspect ratio of 5 or more. It was proposed to provide a layer containing a decolorizing colorant in a photographic processing step between a silver halide photographic emulsion layer containing grains and a reflective support. More specifically, such colorants include colloidal silver dispersions, various filter dyes, and combinations of these dyes and mordants.Mordants include imidazole rings, pyridine rings, Polymer compounds having a basic group such as homopolymers and copolymers having an alkylaminoalkyl group or a quaternary salt thereof, an aminoguanidine group, etc. are useful.

However, in the case of reflective photosensitive materials containing high silver chloride emulsions containing 90 mol% or more of silver chloride, which are useful for rapid processing, it is necessary to use water-soluble dyes to improve image sharpness and color reproducibility. There are some difficulties.

That is, firstly, when the whiteness of the reflective (first type diffuse reflective) support is increased, halation increases. Second, when a high silver chloride emulsion is used, not only does the reflected light become stronger, but also the multilayer effect and interimage effect due to development are reduced, and the sharpness is deteriorated. Third, increasing the amount of conventional water-soluble dyes used not only reduces sensitivity due to light absorption caused by dyes that are not effective in preventing halation, but also reduces spectral sensitization.
damage, the occurrence of spectral sensitivity by itself, desensitization, capri and residual color increase.

Therefore, it is necessary to effectively absorb scattered light with a small amount of use.

In addition, cationic polymers used as mordants are
When dispersed in gelatin, there is a problem that agglomeration generally occurs and the surface quality of the coating deteriorates, and this defect is particularly noticeable in the case of color printing fibers.

(Problems to be Solved by the Invention) Therefore, the purpose of the present invention is to solve the above-mentioned problems, and specifically, firstly, to provide high-chloride silver with excellent image sharpness, coating, and surface quality. The object of the present invention is to provide an emulsion-containing photographic material, and a second object is to provide a photographic material for color printing which has excellent whiteness and improved color reproducibility.

(Means for Solving the Problems) The above objectives can be effectively achieved by the following invention (1), and more preferably by invention (2).

(1) In a silver halide photographic material comprising at least one light-sensitive emulsion layer containing silver halide grains coated on a reflective support, the at least one emulsion layer contains all the halogens contained therein. Silver chloride grains contain silver chlorobromide or silver chloride with an average silver chloride content of 90 mol% or more, and contain a polymer compound containing a repeating unit having a guanidyl ketimine residue in the vicinity of the emulsion layer. 1. A silver halide photographic light-sensitive material, which further contains a mercaptoazole compound in any one of a cough polymer compound-containing layer, a silver halide emulsion layer, and a layer located between these layers.

(2) The photosensitive emulsion layer containing silver halide grains contains silver chlorobromide or normal crystals of silver chloride in which the average silver chloride content of all the silver halide grains contained therein is 90 mol% or more. , and at least 50% by weight of all the silver halide grains contained therein have a localized silver bromide phase inside or on the surface of the grains (1).
).The silver halide photographic material described in ).

The polymer compound having a guanidyl ketimine residue used in the present invention has a particularly strong affinity with gelatin as a hydrophilic colloid, and has the advantage of being easily dispersed therein without producing lumps.

However, the following defects were found. The guanidylketimine residue forms a complex compound with silver ions, has the effect of helping to dissolve silver chloride, and has reducing properties in an alkaline aqueous solution. Therefore, the photosensitive silver halide grains are silver chlorobromide or silver chloride grains with a high silver chloride content,
When a compound having a guanidyl ketimine residue comes close to this, physical development tends to be accelerated during the color development process and fogging tends to occur strongly. In order to prevent this, it is preferable to use high silver chloride grains having a silver bromide localized phase on the surface of the silver halide grains. Furthermore, by using a mercaptoazole compound among adsorbent substances that inhibit physical development on silver halide grains in advance, it is possible to more effectively put the polymer compound having a guanidyl ketimine residue according to the present invention into practical use. can.

The polymer compound having a guanidyl ketimine residue used in the present invention is "preferably" a compound selected from polymers having a repeating unit structure represented by the following general formula (I).

General 2N) CHs CHz NH '+1Cffi, HgSO4, H, p. 4□F. $V
6 h 6゜The above-mentioned polymer compound having a guanidyl ketimine residue is disclosed in U.S. Patent Nos. 3,282,699 and 3
It can be obtained by the methods described in British Patent No. 740.228, British Patent No. 3,625,691, British Patent No. 1,381,263, and British Patent No. 1,381.264. More specifically, various products can be easily produced by condensing the carbonyl group of a polymer having a repeating unit structure of 1,1-dimethyl-3-oxobutylacrylamide as shown below with aminoguanidine or a salt thereof.

+cuz-c→-CH.

I C0NII -C-CI□-COCHsThe polymer having a guanidylketimine residue may be a homopolymer,
Preferably, the copolymer has a monomer content of 20% or more (molar ratio) having a guanidyl ketimine residue. Examples of comonomers constituting the copolymer include vinyl monomers such as acrylic esters, methacrylic esters, acrylamide and derivatives thereof, styrene, vinylpyrrolidone, 2-alkylvinylimidazole derivatives, and vinyl esters. Also, there are fewer anionic water-soluble groups than guanidylketimine residues (molar ratio).
It can also be contained as part of the amount. Further, the polymer can also be made diffusion resistant by crosslinking using a crosslinking agent such as divinylbenzene.

The polymer compound having a guanidyl ketimine residue used in the present invention is preferably a polymer having molecules is, ooo to 1oo, ooo.

Specific examples of polymers having guanidyl ketimine residues are shown below, but the invention is not limited thereto.

x, y, and z indicate the content (molar ratio) of each component.

(+)-(11 CHy Ctl:+CHs
NHzx/y=5015〇=(2) Ctl+ Cl13 CHjNHzx
/ y = 20/80 x / y = 10/90 = (4) X / F = 50150 X / 1 / z = 30/ 20/ 5OCI+
3 , polyvinyl alcohol or a mixture thereof, and after adding a suitable dye, it is preferably applied as an antihalation layer or filter layer on a support. In this case, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, hardeners, stabilizers for silver halide emulsions, etc. can be added as coating aids.

In the present invention, it is preferable to use an anti-capri agent, an anti-stain agent, an anti-color mixing agent, etc. together with the dye.

The amount of the polymer of the present invention added is preferably 1 to 50% by weight, more preferably 2% by weight, based on the hydrophilic colloid, such as gelatin.
It is preferable to add 0 to 40% by weight.

The dye used in the present invention is particularly preferably an acid dye, which has spectral absorption characteristics that match the spectral sensitivity of the silver halide emulsion layer of the light-sensitive material of the present invention, and particularly has a molar absorption coefficient of 10" 1 mol. -cm-' or more is preferable. In color light-sensitive materials using a reflective support, dyes that do not leave any residual color by being decolorized or eluted during the development process are preferable.

The dyes used in the present invention include commonly known dyes, such as azomethine dyes, styryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, diarylmethane dyes, and triaryl dyes. It can be selected from the group of methane dyes, azomethine dyes, azo dyes, metal chelate dyes, anthraquinone dyes, stilbene dyes, chalcone dyes, and indophenol dyes. For example, U.S. Patent Nos. 3,880,658, 3,931,144, and 3
, No. 932,380, No. 3,932,381, No. 3,
No. 942,987, J. Fabian, H. Hartmann (J, Fabian,) I.

Hartlmann), ``Light Absorption of Organic Colorants'' (Light^
bsorption of Organic Co1o
rants), (Springer filter layer (
Springer-Verlag) (or diffusion-resistant analogues) can also be selected. The dyes used in the present invention are the functional dyes disclosed in Japanese Patent Application No. 106892/1982, and the functional dyes disclosed in Japanese Patent Application No.
Specification No. 1-88625, Specification of Japanese Patent Application No. 136947 (1988) (pages 109 to 117) and Japanese Patent Application No. 1988-4
No. 3704 and the dye represented by the general formula (1) of Japanese Patent Application No. 62-153132, JP-A No. 62-226
Among the dyes represented by the general formula (I[) in the specification of No. 131, it is also possible to select dyes that match the spectral absorption characteristics and do not leave any residual color after development. In order to prevent halation, dyes that absorb light in the spectral sensitivity wavelength range of the photosensitive layer provided on the cationic polymer-containing layer are used, and in order to correct the spectral sensitivity distribution, dyes that absorb light in the spectral sensitivity wavelength range are used. Dyes that absorb light are used. 80% of dyes used in photographic emulsion layers or other window material constituent layers
The above is preferably included in the cationic polymer-containing layer. Also, the amount of dye added is relative to the number of cation sites.
It is advantageous for the number of anionic groups in the dye to be from 0.01 to 10, preferably from 0.2 to 1.

