JPS6275444A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the spectral characteristics and color reproducibility by incorporating a 1-naphthol type cyan dye forming coupler having a mono- substituted amino group at the 5-position and a phenol type cyan dye forming coupler having an arylureido group at the 2-position and a carbonamido group at the 5-position. CONSTITUTION:At least one photosensitive silver halide emulsion layer contg. at least one kind of 1-naphthol type cyan dye forming coupler having a mono- substituted amino group at the 5-position and at least one kind of phenol type cyan dye forming coupler having an arylureido group at the 2-position and a carbonamido group at the 5-position is formed on a support. Considerable subsidiary absorption in the blue region by the 1-naphthol type cyan dye forming coupler and that in the green region by the phenol type cyan dye forming coupler are avoided by combinedly using the couplers, so a photographic sensitive material having superior color reproducibility is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material. This invention relates to silver halide color photographic materials.

(Prior Art) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer reacts with a dye-forming coupler (hereinafter abbreviated as coupler). A color image is formed.

Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images.

In color photography, color-forming couplers are added to the developer solution or incorporated into a light-sensitive photographic emulsion layer or other color image-forming layer and react with the oxidized form of the color developer formed by development. This forms a non-diffusible dye.

The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and couplers with hydrogen atoms at this active site have 4
Equivalent couplers, ie, require stoichiometrically 4 moles of silver halide to form 1 mole of dye.

On the other hand, those with t and H groups that can be separated as anions at the active sites are 2-equivalent couplers, that is, stoichiometrically only 2 moles of silver halide with development nuclei are required to form 1 mole of dye. It is a coupler, and therefore, compared to a 4-equivalent coupler, the amount of silver halide in the photosensitive layer can be generally reduced and the film thickness can be made thinner, which makes it possible to shorten the processing time of the photosensitive material and improve the sharpness of the color image formed. will improve.

The performance requirements for a coupler include excellent stability, excellent color development, and excellent processing suitability.
The hue of the coloring dye is sharp, and the fastness of the color image is excellent.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan couplers.

In particular, 1-naphthol couplers have a long wavelength absorption maximum (λmax) of the coloring dye produced, have little side absorption in the edge region, and are excellent in color reproduction, and many couplers with excellent coloring properties have been found. As a result, it has been widely put into practical use in color negative photosensitive materials.

However, the phenolic couplers and naphthol couplers that have been widely used in the past cannot be used in the bleaching or bleach-fixing process of color development when the bleaching or bleach-fixing solution is exhausted or when a bleaching agent with weak oxidizing power is used. had the disadvantage that a sufficient color image could not be obtained. This phenomenon is caused by the first product produced during the bleaching or bleach-fixing process.
It is thought that the reduction of cyan dye by iron ions causes fading. Furthermore, the cyan images formed by these couplers have a drawback of low fastness.

Among the phenolic couplers and naphthol couplers known as cyan dye-forming couplers, the phenolic cyan coupler, which has a phenylureido group at the 2-position and an acylamino group at the 5-position, is more effective than other cyan couplers. In JP-A-5, it was discovered that the color images produced by color development have excellent fastness to heat and light.
No. 6-65134, No. 57-204543, No. 57-
No. 204544, No. 57-204545, No. 58-3
It is disclosed in No. 3249, No. 58-33250, etc.

These couplers have the advantage that the color images produced are of a favorable hue and are fast, and that there is almost no decrease in color density even when processed with a bleaching solution with weak oxidizing power or a bleaching solution that is exhausted. This has the disadvantage that the absorption is large, which deteriorates color reproducibility, and that even with a 2-equivalent coupler, a sufficiently high coloring property cannot be obtained.

On the other hand, JP-A No. 59-46644 is characterized in that a phenolic cyan coupler having a phenylureido group at the 2-position and a carbonamide group at the 5-position is used in combination with a conventional naphthol-based cyan coupler. A silver halide color photographic material is disclosed. However, since this method still uses a conventional naphthol-based cyan coupler, it suffers from the disadvantages that sufficient color density cannot be obtained by processing using tired or weakly oxidizing bleach or bleach-fix solutions, and cyan couplers. It had the disadvantage of low image fastness.

(Object of the present invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent spectral absorption characteristics of cyan color images and excellent brown color reproducibility.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which the cyan color density decreases extremely little even when a bleach or bleach-fix solution that is tired or has weak oxidizing power is used during bleaching or bleach-fixing processing. It is to be.