Preferred dyes used in the present invention include Japanese Patent Application Nos. 61-287295 and 61-31 for preventing halation.
No. 4428, No. 62-79483, No. 62-1103
No. 33, No. 62-226131, No. 62-27766
No. 9, No. 62-284448, etc., and for correction of spectral sensitivity, Japanese Patent Application No. 62-34264,
Examples include dyes described in No. 62-239032, No. 62-264396, No. 62-26 +, No. 052, and No. 62-247477.

Particularly preferred dyes include those described in Japanese Patent Application No. 61-287295, 62-79483, 62-153132, 62-226131, 62-284448, and 62-123454. It will be done.

Next, specific examples of dyes used in the present invention will be shown.

However, it is not limited.

Dye-1 SO, K SO3 to SO3Na 5OJa ((:8K
) 2SO3K (C1l□), 5OI
KCHzCll□5O3K CHzCH
□SO3 to SOzNa 5O
Ja) l 5OJ 5OJ 15 CH3 I (CHz) 3sO+, K (CHz)s
sOJ (CH2) tsOJ (CH
2) 2SOJ0■ C, I+.

N(C113)Z (CL) aSOx-((Jlt) *5ChK(CI
lt) 2S03゜(CL),so,ni(CII2)
, 503e (CIlt) asoJ1
] (CHz) 2SO:IK (C112)
zsOa to □ OJ 03Na OJa :31 (C!(2) 4SO3゜(CI+□)4SO3 to Ct
ltCOOK CH□C00KCH2CH
2SO, It is preferable that a layer containing a high molecular compound containing a polymer compound is provided. The silver halide grains contained in the silver halide emulsion used are substantially silver chlorobromide or silver chloride; 1. Preferably, the average silver chloride content of the norogenated grains is 95 mol % or more.

"Substantially" means grains containing less than 1 mol % or no silver iodide and less than 1 mol % or no other silver salts such as silver rhodan.

The silver halide grains of the present invention may have any shape, but preferred grains are normal crystal grains, such as cubes, rectangular parallelepipeds, dodecahedrons, tetradecahedrons, octahedrons, etc. Particularly preferred are cubic grains. A silver halide grain having a localized silver bromide phase containing more silver bromide than the surrounding phase inside or on the surface of the grain. For localization,
It can exist in layers or as isolated islands or discontinuous phases. Particularly preferred is a form in which it exists in the form of isolated islands on the surface or in a thin (for example, 0.01 μm or less) layer form on the surface. When using normal crystal particles, their light scattering or reflection is relatively weak compared to other irregular particles, and it is easier to obtain sharp highlight gradations, giving them a superior appearance. , which is advantageous for improving sharpness. High silver chloride-containing grains with localization properties also tend to provide rapid developability and interimage effects.

The silver bromide content of the silver bromide localized phase is preferably 5 to 100 mol% of silver chlorobromide or silver bromide, more preferably 15 to 70 mol%, particularly preferably 20 to 100 mol%. It is in the range of 60 mol%. The silver salt of the silver bromide localized phase may be a salt other than silver chloride, such as Rodan's salt. The localization preferably consists of 0.1 to 20 mol% of silver stars, particularly 0.5 to 7 mol% of the total 1 Uffi constituting the silver halide grains.
Preferably, it is composed of silver.

The silver bromide content for localization can be determined using the X-ray analysis method (for example, described in the bulletin of "Japanese Chemical Complete Edition, New Experimental Chemistry Course 6, Structural Analysis") or the XPS method (for example, "Surface Analysis, -
1MA, Ausch electron, application of photoelectron spectroscopy (described in Kodansha), etc. can be used for analysis.

The interface between the localized phase and other phases may be clear or may have a gradually changing short dislocation region.

The localization phase and other phases (substrates) each contain different types and amounts of Group Ⅰ dissimilar metal ions, such as I'', Rh, Pt.
, Fe, Pd, etc. are preferably contained.

As the production method for the localization, various methods used for conventional silver halide formation can be used. For example, a localized silver salt can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, it is also possible to form localized silver using a so-called conversion method, which involves adding a Br supplying agent to already formed high silver chloride to partially convert it into silver halide with a smaller solubility product. can. Alternatively, localized particles can also be formed by adding silver bromide fine particles and recrystallizing them on the surface of silver chloride particles.

Preferably, the localization agent is deposited with at least 50% of the total iridium added during the preparation of the silver halide grains.

Here, depositing the localized compound together with iridium ions refers to supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver and/or halogen to form the localized compound. say.

Other Group (I) dissimilar metal ions can also be contained in the same manner.

The high silver chloride grains of the present invention can be used even if they are not regular crystal grains but irregular crystal grains or tabular grains.

However, it is preferable to have the localized phase.

The silver halide grains used in the present invention preferably have an average grain size of 0.1 to 1.5 μm.

Monodispersed emulsions are particularly preferred.

The preferred high silver chloride monodisperse emulsion of the present invention has a ratio of statistical standard deviation (s) to average grain size (d) (S/d).
is preferably 0.2 or less, particularly preferably 0.15 or less. Particle size can be expressed as the diameter of a circle equivalent to the projected area. It is sufficient that at least one type of monodisperse emulsion is contained in the photographic layer, and a monodisperse emulsion and a polydisperse emulsion may be mixed, or two or more types of monodisperse emulsions having different average grain sizes may be mixed. good. In this case, the coefficient of variation of the mixed emulsion may exceed the above values.

The surface of the silver halide grains used in the present invention must be chemically sensitized to a certain extent to be substantially of the surface latent image type. Chemical sensitization includes sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); monotin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds)
Reduction sensitization method using metal compounds (for example, total complex salts, pt, Ir, , Pd, , Rh, Fe, etc.)
Noble metal sensitization method using complex salts of group metals, etc. alone,
Alternatively, they can be used in combination. Among these chemical sensitizations, sulfur sensitization is preferably used.

The light-sensitive material made of silver halide grains prepared in this way has excellent rapid processing properties, high sensitivity, high contrast, and little reciprocity failure, as well as high latent image stability and excellent handling properties. Ta. These overturn the common sense of conventional silver chloride emulsions, and can also reduce the occurrence of fog that occurs when a polymer having a guanidyl ketimine residue used in the present invention is used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, mercaptoazoles, such as mercaptothiazoles, mercaptohendithiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazole v1 (especially!-Phenyl-5
- mercaptotetrazoles and those substituted with an N-methylureido group at the m-position of the phenyl group), mercaptopyrimidines, mercaptotriazines, mercaptotriazoles, mercaptothiazoles, etc.; other azoles, e.g. Benzothiazolium salts, nitroimidazoles, nitroheczimidazoles, chloroheczimidazoles, promohenzimidazoles, aminotriazoles, henctriazoles, nitrobenzotriazoles, etc.; thioketo compounds, such as oxadolinthion, etc. ; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3°3a,7)tetraazaindene);
Many compounds known as antifoggants or stabilizers can be added, such as pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

In the present invention, by providing a polymer-containing layer having a guanidyl ketimine residue, a mercaptoazole compound, particularly the following general formula (It), (I[l) or CI+ It can be suppressed by adding a compound represented by /). The amount added is lXl0 per mole of silver.
-5 to lXl0-3 mol is preferable. It is also useful to add precursors of mercapto azole groups or DIR-compounds which adsorb onto the silver particles only in the color developer.

-Noshiro (n) N=N x In the formula, R represents an alkyl group, an alkene group, a nyl group, or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group, or a precursor.

The alkali metal atom is, for example, a sodium atom, a potassium atom, etc., and the ammonium group is, for example, a tetramethylammonium group, a trimethylhensyl ammonium group, etc. In addition, the precursor is X under alkaline conditions.
=H or a group that can be an alkali metal, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Examples of substituents for substituted alkyl groups include halogen atoms.

Nido/tetragroup, cyano group, hydroxyl group, alkoxy group, aryl group, acylamino group, alkoxycarbonylamino group, ureido group, amino group, heterocyclic group, anlu group, sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group , an alkylthio group, an arylthio group, a heterocyclic thio group, and further a carboxylic acid group, a sulfonic acid group, or a salt thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the nyl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and the substituents of the alkyl group listed above.

- Noshiro (I[[) In the formula, Y represents an oxygen atom or a sulfur atom.

L represents a divalent linking group, R is a hydrogen atom, an alkyl group,
Represents an alkenyl group or an aryl group. The alkyl group, alkenyl group and X of R have the same meanings as in general formula (II).