A third object of the present invention is to provide a silver halide color photographic material with excellent cyan image fastness.

(Means for Solving the Problems) The above aspects of the present invention include at least one photosensitive silver halide emulsion layer on a support, and at least one type of silver halide emulsion layer having a monosubstituted amino group at the 5-position. Silver halide color photographic photosensitive material containing a 1-naphthol cyan dye-forming coupler and at least one phenolic cyan dye-forming coupler having an aryl ureido group at the 2-position and a carbonamide group at the 5-position. achieved by the material.

The 1-naphthol cyan dye-forming coupler having a monosubstituted amino group at the 5-position, which is used in the present invention, has an aryl ureido group at the 2-position and a carbonamide group at the 5-position according to general formula [I]. The phenolic cyan dye-forming coupler having the formula is preferably one represented by the general formula [II].

λ In the above formula, R is -CON Rs R6, -NHCOR
5, -NHCOOR, -NH3O,R, -NHCONR5R, or -NH
3OiNRsRs, R2 represents a group that can be substituted on the naphthol ring, m represents an integer from 0 to 3, and R1 represents a monovalent organic group. Further, R4 represents an aliphatic group, an aromatic group or a heterocyclic group, and Ar represents a substituted or unsubstituted aryl group,
X represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, R3 and R6 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R7 represents an aliphatic group, an aromatic group or a heterocyclic group. In the formula, when m is plural, R2 may be the same or different, or may be bonded to each other to form a ring. R2 and Rff or R3 and X may be bonded to each other to form a ring.

Here, the aliphatic group refers to an aliphatic hydrocarbon group (the same applies hereinafter), and includes straight, branched, or cyclic alkyl, alkenyl, or alkynyl groups, and may be substituted or unsubstituted. Good too. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring.

The term "heterocycle" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

The substituents in general formulas [I] and [■] will be described in detail below.

R1 is the group described above, and examples of R5, R8 and R2 include an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms.

R2 represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic Examples include a sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group, and the number of carbon atoms contained in R2 is 0 to 30. An example of cyclic R2 when m=2 is a dioxymethylene group.

R8 represents a monovalent organic group, and is preferably represented by the following general formula Cml.

R, (Y), -... [I[[] Here, Y represents >NHl>CO or >SO□, n
is zero or 1, R8 is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, -0R3, or -3O20R, represent Here, R3, RIG and R11 are each the above-mentioned Rs.
, Rs and R7.

They may be combined to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

R4 represents an aliphatic group having 1 to 36 carbon atoms, an aromatic group having 6 to 36 carbon atoms, or a heterocyclic group having 2 to 36 carbon atoms, preferably a tertiary alkyl group having 4 to 36 carbon atoms or a tertiary alkyl group having 7 carbon atoms.
-36 is a group represented by the following general formula [rV].

In the formula, RI2 and RI3 may be the same or different, and are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms, or 6 carbon atoms.
-30 aromatic group, R14 represents a monovalent group, and Z represents 10-1-S-1-SO- or -802-. β represents an integer from 0 to 5, and when l is a plurality of numbers, the plurality of R+4s may be the same or different. Preferred substituents include R12 and RI3 each representing a straight chain or branched alkyl group having 1 to 18 carbon atoms, and R14 representing a halogen atom, aliphatic group, aliphatic oxy group, carbonamide group, sulfonamide group, carboxy group, or sulfo group. , cyan group, hydroxyl group, carbamoyl group, sulfamoyl group, tell
The fl group oxycarbonyl group and aromatic sulfonyl group are Z
can list 10- respectively. Here R14
The number of carbon atoms is preferably 0 to 30, and β is preferably 1 to 3.

Ar represents a substituted or unsubstituted aryl group, and may be a condensed ring. Typical substituents for Ar include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group,
-COOR,S, -COR,S, -8O7OR1s, -
NHCOR1s can be done. R+s and R+6 may be the same or different and represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R17 represents an aliphatic group, an aromatic group or a heterocyclic group. Ar has 6 to 30 carbon atoms, and is preferably a phenyl group having the above-mentioned substituents.

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include halogen atom, -OR,, -3R,B, -0
CR,,,N HCOR+ e, aromatic azo group having 6-30 carbon atoms, heterocyclic group having 1-30 carbon atoms and connected to the coupling active position of the coupler with a nitrogen atom (succinimide group, phthalimide group, (hydantoinyl group, pyrazolyl group, 2-benztriazolyl group, etc.). Here, R11+ is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or an aromatic group having 2 to 30 carbon atoms.
represents a heterocyclic group.

As mentioned above, the aliphatic group in the present invention is saturated, unsaturated,
It may be substituted or unsubstituted, straight, branched, or cyclic. Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group,
Methoxyethyl group, n-decyl group, n-dodecyl group, n
-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2.4-
Di-tert-amylphenoxypropyl group, 2.4-
Di-tert-amylphenoxybutyl group, etc. are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group,
2-chloro-5-dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-
Contains hydroxyphenyl groups, etc.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
Includes 2-furyl group, 4-chenyl group, quinolinyl group, etc.

Preferred examples of substituents in the present invention will be explained below. R
1 is preferably -CONR3R, specific examples include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,4-di-tert-amyl group. Examples include phenoxypropyl group and 2,4-di-tert-amylphenoxybutyl group.

Regarding R2 and m, it is most preferable that m=0, that is, unsubstituted, and the next preferable substituents for R2 include a halogen atom, an aliphatic group, a carbonamide group, and a sulfonamide group.

Preferred R3 is the general formula [■] in which n is zero, and R
8 is -COR, (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), -COOR.

(methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -3O2R,, (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.), -CON
R, R, (N.

N-diethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbonyl group, 3゜4-dichlorophenylcarbamoyl group, 4-methane sulfonylphenylcarbamoyl group), -8○2NR,R,, (N,N-dimethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) . Particularly preferable R3 are -COOR3, -COR, and -SO□R11, and among these, -COOR is more preferable.

Preferred examples of X include a hydrogen atom, a halogen atom, and an aliphatic oxy group having 1 to 30 carbon atoms (methoxy group, 2-methanesulfonamidoethoxy group, 2-methanesulfonylethoxy group, carboxymethoxy group, 3-carboxypropyloxy group). , 2-carboxymethylthioethoxy group, 2-
methoxyethoxy group, 2-methoxyethylcarbamoylmethoxy group, etc.), aromatic oxy group (phenoxy group, 2-methoxyethylcarbamoylmethoxy group, etc.),
-chlorophenoxy group, 4-methoxyphenoxy group, 4
-tert-octylphenoxy group, 4-carboxyphenoxy group, etc.), heterocyclic thio group (5-phenyl-1,
2,3,4-tetrazolyl-1-thio group, 5-ethyl-
1,2,3,4-tetrazolyl-1-thio group, etc.) and aromatic azo groups (4-dimethylaminophenylazo group, 4-dimethylaminophenylazo group, etc.)
-acetamidophenylazo group, 1-naphthylazo group,
2-ethoxycarbonylphenylazo group, 2-methoxycarbonyl-4,5-dimethoxyphenylazo group, etc.)
It is.

Preferred examples of R4 include 1-(2,4-di-tert-amylphenoxy)amyl group, 1-(2,4-di-tert-amylphenoxy)amyl group,
rt-amylphenoxy)hebutyl group, 1-butyl group, etc.

Particularly preferable A's include 4-cyanophenyl group, 4-
Alkylsulfonylphenyl groups (4-methanesulfonamidophenyl group, 4-propanesulfonamidophenyl group, 4-butanesulfonamide group, etc.) and halogen-substituted phenyl groups (4-fluorophenyl group, 4-chlorophenyl group, 3.4- Dichlorophenyl group, 2.4.5-
)! J dichlorophenyl group, etc.).

The coupler represented by general formula [I] has substituents R,, R
2, R3 or may be formed. In this case, the carbon number range shown in each of the above-mentioned substituents may be outside the specified range.

When the coupler represented by the general formula [■] or [IN] forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. This is an example. In this case, the multimer contains repeating units of the general formula [■], and one or more types of cyan coloring repeating units represented by the general formula [■] may be contained in the multimer, and non-containing as a copolymerization component. It may also be a copolymer containing one or more color-forming ethylene type monomers.

In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A is -CONH-1-COO- or a substituted or unsubstituted phenylene group, and B is a substituted or unsubstituted phenylene group. represents an alkylene group, phenylene group or aralkylene group, L is -CONH-1-NHCONH
-1-NHCOO-1-NHCO-1-0CONH-1
-NH-1-COO-1-OCO-1-CO-1-〇-
Represents 1-SO2-1-NH3O2- or -3O,NH-. a, b, c represent O or 1. Q is the general formula [
This shows a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1st position has been removed from the compound represented by [I] and [■].