Specific examples of the divalent linking group represented by the above are -N-1-N C0-1-N5O□-1-N-C-N-
11111ll R'R'R'R'
OR"■ -N -C-N--1-s-1-CH-3-C-1R'
Examples include SR"R'R", etc., and combinations thereof.

n represents O or 1, and RO8R1 and R2 each represent a hydrogen atom, an alkyl group, or an aralkyl group.

General formula (IV) In the formula, R and X have the same meaning as in general formula (II), and L has the same meaning as in general formula (III).

R3 has the same meaning as R, and may be the same or different.

Specific examples of the compounds of the general formula (IT), -Noshiro (III) and -Noshiro (TV) are listed below, but the invention is not limited thereto.

(1) N = N +1 Sl+ (2+ N=N Sl+ (31N=N ) l (61N = N N -(C1b) 4 Hs NlIC0CHz H3 General formula (V) Cp-X General formula (Vl) AI P Ar Q In the formula At, Cp
is a coupler residue that cuffs with the oxidized form of a color developing agent to form a substantially colorless compound, or a compound that can be eluted or diffused out of the layer in the light-sensitive material by coupling during the color development process. represents a coupler residue to be formed, and X represents a coupling-off group.

A, and A! each represents a hydrogen atom or a group that can be cleaved by an alkali, P and Q each represent an oxygen atom or a sulfonylimino group, Ar represents an aromatic group,
AI-P at the 1,2- or 1.4-position of the aromatic group
- and -0-AI bind.

Next, the compound represented by general formula (V) will be explained in detail.

There are two types of compounds produced immediately after the coupler represented by the general formula (V) undergoes a coupling reaction with an oxidized developing agent: colored or substantially colorless. In the former case, the dye is not utilized for image formation in the present invention. That is, when the dye generated during development becomes alkali-soluble and diffuses from the photographic layer, or when it flows out into the developer, or when the components contained in the developer,
For example, a preferred example is when it reacts with sulfite ions or hydroxyl ions and becomes substantially colorless. They may occur at the same time, but in any case - Noshiro (
The amount of the colored compound generated during development due to cambling between the coupler represented by V) and the oxidized developer remains in the photographic layer after the development process is preferably 10% or less, more preferably 5% or less. be.

In the above, the dye is alkali-soluble when the dye has a hydrophilic group, preferably a dissociable group. The degree of alkali solubility varies greatly depending on the environment during development processing, for example, the I) H1 processing time of the processing solution and the structure of the developing agent. However, -11 formula (V
) can be adjusted to a desired degree by selecting the substituent included in Cp.

In the above, the case where the dye reacts with the components contained in the developer and becomes substantially colorless refers to, for example, "Journal of the Photographic Society of Japan," p. 27172 (1964) and "Journal of the American・Chemical Society J
(J, Amer, Chem, Soc,) Volume 84, 20
There is a reaction described on page 50 (1962). The speed of the colorless reaction depends on the type and amount of components contained in the developer, but can be adjusted to a desired degree by selecting the structure of the group represented by Cp and the substituent.

A usual coupler residue can be used as the group represented by cp. yellow coupler residues (e.g. open-chain ketomethylene type coupler residues), magenta coupler residues (e.g. 5-pyrazolone type or pyrazolotriazole type coupler residues), cyan coupler residues (e.g. phenol type or naphthol type coupler residues). ) and colorless coupler residues (e.g. indanone-type, acetophenone-type coupler residues), and U.S. Pat.
No. 15,070, No. 4,183,752, No. 3,96
It may be a heterocyclic coupler residue described in No. 1,959 or No. 4,171.223.

The compound represented by general formula (V) preferably has a diffusion-resistant group. The anti-diffusion group is a group that prevents the compound of general formula (V) from migrating from the added layer and diffusing into other layers.

Usually, organic substituents are used to increase the molecular weight.

When the group represented by Cp in general formula (V) is a yellow coupler residue, magenta coupler residue or cyan coupler residue, a preferred example is when the diffusion-resistant group is included in the group represented by X.

Here, X may contain one or more groups represented by Cp, such as those forming a bis-type, telomer-type, or polymer-type coupler. When it is a color-forming coupler residue, the diffusion-resistant group may be included in either Cp or the group represented by X. Here, cp contains two or more colorless coupler residues, or X is a bis-type containing one or more Cp,
It may also form a telomer type or polymer type coupler.

The group represented by X in the general formula (V) does not represent a campling leaving group, but may be a group that reacts with the oxidized developing agent after leaving or a group that does not react with the oxidized developing agent. X
represents a group that reacts with the oxidized developing agent, X is Cp
It is a group that becomes a coupler when cleaved from Cp, or a group that becomes a redox group after being cleaved from Cp.

For example, in the case of a phenol type coupler, the group in which X serves as a coupler is a group that is bonded to Cp at an oxygen atom other than a hydrogen atom of a hydroxyl group. In the case of a 5-pyrazolone type coupler, it is bonded to Cp at an oxygen atom obtained by removing a hydrogen atom from a tautomerized hydroxyl group of 5-hydroxypyrazole.

In these examples, X becomes a phenol type coupler or a 5-pyrazolone type coupler only after it is separated from Cp. A preferred example is that the coupling position has a coupling-off group containing a diffusion-resistant group.

On the other hand, when the group represented by X in -Noshiro (V) represents a redox group, X is preferably hydroquinones, catechols, pyrogallol a, i.

These are 4-hydroxynaphthols, sulfonamidophenols, or 1,2-hydroxynaphthols.

Preferably, these reducing agents have a diffusion-resistant group.

Preferred ranges for the compound represented by general formula (V) will be described in detail below. That is, preferred couplers are indicated by Noshiro (■) below.

-Noshiro (■) Cpp (Sob).

X′ In the formula, S07! represents an alkali-solubilizing group, b represents an integer of 1 to 3, cpp represents a group that cleaves X' in a curing reaction with an oxidized developing agent;
X' represents a campling-off group containing a diffusion-resistant group.

-i In formula (■), Sol represents a dissociative group or a quaternary ammonium salt, preferably a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a sulfinic acid group or a salt thereof, or a hydroxyl group. Examples of the salt include sodium salt, potassium salt, or ammonium salt.

Soj! is particularly preferably a carboxylic acid group, a sulfonic acid group or a salt thereof.

-i Among the compounds represented by formula (■), preferred are the following - Noshiro (Cp-1), (Cp-2), (Cp-
3), (Cp-4), (Cp-5), (Cp-6), (
Cp-7) or (Cp-8).

General formula (Cp-1) LVG.

General formula (Cp-2) VGI General formula (Cp-3) 1? ss General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) H ■ LVG.

General formula (Cp-7) H ■ LVG4 General formula (Cp-8) H LVG.

RSI to R6z, LvG1 to LvG4, p and h will be explained below.

In the above formula, RS I % RS Z, R53, R54
% R55, R5b, Rst, R58% RIt, R6
゜, R61, and R6□ preferably have a total number of carbon atoms of 15 or less. Also, R5I, Rsz, R53, Rss, R5
8% R60 or R61 represents a group that may contain a Sol group as a substituent.

R54, R5hs k, R59 or R14 is So7!
Indicates a group that may contain a group or a Son group itself.

In the following explanation, R4I is an aliphatic group, an aromatic group, or ? ! [Represents a hydrogen atom, R43, R44 and R1° represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R1, represents the same meaning as Ro. Rsz and R5f
Each f represents an aromatic group or a heterocyclic group.

Rs<(same meaning as Rn+ 6 groups) In addition, R4, coN-
? group, R,, N- group, R,, SO2N- group, Ra 1 S
- group, R41RJ:l R430-%, R,5NCON-5, Raz OOC
-W,] l R41R44 R, also represents an NGO- group or an N30- group. R55R
a3 represents a group having the same meaning as Ra (R5h and Rsq
In addition to the groups having the same meaning as the R43 group, each represents a Ra+S- group,
R4, o- group, carboxyl group, R4IC0N- group, R
a lN- group, R4IC0N- group, R,, NC0N- group, 1 +1R,j
Ra3 Ra4 Ras or R4+
Represents 5OzN-. R5ff is the same as R41 and represents a meaningful group. Rsq is a group having the same meaning as R4I, and R
= + CON- group, R4,0CON- group, I R43R8 R,, NSO, N- group, sulfonic acid group or its salt, R4
4R,.

R2O- group, Ra+S- group, halogen atom or R,,
Does not represent an N-group. p represents O to 3;

(2) When p is a plurality of R5Os, the plurality of R5Os may represent the same substitution method or different substituents, or 8% of each R5O may be a divalent group and be continuous to form a cyclic structure.

An example of a divalent group for forming a cyclic structure is az R4 co ! g represents an integer from 0 to 2, and g represents an integer from 0 to 2, respectively.

R5° represents a group having the same meaning as R41, R51 represents R4
Represents a group with the same meaning as 1. In addition to the group having the same meaning as R4, R62 is a R4IC0NH- group, R41OCONH
- group, Ra + S OZ N H- group, carboxyl group, sulfonic acid method or its salt, Ra s N CON
- group, R4s N S Oz N- group 0. Ra30- group, R44Ras R44R45 Ra lS- group, halogen atom or Ra + N- group are also Table 4ff aRh3 and R, 64 each represent an alkyl group, and may be linked to each other to form a ring. h represents an integer of 4. When there are multiple R1 and v, each represents the same thing or different things.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms. Examples include methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, (t)-butyl group, (1)
-butyl group, (tl-amyl group, hexyl group, and cyclohexyl group).

The aromatic group is a phenyl group having 6 to 1 carbon atoms, preferably substituted or unsubstituted.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 15 carbon atoms, preferably 1 to 5 carbon atoms, preferably a 3- to 6-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

Typical examples of heterocyclic groups include 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 2-furyl group, l-imidazolyl group, phthalimide group, and 1,3゜4-thiadiazol-2-yl group. , 2-quinolyl group, tetrazolyl group, 2
．． 4-dioxo-1,3=imidapridin-5-yl group, 2,4-dioxo-1,3-imidazolidin-3-yl group, succinimide group, 1,2.4-)lyazole-
A 2-yl group or a l-pyrazolyl group may be mentioned.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, R, o-1, Ra, S- group, R4? CON- group, R,? NGO- group, Ra b OCON- group, Ras
Ras R4tR4bS
O≧- group, R4?0CO- group, R4,NC0N- group, R
411R49 group or a salt thereof, R-703Oz- group, cyano group or nitro group. Here, R46 represents an aliphatic group, an aromatic group, or a heterocyclic group, and RJ? , R4! l and R
49 each represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and the meaning of aliphatic group, aromatic group or heterocyclic group is the same as defined above.

Next, preferred ranges of R3I to R61sp and h will be explained.

R5I is preferably an aliphatic group or an aromatic group.

RSzs Rss and RSs are preferably aromatic groups.

Rsa is Ra + CON H- group, or Ra + N-
Groups are preferred. R8 & and R5? is an aliphatic group, Ra
+ O- group or R4,S- group is preferred. RS is preferably an aliphatic group or an aromatic group. General formula (Cp-6
), R8I is preferably a chlorine atom, a fluorine atom, an aliphatic group, or a R, CONH- group. p is preferably an integer of 0 to 2, and R6° is preferably an aromatic group.

In general formula (Cp-7), R54 is a chlorine atom, R,,
C0NH- group is preferred. In general formula (Cp-7), h is preferably 0 or 1. R61 is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), h is 0
or 1 is preferable, R53 is Raz OCO
NH- group, R4, C0NH- group, all! Ra+sOz
An NH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring.

Next, typical examples of R5I to R6□ will be explained.

Examples of R51 include (1)-butyl group, 4-methoxyphenyl group, phenyl group, methyl group, 4-carboxyphenyl group, and 2-chlorophenyl group.

Rsi, R53 is 3-carboxyphenyl group,
3.5-dicarboxyphenyl group, 2-chloro-5-methoxycarbonylphenyl group, 2-chloro-5-(3-
carboxypropanamido) phenyl group, 2-chloro-
5-ethoxycarbonylphenyl group, phenyl group, 2-
Examples include methoxy-5-methoxycarbophenyl group and 2-pyridyl group.

R54 is a 3-acetamidobenzamide group, a benzamide group, a 3-phenoxypropanamide benzamide group, a 3-carboxybenzamide group, a 2-chloro-
Examples thereof include a 5-ethanamide anilino group, an anilino group, a 5-phenoxyacetamidoanilino group, a 3-carboxyanilino group, and a 3.5-dicarboxyanilino group.

As Rss, 2,4.6-dolichlorophenyl group,
2-chlorophenyl group, 4-carboxyphenyl group, 2
．． 5-dichlorophenyl group, 4-sulfophenyl group, 2
．． 3-dichlorophenyl group, or 2,6-dichloro-
A 4-carboxyphenyl group is mentioned.

R5 & is a methyl group, an ethyl group, a 2-carboxyethyl group, an isopropyl group, a propyl group, a methoxy group, an ethoxy group, a methylthio group, a phenyl group, an ethylthio group,
Or a 3-phenylureido group may be mentioned. As R3, 3-phenoxypropyl group, t-butyl group, 3
- (2-methoxyethoxyphenyl)propyl group, carboxymethoxy group, ethoxy group, carboxymethylthio group, 4-carboxyphenyl group, ethylthio group, methyl group, carboxyethyl group, or phenylthio group. Ro means 2-chlorophenyl group, 3-
Examples include carboxypropyl group, 2-carboxyethyl group, carboxymethyl group, 3,5-dicarboxyphenyl group, butyl group, ethyl group, methyl group, and furyl group. Rsq is a chlorine atom, a fluorine atom, a methyl group,
Examples include carboxyl group, ethyl group, butyl group, isopropyl group, 2-carpoxyethyl group, and 2-phenoxyacetamide group. Examples of R7° include 4-cyanophenyl group, 2-cyanophenyl group, 4-methanesulfonylphenyl group, 2-carboxyethyl group, 4-carboxyphenyl group, or 3-methoxyluponylphenyl group.

As R6, 2-carboxyethyl group, 4-carboxyphenyl group, butyl group, 3-phenoxypropyl group, 1-carboxymethyl group, 1-carboxyethyl group,
Examples include 3-phenoxybutyl group and 1-naphthyl group. Examples of Ro include an inbutyloxycarbonylamino group, a methanesulfonamide group, or an acetamido group.

Next, LVGI to LVG4 will be explained.

LVG preferably includes an RthsO- group, an imide group bonded to the coupling position and a nitrogen atom, a 5- or 6-membered unsaturated nitrogen-containing heterocyclic group bonded to the coupling position and a nitrogen atom, or an R15- group. represent.

LVGt is preferably R6,3- group, R6,〇- group, R
as N=N- group or a 5- or 6-membered unsaturated nitrogen-containing heterocyclic group bonded to the coupling position through a nitrogen atom.

LVG is preferably an RbbS- group or a 5- or 6-membered unsaturated nitrogen-containing heterocyclic group bonded to the coupling position through a nitrogen atom.

LVG is preferably an RbbO- group, R,, -N=N-
or R-S- group.

In the above, Ro is an aromatic group or ? ! It represents a monocyclic group, and Ra6 represents an aliphatic group, an aromatic group or a heterocyclic group. Aromatic groups, heterocyclic groups, and aliphatic groups are preceded by Ra1
has the same meaning as explained above, except that the total number of carbon atoms contained in R and R is 10 or more and 40 or less, preferably 12 or more and 40 or less.

When LVGt, t, vc, and LVG3 represent an unsaturated nitrogen-containing heterocyclic group, examples of the ring structure of the heterocyclic group include a 1-pyrazolyl group, a 1-imidazolyl group, or l, 2.
4-) riazolyl group.

These have a substituent, and the total number of carbon atoms including the substituent is 10 or more and 40 or less, preferably 12 or more and 40 or less. Representative examples of the substituent include the substituents listed above when R41 represents a heterocyclic group.

When LVG represents an imide group, examples of the ring structure of the imide group include 2,4-dioxo-1,3-imidazolidin-3-yl group, 2,4-dioxo-1,3-oxazolidine-3 -yl group, 3°5-dioxo-1,2,4-
A triacylidin-4-yl group or an octadecenylsuccinimide group may be mentioned. These have a substituent, and the total number of carbon atoms including the substituent is 10 or more and 40 or less, preferably 12 or more and 40 or less. As a substituent, R4
The substituents listed when 1 represents a heterocyclic group are representative examples.

Then LVGt, LVGz, LVG3 and LVG4
A typical example will be explained.

LVG, 1-benzyl-5-hexyloxy-2,4-dioxo-1,3-imidazolidine-3-
yl group, 1-hensyl-5,5-dioctyl-2,4-
Dioxo-1,3-imidazolidin-3-yl group, 4-
(4-hexadecyloxinphenylsulfonyl) phenoxy group or 1-(3-hexadecyloxycarbonylphenyl)tetrazolyl-5-thio group.

LvGz includes 4-(3-(2-decyl-4-methylphenoxy)acetyloxy)propyl-1-pyrazolyl group, 4-tetradecyloxyphenylazo group, 2-
Butoxy-5-(1,1-dimethyl-3,3-dimethylbutyl)phenylthio group or 4-tetradecylcarbamoylphenoxy W can be mentioned.