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of the general formula [■] and a non-color-forming ethylene-like monomer shown below is preferred.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, -butyl acrylate), iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β
-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene) ), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride,
Vinyl alkyl ethers (eg vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the general formula CV] depends on the physical and/or chemical properties of the copolymer to be formed. can be selected such that, for example, solubility, compatibility with binders such as gelatin of the photographic colloidal composition, its softening temperature, flexibility, thermal stability, etc. are favorably influenced.

The cyan polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above general formula [■] in an organic solvent, and adding the resulting latex solution to an aqueous gelatin solution. It may be made by emulsion dispersion in the form of , or it may be made by direct emulsion polymerization method.

U.S. Pat. No. 3.4 describes a method for emulsifying and dispersing lipophilic polymer couplers in an aqueous gelatin solution in the form of latex.
No. 51.820 and U.S. Pat. No. 4.820 for emulsion polymerization.
080.20 and 3.370.952 can be used.

Next, specific examples of the coupler represented by the general formula [I] will be shown, but the coupler used in the present invention is not limited to these. Each of the following structural formulas is represented by % formula %.

death! □ [:, l(2, (I -22)) ■ CI2825 (I-24) (I-25) NHCOC (C113) 3 (1-38) DOH - (l - (CH2CHh-1---→CH2CH) 7[Jl-
1:H2CHh-(CI(2CH, NflCOCO[l[nee Hs = 70:30 (molar ratio)) (I-44) :y = 50:50 (molar ratio) -(CH2CHh parts --- complete set [: 11 □CH'h-
1iroH2CHh---beC8C4HsOCONHx:y=60:40 (mole ratio)N-46)2CH)y-C00C4H.

C2HsOCONHN /゛~1] [1\nCH3CH3(l-50) Next, specific examples of the coupler represented by the general formula [■] are shown below.

CsL 1(t) (II-7) (n-8) (n-9) (I[-10) (n-11) (If-12) 'C5HII(t) e,H,t(o (II -16) Mouth 5Hz (t
) j:5Hz(t) CooH([[-18) Cf! e8h, o) (I[-19) UI''1 NHC[1CH3 (n -26) (II -27) The coupler of general formula [■] and the coupler of general formula [■] are contained in the same layer. When they are contained in the same layer, they may be emulsified separately or co-emulsified.

Further, the usage ratio of the general formulas [■] and [■] is CID/CI]=0.2 to 5.0 in terms of molar ratio, preferably 0.5 to 2.0. This molar ratio is expressed by the general formula [I]
When two or more types of cyan couplers represented by [I[] are used, the total molar ratio is 9, and for polymer couplers, the number of moles of the coupler residue is used as the standard.

In order to introduce the two cyan couplers of the invention into a silver halide photographic light-sensitive material, it is possible to follow methods known to those skilled in the art for introducing generally diffused diffusion-resistant couplers into a hydrophilic colloid layer. That is, it is convenient to follow the so-called emulsification dispersion method.

Patent application for synthesis of cyan coupler of general formula [■] of the invention 1982
~93605, 59-264277 and 59-2
68135.

These 1-naphthol-based cyan couplers having a mono-substituted amino group at the 5-position have poor color image fastness (and the color density even when processed with the aforementioned tired or weakly oxidizing bleach or bleach-fix solutions). It is excellent in that there is almost no decrease in

Furthermore, it is possible to obtain a combination of couplers with extremely high color-forming properties by using a coupler of the general formula [■] which has been made into two equivalents, and furthermore, it is also possible to obtain a combination of couplers with extremely high color-forming property. It is excellent in that it does not cause shortening of the dominant wavelength as described in Japanese Patent No. 82837, and is particularly suitable for obtaining highly sensitive photosensitive materials. In addition to these advantages, especially according to the present invention, by using the coupler of the general formula [II] in combination, the disadvantage of the 1-naphthol cyan coupler having a monosubstituted amino group at the 5-position, that is, in the blue region, can be overcome. It has a large sub-absorption, and the drawback that this sub-absorption deteriorates the color reproducibility of photosensitive materials can be overcome.

The coupler of the present invention and other couplers used in combination can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, more preferably oil-in-water dispersion method, etc. can be cited as a typical example.