LVGff is 2-butoxy-5-(1,1-dimethyl-3,3-dimethylbutyl)phenylthio group or 2-methoxyethoxy-5-(1゜1-dimethyl-3,
A 3-dimethylbutyl) phenylthio group is mentioned.

LVG, specifically 4-(1,1-dimethyl-3゜3-dimethylbutyl)phenoxy group, 4-(4-(2,4-
Di also monoamylphenoxy)butanamido) phenoxy group, 4-(2-(2,4-di(-amylphenoxy)butanamido)phenoxy group, 3-(2,4-di-
t-amylphenoxy) propylcarbamoylmethoxy group or 4- (2゜4-di-monoamylphenoxy)
A butylcarbamoylmethylthio group may be mentioned.

Among the general formulas (Cp-1) to (Cp-8), particularly preferred couplers are those represented by the general formulas (Cp-6) to (Cp-8).

- The compound represented by Noshiro (V) can be dispersed in a hydrophilic colloid according to a conventional dispersion method for image-forming couplers (e.g., oil-in-water dispersion method, polymer dispersion method, etc.), or can be dispersed in alkali solubilization. Those with groups can be added to hydrophilic colloids as an aqueous solution.

The amount of this compound to be used is not particularly limited, but may be in the range of 10-6 to 10-' mol per mol of silver halide.

Next, specific examples of the compounds of the present invention are shown below. However, it is not limited to this.

1ll V - (2+ H Csll+I (t) V −+31 V-(4) 0 ■ V −+51 V - (6+ V - (71 scolding V-f81 H Ni+ " COClIC,ll.

■ C, I+.

V-(91 "■-αφ ■-〇〇C(CI31zCII□C(Clh)i■-(2) ■-〇turbidity V-051 ■-αQ ■-αη -QI V-a@ v -(21) V - (22) v - (23) V - (24) V - (25) NHS (hC+□Ls V - (26) O1+ The above compound was synthesized by a synthesis method similar to that of known two-equivalent couplers. Yes, for example, JP-A-61-86
No. 751, No. 59-113438, No. 59-1134
40, No. 51-171955, etc., or similar methods such as changing substituents.

Next, the compound represented by the general formula (Vl) will be explained in detail.

In the compound represented by general formula (Vl), A.

and A! When is not a hydrogen atom, it is hydrolyzed by an alkali during development to produce a compound represented by -Noshiro (VT-a).

General formula (V[-a) H-P-Ar-Q-H In the formula, P, Ar and Q represent the same meanings as explained in the general formula (Vl). - The compound represented by Noshiro (Vl-a) can reduce the oxidized product of the developing agent.

That is, compounds that generally exhibit reducing ability are Kendal
It is known that it follows the l-Pelz law (for details, see T, H,
James, The Theory of thep
photograpt+ic Process+4th edition,
298-300, Macmillan Publishing Co., 1976), -Noshiro (■-a) is within that structural range.

The compound represented by the general formula (Vl) is preferably represented by -Noshiro (■) below.

General formula (■) (L) - In the formula, A1 and Q represent the same meanings as explained for the general formula (V[), and -Q-H is 2 for A and -O.
Attaches to the 4th or 4th position. R represents a group that can be substituted on the benzene ring, and a represents an integer of 1 to 4. Here, when a is 2 or more, multiple R1's represent the same or different things, and when two R1's are adjacent substituents, they each represent a divalent group and are linked to each other to form a cyclic structure. You can.

Examples of the ring structure when two R1s are linked to form a ring structure include naphthalenes, benzonorbornenes, chromans, and indoles. These fused rings may further have a substituent, and examples of the substituent and preferred examples of R1 when R+ does not form a fused ring are listed below.

That is, R2- group, R)O- group, R,S- group, R,+
C0N- group, R25O, N- group, R20CON- group, R
, R3R3 R, NC0N- group, R3N- group, R, NGO- group, 1
1 l IR= Rs
R4RaR300C- group, R25OR- group, R,N5Ch- group, R3CO-M, halogen atom, cyano group, R103O□- group, Rzcoo- group, R,N
SO□N- group, R, R.

or Rz so- group. Here, R2 represents an aliphatic group, an aromatic group, or a heterocyclic group, and Rs, Ra, and R2 represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. The definitions of aliphatic group, aromatic group or heterocyclic group have the same meaning as explained above (for example, as explained for R66).

The total number of carbon atoms contained in R1 is preferably 1 to 40, and it is particularly preferred that at least one Ro among the a groups is a group having 6 or more carbon atoms in total.

- When A1 in Noshiro (■) represents a group that can be cleaved by hydrolysis, it is preferably an acyl group (e.g. acetyl,
benzoyl), alkoxycarbonyl groups (e.g. ethoxycarbonyl), aryloxycarbonyl (e.g. phenoxycarbonyl), and U.S. Pat.
Examples thereof include a precursor group (eg, cyanoethyl group) that utilizes the reverse Michael reaction described in No. 029.

- In Noshiro (■), when Q represents a sulfonylimino group, a group represented by R, So□N- is preferred. Here, R6 is a group having the same meaning as R2.

In the general formula (■), A is particularly preferably a hydrogen atom.

In the general formula (■), R1 is particularly preferably an aliphatic group, an acylamino group or a sulfonamide group.

Next, specific examples of the compound represented by the general formula (Vf) will be shown. However, it is not limited to these.

■-fi+ ■ HV[-+21 H VT -+31 0■ Vr -(41 il H Vl -(51 H Vl-(61 Vl -(71 H H Vl -481 0■ Vl -(91 H VI -(101 ■-αKa■ -圓■〜09 Cd1q(t) l-061 H T-071 1-Q81 H vr-I2... 1-an The high silver chloride emulsion according to the present invention contains sensitizing dyes, particularly monomethine, trimethine, and pentamethine. Or selectively spectral sensitization in the blue, green, red, or infrared wavelength ranges using methine dyes such as hexamethine cyanine dyes and merocyanine dyes. For example, Japanese Patent Application No. 63-6861 - Noshiro (
A sensitizing dye represented by r/> is used.

A sensitizing dye may be added, at least in part, to the high silver chloride emulsion according to the invention during or before the chemical sensitization process. For example, Japanese Patent Application No. 62-86252, Japanese Patent Application No. 62-86165
It is preferable to use the sensitizing dye and addition method described in Japanese Patent No. 62-152330. This method can further reduce the occurrence of stains.

In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarbocyanine dyes are preferably used.

The sensitizing dye used in the present invention is preferably added during or before chemical sensitization, or during or after the formation of silver halide grains.

In the present invention, "preferable" means that the effect of using the polymer having a guanidyl ketimine residue according to the present invention is more remarkable than when it is not used.

The polymer having a guanidyl ketimine residue, which is used in the present invention, has the effect of capturing iodide ions eluted during development or fixing of silver halide and increasing the processing speed.

Furthermore, it has the effect of stabilizing the color development process and increasing the development process speed by capturing the bromine ions that are eluted during the silver halide development process or brought into the developer solution or from the outside. In addition, the present invention has a particularly great effect of suppressing changes in photographic properties due to variations in processing conditions, and in particular, improves the stability of gradations at the legs and shoulders in the characteristic curve.

This effect is particularly noticeable when a high-silver chloride emulsion (preferably Agi, a silver chlorobromide emulsion of 98 mol or more) in which silver bromide is localized on the grain surface is used and subjected to high-temperature rapid processing.

When the polymer dispersion having guanidyl ketimine residues in the present invention is used as a mordant, it is possible to prevent halation by selecting a dye with spectral absorption characteristics matching the spectral sensitivity of the silver halide emulsion layer. Effectively used in filters for modifying spectral sensitivity.

In the color light-sensitive material of the present invention, since a reflective support is used, the effect of the polymer dispersion/mordant layer of the present invention is remarkable, and furthermore, the halogenated ill used is, for example, 9.9 g/n of silver (hereinafter referred to as Preferably 0.7g/
d or less, and by selecting the size and shape of the silver halide particles to increase the light transmittance of the coating film, the effect of improving image sharpness and color reproducibility by the polymer dispersion/mordant layer of the present invention can be improved. noticeable.

In the color light-sensitive material of the present invention, a yellow coupler, a magenta coupler and a cyan coupler, which develop yellow, magenta and cyan colors respectively when coupled with an oxidized product of an aromatic amine color developer, are usually used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as hendiylacetanilide and pivaloylacetanilide are preferred.

Among them, yellow couplers have the following general formula (Y-
Those represented by 1) and (Y-2) are preferred.

For details on the pivaloylacetanilide type yellow coupler, see U.S. Pat. It is described in line 41 of column 19.

For details on hendiylacetanilide type yellow couplers, see U.S. Pat. Nos. 3,408,194 and 3,93
No. 3,501, No. 4,046,575, No. 4,133
．． It is described in No. '958, No. 4,401゜752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (y
-39), among them (Y-1), (Y
-4), (Y-6), (Y-7), (Y-15), (Y
-21), (Y-22), (Y-23), (Y-26)
, (y-35), (Y-36), (Y-37), (Y-
38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623.616
Compound examples (Y-1) to (Y-33) in columns 9 to 24i can be mentioned, among which (Y-2), (Y-7)
, (Y-8) , (Y-12) , (Y-20
), (Y-21), (Y-23), (
Y-29) and the like are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical example (3
4) Compound examples αe and Ql described in column 8 of specification No. 3,933,501, example compounds (9) described in columns 7 to 8 of specification no. 4,046,575, 4,133,9
Compound Example (1) described in columns 5 to 6 of Specification No. 58, Example 1 of compound described in No. 5MA of Specification No. 4,401,752, and Specification No. 29 of Japanese Patent Application No. 1983-263318
Compounds a to g described on pages 1 to 30 can be mentioned.

Examples of the magenta coupler that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. 5-The 3rd position of the pyrazolone coupler is completed.
Couplers substituted with a lamino group or an acylamino group are preferable from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Patent Nos. 2,311,082 and 2
, 343.703, 2,600,788, 2.908,573, 3,062.653, 3,152,896 and 3.936.015
It is written in the number etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Patent No. 4,310,619
The nitrogen atom leaving group described in No. 4, 3 of U.S. Pat.
The arylthio group described in No. 51.897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo[:5,1-C)(1,2,4)) lyazoles as described in U.S. Pat. 24220 (
Virazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (198
Examples include the pyrazolopyrazoles described in June 2003). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1>
, (M-2) or (M-3).

hz ”-, -z Among pyrazoloazole couplers, U.S. Pat.
The imidazo(1,2-b) pyrazoles described in U.S. Pat. No. 500,630 are preferred, and the pyrazolo(1,5-b) (1,2,4)
1-Riazoles are particularly preferred.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245, and as described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226,849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

The most typical cyan couplers are phenolic cyan couplers and naphthol cyan couplers.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4.51
1647 and 3,772,002, which have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position (including polymer couplers). Canadian Patent No. 625,8
Coupler of Example 2 as described in No. 22, U.S. Pat. No. 3,77
Compound fi+ described in No. 2.002, No. 4,564°5
Compounds (1-4) and (r-5) described in No. 90, compounds fil, (2), (
3), (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772, 162, 2. 89'5. No. 826,
There are 2,5-diacylaminophenol couplers described in U.S. Pat. No. 4,334,011, U.S. Pat. Compound (■) described in No. 895.826, compound 01 described in No. 4゜557.999,
Compound (2) described in No. 4,565.777, ano,
Compound (4) described in No. 4,124.396, No. 4,
Examples include the compound (1-19) described in No. 613゜564.

As a phenolic cyan coupler, U.S. Pat.
, No. 327, 173, 4. 564. No. 586, No. 4,430,423, JP-A No. 61-390441, and Japanese Patent Application No. 61-100222, there are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus. are the couplers (1) and (3) described in U.S. Pat. No. 4,327,173, the compound (3) described in U.S. Pat. No. 4,564,586, and the compound described in U.S. Pat. No. 4,430.423. (1), (3), and the following compounds can be mentioned.

(C-1) (C-2) II L;sll+ +
(t) (C-3) (C-4> 1I 1 C7! (C-5) NH3O□C, II.

(C-6) c'g (C-6> Cs1l++ Other examples of phenolic cyan couplers include U.S. Pat. No. 4,333,999, U.S. Pat. No. 4,451.
, 444,872, 4,421.161, 4,
No. 579.813, European Patent (EP) 067.689B
There are ureido couplers described in U.S. Pat. No. 4,333,999, coupler fil described in U.S. Pat. Coupler 04) described in No. 4,444,872), coupler (3) described in No. 4,427,767, coupler (6) described in No. 4,609.619.
) and (24), coupler (1) and 0υ described in 4,579,813, European Patent Tube (BP) 067.689B
Coupler (45) and (50) described in No. 1, JP-A-61
Coupler (3) described in No.-42658 can be mentioned.

Examples of naphthol cyan couplers include those having an N-alkyl-N-carbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586);
Those having an alkylcarbamoyl group at the 2-position (e.g., U.S. Pat. No. 2,474.293, U.S. Pat. No. 4,282.312)
, those having an arylcarbamoyl group at the 2-position (for example, Japanese Patent Publication No. 114523), those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A No. 60-23)
No. 7448, No. 61-145557, No. 61-153
640), those with aryloxy leaving groups (e.g. U.S. Pat. No. 3.476.563), and those with substituted alkoxy leaving groups (e.g. U.S. Pat. No. 4,296.199).
No.), those with a glycolic acid leaving group (e.g.
0-39217).

In addition, as a cyan coupler, European Patent (EP) No. 0
．． The diphenylimidazole cyan coupler described in 249,453A2 can also be used alone or in combination with the above-mentioned cyan couplers.

Specific examples include the following.

(C-8) (C-9) (C-10) 4H9 (C-12) The photosensitive material produced using the present invention contains hydroquinone m4, aminophenol derivatives, gallic acid derivatives, It may also contain ascorbic acid derivatives.

In addition, as a dye image stabilizer, for example, JP-A-59-
Catechol derivatives described in JP-A-60-262159 and the like can also be used.

Reflective supports used in the present invention include paper, baryta paper, synthetic paper, paper coated with or laminated with an olefin polymer (especially an α-olefin polymer having 2 to 10 carbon atoms such as polyethylene, polypropylene, and ethylene butene copolymer); Examples include plastic supports containing white pigments such as titanium oxide, barium sulfate, and magnesium oxide (eg, cellulose acetate film, polyester film, polyethylene terephthalate film, polycarbonate film, and polyvinyl chloride resin). Further, a support having a specular or diffusely reflective metal layer or metal foil (for example, a support having an aluminum layer or aluminum foil) is used. By providing an undercoat layer on these supports using styrene-butadiene (SBA) resin, vinyl chloride resin, etc., or by roughening the surface of the support as shown in Japanese Patent Publication No. 19068/1983. can improve adhesion with polymeric substances. Further, an undercoat layer may be provided using an ultraviolet curable resin. Furthermore, in order to improve the adhesion with the layer formed thereon, the surface of the support is preferably subjected to a preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. The fine particle dispersion of the cationic polymer according to the invention can be used in the undercoat layer.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may be used as a coating aid, an emulsifying dispersant, an anti-adhesive agent, and to improve photographic properties (e.g., development acceleration, high contrast, sensitization), antistatic and anti-slip properties. A surfactant may be included for various purposes such as improving properties.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Alkylamides or amides, silicone polyethylene oxide adducts t1'i), glycidol derivatives (
Nonionic surfactants such as alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, and alkyl hanzene sulfonates. , alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkylclaric acids, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, etc.
Anionic surfactants containing acidic groups such as phosphate groups;
Amino Kl, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used. Among these surfactants, polyoxyethylene surfactants and fluorine-containing surfactants are particularly preferably used.

In particular, when the dispersion of a polymer having a guanidinyl ketimine residue according to the present invention is used in combination with the above-mentioned cationic surfactant, the surface condition, p9 quality, or adhesion to an adjacent layer can be improved.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. Nos. 3,314,794 and 3,352°681), ), benzophenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g., U.S. Pat. No. 3,705
．． No. 805, as described in No. 3,707.375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
(as described in US Pat. No. 3,700,455) or benzoxidol compounds (such as those described in US Pat. No. 3,700,455). UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
Ultraviolet absorbing polymers may be used. These ultraviolet absorbers may be mordanted in a specific layer. Various other additives may be used in the color photosensitive material of the present invention, but these The additives are listed in Research Disclosure Magazine Fish 1.
7643 (December 1978) and 18T16 on the same floor
(November 1979), and the relevant sections are summarized in the table below.

Additive type 'RD17643 RD1871
61 Chemical sensitizers Page 23 Page 648 Right column 2 Anger intensity increasing agents Same as above 4 Brightening agents Page 24 8 Dye image stabilizers Page 25 9 Hardening agents Page 26 Page 651 Left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 Page 650 right column 1
4 Color Coupler Pages 24-25 Pages 649 A color developing solution is generally used for the development of the light-sensitive material of the present invention. The color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 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 lithic salts, hydrochlorides, or p-toluenesulfonates. 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, benzothiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfone M[,) lyethylenediamine (1,4-diazabicyclo[2゜2.2]octane) Various preservatives such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, caplase agents such as sodium boron hydride, 1 -phenyl-3-
Auxiliary developing agents such as birapritone, viscosity-imparting agents, various oxidizing agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. , diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■
-Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N.

N-1-rimethylenephosphonic acid, ethylenediamine-N
, N,N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

The pH of these color developing solutions is generally 9-12, preferably 10-11. The replenishment amount of these developing solutions is generally 31 or less per square meter of photosensitive material, and can be reduced to 500 or less by reducing the bromide ion concentration in the replenisher. 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. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The bleaching process may be carried out simultaneously with the fixing process (a white fixing process), or may be carried out 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 in two continuous 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. Examples of bleaching agents include iron (■), Kobal) (
1), compounds of polyvalent metals such as chromium (■) and copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I[+) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrohenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (III) tW salts and persulfates, including iron ethylenediaminetetraacetate ([[[) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminopolycarboxylic acid iron (II) ti 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 may be lowered. can.

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

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat.
The compounds described in JP-A-53-95,630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the window material.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfates are the most commonly used. Can be used widely. 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 countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in ``Journal of the Society of Motion.''
Picture End Television Engineers J
(Journal of the 5ociety
of MotionPtcture and Te1
et(ision Engineers) No. 64＼2
By the method described on pages 48-253 (May 1955 issue),
You can ask for it.

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. The problem arises. 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 JP-A-62-288838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8,542, and other benzotriazoles, as well as other antibacterial and fungicides by Hiroshi Horiguchi, It is also possible to use disinfectants described in "Chemistry", Sanitary Technology Metals "Sterilization, Disinfection, and Antifungal Technology of Microorganisms", and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science Metals.

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 be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15-45°C is selected, preferably 30 seconds = 5 minutes at 25-40°C. Furthermore, the photosensitive 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 No. 57-8,543, 58-14゜8
All known methods described in No. 34, 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 from water washing and/or replenishment of the stabilizing liquid can be reused in other 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 the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent 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
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64,339 and JP-A-57-144,547.
No. 58-11.5.438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. 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.

In order to fully exhibit the excellent features of the silver halide photographic light-sensitive material of the present invention, the silver halide color photographic light-sensitive material must be substantially free of benzyl alcohol and contain 0.00%
It is preferable to process with a color developing solution containing 2 mol/1 or less bromide ions for a developing time of 2 minutes 30 seconds or less.

The term "substantially free of benzyl alcohol" mentioned above means 2 or less, preferably 0.5 or less, and most preferably no benzyl alcohol at all per 11 parts of the color developer.

(Example) Next, the present invention will be explained in more detail based on examples.

Example-1 Samples 1 to 4 for multilayer color printing having the layer structure shown below were placed on a paper support laminated on both sides with polyethylene.
, A, B and C were produced.

The composition of each layer is shown below, and the numbers represent the coating amount (g/M). However, for silver halide emulsions, the coating amount is in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOx) and a bluish dye (ulmarine blue). ] Layer-1 (Haley silane prevention layer) Gelatin (shown in Table 2) Cationic polymer I dye
〃Second layer (blue-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion m (EM-1) added with a spectral sensitizer (Sen-1) 0.16 Spectral sensitizer (Sen-1)
-1) Monodispersed silver chlorobromide emulsion (EM-2)
0.10 Antifoggant (Cpd-5) 0.0
002 Anti-capri agent (Cpd-1) 0.002
Gelatin 1.83 Yellow coupler (ExY-1) 0.83 Color image stabilizer (Cp
d-2) 0.03 poly? -(Cpd-3)
Q, O8 solvent (Solv-1 and 5ol
v-'1 Volume ratio 1:1) 0.35 Hardener (I
fd) 0.02 Third layer (color mixing prevention layer) Gelatin 1.25 Color mixing prevention agent (Cpd-4) 0.04 Solvent (Solv-3
and 5olv-4 volume ratio 1:1) 0.20 hardener (
Hd) 0.02 Quaternary N (Green Anger Silver Halide Emulsion Layer) Monodisperse Silver Chlorobromide Emulsion (EM-3) Added Spectral Sensitizer (Sen-2, 3) 0.05 Spectral Sensitization Agent (Sen
-2,3) Monodisperse silver chlorobromide emulsion (EM-4)
0.11 Anti-capri agent (Cpd-5) 0
．． 001 gelatin l/79
Magenta coupler (ExM-1>0.32 color image stabilizer (Cpd-6) 0.20 color image stabilizer (C
pd-7) 0.03 color image stabilizer (Cpd-8
>0.03 solvent (Solv-3 and 5olv-
5 Volume ratio 1:2) 0.65 Hardener (H
d) 0.01 Fifth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent
-6) 0.34 Hardener (Hd)
0.01 Sixth layer (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-5) added with a spectral sensitizer (Sen-4, 5) 0.07 Spectral sensitizer (Scn
-4,5) Monodisperse silver chlorobromide emulsion (EM-6)
0.15 anti-capri agent (Cp, J-9)
0.0002 gelatin 1.3
4 Cyan coupler (ExC-1) 0.33 Ultraviolet absorber (UV-1/3/4 molar ratio 13:3) 0.17 Solvent (So
lv-1) 0.23 Hardener (Hd)
0.01 Seventh N (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.21 Solvent (S
olv-6) 0.08 Hardener (Hd)
0.01 Eighth layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol, degree of modification 17%) O', 17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample It is shown in Table 1.

These emulsions are described in Example 1 of Japanese Patent Application No. 62-263318.
It was made according to the method described in.

Table 1 (Sen-1) 6X10-' mol/Ag mol (C
1lz)4SOff-(CI+ri4SOffll・N(
C, Its) + (Sen-2) 4X10-' mol/Ag mol (Sen-3) axlo-' mol/Ag
Mol (cHt), SO, H-N (Cffil15>
3(S en -4) 1.8X ], ]0-'
mol/Ag mol 1sH++ I-CJs (Sen-5) 3X10-'' mol/Ag mol Na H (Cpd-2) (Cpd-3) (Cpd-4) H (Cpd-6) and H,1,.

(Cpd-7) cooctns (Cpd-9) ■ xM-I xC-1 xC-2 H I xC-3 H (UV-1) (UV-2) Csll+ + (t) (UV-3> (IJV- 4) 01+ (Solv-1) CJ + t C1l cl+(-al12÷, c
OOcall+7(n)\1 (Solv-2) 0 = P+OCqH+q(iso)):+(3o1v
-3) (Solv-4) (So LV-5) C,H.

0 = P +OCHzCHC4Hz)z(SOIV-
6) COOCHzCH(CzHs)CnHq(CHz)a COOCH2CH(C2Hs)CsHq Table 2 (The numbers of the polymer dyes below represent the numbers of the specific compounds exemplified above.) Sample level I Layer 11 Geladine 0 .80g/++(j cationic polymer +31 0.15"i dye (21
' 2.9■/Po: f3+
4.5〃21 Gelatin 0.
80g/mi cationic polymer f31 0. 15
〃i dye (214,3■/d i (316,8〃 31 gelatin 0.80g/rr+i cationic polymer (310,15~i dye (2)
5.8 〃/%1 (319,1〃 41 gelatin 0.80g/ml1 cationic polymer f31 0.15〃1 dye f2)
8.7■/rrri (3113
, 6 ~ Sample Seed 1 - Layer A 1 Gelatin o, 80 g/n (B;
Gelatin 0.80g/bo; Dye (218
,7■/M i (3113,6~ The cationic polymer was mixed in advance as a 5% aqueous solution with an aqueous gelatin solution, and further mixed and dispersed with a 1% aqueous solution of the dye.As a coating aid. used saponin.

In sample 2, Cpd-5 from the second layer and C from the fourth layer.
Sample C was obtained in the same manner except that Cpd-9 was further removed from the sixth layer of pd-5.

For samples 1 to 4 and samples A, B, and C, Fuji Photo Film ■, photosensitive needle FWH type (light source color temperature 320
Light simulation exposure was performed using blue, green, and red filters using 0°K). On the other hand, in order to measure resolution, the rectangular wave pattern for CTF measurement was brought into close contact with the photosensitive surface of the sample using the photosensitive needle, and exposure was performed.

Table 3 shows the results obtained by carrying out the following color development treatment and then measuring the density.

After the above photosensitive material was imagewise exposed, it was processed in the following processing process.

! A! 1J=M 1Noho color development 38℃ 60 seconds bleach fixing 35℃ 60 seconds rinse■ 33-35℃ 20 seconds rinse■ 3
Rinse for 20 seconds at 3-35℃ Dry for 20 seconds at 33-35℃
70-80°C for 50 seconds The composition of each treatment solution is as follows.

Sadan Eriri Statue Blood and Two Waters
800-Diethylenetriaminepentaacetic acid 1. Og nitrilotriacetic acid
2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Benzyl alcohol 16-dinythylene glycol
lQml Sodium Sulfite
2.0g potassium bromide 0.5g
Potassium carbonate 30g N-Ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.5g Hydroxylamine sulfur salt 2.0g Optical brightener (WRITE)
X4 (manufactured by Sumitomo Chemical) Add 1.5g water to 1000dpH (25℃')
10.20 star crossing i wave
0 phlegm water
400-ammonium thiosulfate (70%)
80TR1 Ammonium Sulfite
24g Iron ethylenediaminetetraacetate (I [[) ammonium 30g Disodium ethylenediaminetetraacetate 5g Add water 1000mfp1000℃)
6.50 tons of ion exchange water (3T each of calcium and magnesium) I
) m or less) Samples 1 to 4 according to the present invention show relatively little decrease in effective sensitivity due to the use of dye, and can improve resolution.

The increase in stain (increase in Dmin) of the color print photosensitive material can be suppressed to below the allowable limit.

Exemplary compound (3) of the cationic polymer represented by the general formula (1) according to the present invention is
) or l14) shows a similar tendency. Further, similar effects can be obtained by using ExC-2 to ExC-4 instead of ExC-1.

Example-2 Sample 5 having the following layer structure was produced in the same manner as in Example-1. The coating amounts shown below are in g/n unless otherwise specified. represents. However, the coating amount of the silver halide emulsion is calculated in terms of silver.

Layer - (Antihalation layer) Coating amount Gelatin
180 cationic polymer (3)
0.20 dye 03
0.27 gelatin
1.86 yellow coupler (BxY-
1) 0.82 polymer (Cpd-3)
0.08 Solvent (Solv-4) 0.3
5 Hardener (Hd) 0.02 3rd 1
J (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-4) 0.06 Solvent (Solv-
3 and 5olv-4 volume ratio 1:1) 0.12 Hardener (H
d) 0.02 quaternary N (green-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-8) with added spectral sensitizer (S e n -7,3) 0.45 Gelatin
1.24 magenta coupler (E
xM-1) 0.35 color image stabilizer (Cpd-6)
0.20 color image stabilizer (Cpd-7)
0.03 Color image stabilizer (Cpd-8) 0.
03 Solvent (Solv-3 and 5olv-5 volume ratio 1:2) 0.65 Hardener (
Hd) 0.01 Fifth N (ultraviolet absorption layer) Gelatin 1.20 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent
-6) 0.34 6th layer (middle N) Gelatin 0.50 Cationic polymer (4) 0.05 Dye (40)
5. 3 (■/m') (41)
4.0 (〃) Seventh layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-9) with added spectral sensitizer (Sen-4,5>) 0.20 Gelatin
0.92 diazi coupler (ExC-1
) 0.33 Ultraviolet absorber (UV-1/3/4 molar ratio 1:3:3) 0.17 Solvent (S
olv-4) 0.20 Hardener (Hd)
0.01 Eighth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.21? container
(Solv-6) 0.
08 Hardener (lid) 0.01
Ninth N (Protected N) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 The symbols of the additives used in the above sample are the same as those in Example 1. It is. The structural formulas of other symbols are shown below.

(Sen-6) (CH,)3 5OJ-N(Cztls) 3 (Sen-7) Details of the silver halide emulsion used in the above sample are shown in Table 5. These emulsions were prepared according to the method described in Example 1 of Japanese Patent Application No. 62-263318.

Table 5 *Coefficient of variation - standard deviation/average particle size Book *Confirmed from analysis of diffraction lines using CuKα radiation as a radiation source.

Cpd-1 and Cpd-9 used in Example 1 were added to the above emulsions EM-7 to EM-9, respectively.

In sample 5, omit the sixth layer and add dye (40) to the fifth layer.
Sample 6 was obtained in the same manner except that the same amounts of (41) and (41) were added.

Sample 5 was the same except that the dye used in the sixth layer and the coupler and its dispersion used in the seventh layer contained an organic solvent-soluble polymer as shown in Table 6 below. Samples 6.7.8 were obtained. EM-7
In place of samples 8 and 8, silver chlorobromide emulsions EM-10 and EM-11 having grains with the same halogen composition were used, although no silver bromide-containing localized phase was observed on the surface of the silver halide grains. Sample-9 was obtained in the same manner as above.

Example - Ront (shifting) pre-exposure and exposure for measurement of resolution were carried out, and the following color development treatment was carried out.

Measurements were performed at 29 degrees and the results are shown in Table 7.

*Similar to Example 1, the values are expressed as values that include the reflection of the support itself.

Car * By visual observation, ◎ ○ Good In the present invention, silver halide emulsion E! If Cpd-9 used in vL-7 to vL-9 is not used, stain or fog will increase, and in Table 7, samples 5 to 8, D
min (7 zentas) became 0.24 or more. Sample 5
to Cpd-9 using EM-7 to 28.
In place of - Noshiro (II), (In) and (IV) exemplified compounds (3), (6),
(8), 0υ, θ angle or using (2), Dmin(
magenta) can be suppressed to 0.12 to 0.13.

Especially in samples 5 to 8 in the present invention, Dmin
This shows that it is highly effective in keeping the amount low.

In addition, in sample-5 according to the present invention, Cpd was added to the fifth layer.
-4, along with exemplified compound (V)-Qll, v-a, w
, v-agl, (Vl)-+51, (V[)-(7+ or (Vl)-[81) were used at 0.05 g/m each. We were able to recognize the effect of reducing the

1. compared to sample-9 and sample 8. Although it is within the allowable limit, it can be seen that the temperature is quite high.

1" Fengshi Poetry color development 35℃ 45 seconds bleach fixing 30~36℃ stable for 45 seconds■ 30~37℃ stable for 20 seconds■ 30~37° (stable for 20 seconds■ 30~37℃ stable for 20 seconds■ 30~ Dry at 37℃ for 30 seconds 70-85℃ for 60 seconds (stable)
−■ A four-tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Fu Puni Den a? ('j Wednesday 80
0 is ethylenediaminetetraacid resistant 2.0g triethanolamine 8.0g sodium chloride 1.4g potassium carbonate
25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0gN,N-diethylhydroxylamino 4.2g5.6-cyhydroxyhenzeno 1.2.4- Trisulfonic acid 0.3g Fluorescent brightener (4,4'-diaminostilhene type> 2.0g Add water to 1000 dpH (25℃)
10.10 Counterfeit page Yodokarasui 400
m1,000 ammonium osulfate (70%) 100m
1 Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Disodium ethylenediaminetetraacetate 3g Glacial acetic acid
Add 8g water
1000dpH (25℃) 5.5 n Formalin (37%) 0.1g formalin-sulfite adduct 0.1g 5-chloro-2-
Methyl-4-isothiazolin-3-one 0
．． 02g 2-Methyl-4-isothiazolin-3-one Add 0.01g water
1000+++fpH (25℃) 4
．． 0 (Effect of the invention) According to the present invention, without significantly deteriorating the coated surface quality,
In addition, the cationic properties with guanidyl ketimine residues do not deteriorate color development processability, especially rapid processability, and process independence of gradation and sensitivity (gradation and sensitivity do not change due to fluctuations in processing conditions). By using a polymer-containing layer and a dye in combination, color photographic paper with excellent image sharpness and color reproducibility can be produced.

Furthermore, in color print sensitive materials containing high silver chloride emulsions, color prints with less stain can be obtained by using them in combination with mercaptoazole compounds.

Furthermore, by providing a filter layer between the silver halide emulsion layers, color mixture can be prevented and the saturation of the color image can be improved.

Claims (2)

[Claims] (1) In a silver halide photographic material comprising at least one photosensitive emulsion layer containing silver halide grains coated on a reflective support, at least one emulsion layer contains all halogens contained therein. Silver chloride grains contain silver chlorobromide or silver chloride with an average silver chloride content of 90 mol% or more, and contain a polymer compound containing a repeating unit having a guanidyl ketimine residue in the vicinity of the emulsion layer. 1. A silver halide photographic light-sensitive material, which further contains a mercaptoazole compound in any one of the polymer compound-containing layer, the silver halide emulsion layer, and a layer located between these layers. (2) The photosensitive emulsion layer containing silver halide grains contains silver chlorobromide or normal crystals of silver chloride in which the average silver chloride content of all the silver halide grains contained therein is 90 mol% or more. 2. The silver halide photograph according to claim 1, wherein at least 50% by weight of all the silver halide grains contained therein have a localized silver bromide phase inside or on the surface of the grains. photosensitive material.