In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling organic solvents are U.S. Patent No. 2.322.
It is described in No. 027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenine phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.) ), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate,
trioctyl citrate, etc.), aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (halafine, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

Examples of the steps, effects, and latex for impregnation of latex dispersion methods are described in U.S. Pat. , 54L230, etc.

Various color couplers can be used in combination with the present invention, Research Disclosure, December 1978,
17643■-D section and same, November 1979, 18
The cyan, magenta and yellow dye-forming couplers described in the patents cited in '717 are representative. These couplers can be modified by introducing a ballast group or by
It is preferable that the coupler has diffusion resistance due to multimerization of more than 100%, and may be a 4-equivalent coupler or a 2-equivalent coupler. Coupler that improves graininess by diffusing the produced dye, and DIR that releases development inhibitors and the like during the coupling reaction and produces an edge effect or multilayer effect.
Couplers can also be used.

The vine yellow coupler used in combination with the present invention is preferably an α-pivalol or α-benzoylacetanilide coupler that splits at an oxygen atom or a nitrogen atom.

Particularly preferred examples of these two-equivalent couplers are U.S. Pat.
20, or U.S. Pat. No. 3.973.968, U.S. Pat. West German Application Publication No. 2, 219
．． No. 917, No. 2.261361, No. 2.329
．． Typical examples include the nitrogen atom separation type yellow couplers described in No. 587 and No. 2.433.812. As a magenta coupler, a 5-pyrazolone coupler, pyrazolo[5,1-c] [:1,2,4] described in U.S. Pat. No. 3.725.067 is used.
Triazoles or pyrazolo[5,1-b:] [:1,2.4] as described in EP 119.860
) Riazole etc. can be used. 2 by a leaving group bonded to the coupling active position with a nitrogen atom or a sulfur atom.
A tinted magenta coupler is also preferred.

The two types of cyan couplers of the present invention and the dye image-forming coupler (main coupler) that can be used in combination with the above are usually mixed with a high boiling point organic solvent such as phthalate esters or phosphate esters having 16 to 32 carbon atoms as necessary. The emulsion is dispersed in an aqueous medium using an organic solvent such as ethyl acetate. The standard amount of main coupler used is preferably 0.01 to 0.5 mol for yellow couplers, 0.003 to 0.3 mol for magenta couplers, and 0.003 to 0.3 mol for cyan couplers per mole of photosensitive silver halide. It is 0.002 to 0.3 mole.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. The preferred silver halide is 3
Contains 0 mol% or less of silver iodide. Silver iodobromide or silver iodochlorobromide. Particularly preferred is 2 mol% to 25 mol%.
It is silver iodobromide containing silver iodide up to.

The shape of the silver halide grains in the photographic emulsion is not particularly limited, and may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, or may be spherical. It may have an irregular crystal shape, a crystal defect such as a crystal plane, or a combination thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

Two or more types of silver halide emulsions formed separately may be mixed and used.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1eve, Photogra-a
phy Theory ancl Practice
(1930), p. 131; Guto, Photographic Science and Engineering.
ff, Photographic Science a
nd [Engineering) Volume 14, 248
~257 pages (1970), U.S. Patent No. 4.434.2
No. 26, No. 4.414.310, No. 4.433.
048 and British Patent No. 2.112.157. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. L 027.1
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4.4
44.877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The photographic emulsion used in the present invention may be spectrally sensitized using known photographic sensitizing dyes. In addition, known antifoggants or stabilizers may be used for the purpose of preventing fog or stabilizing the performance of photosensitive materials during manufacture, storage, or photographic processing. U.S. Patent No. 3.954. +174, same number 3.982.94
No. 7, Special Publication No. 52-28660, Research Disclosure 17643 (December 1978) VIA or VIM, and Birr, "Stabilization of Silver Halide Photographic Emulsions," Focal Press Co., Ltd. (Shi, J. Birr,
5tabilization of Photogr
aphic 5ilver l1alide Emul
ions ll, Focal Press.

1974) and others.

The light-sensitive material of the present invention may contain hydroquinones, aminophenols, sulfonamidophenols, and the like as a color antifogging agent or color mixing inhibitor. Various anti-fading agents can be used in the photosensitive material of the present invention,
There are organic inhibitors such as 5-hydroxycoumarans and spirochromans, and metal complex inhibitors such as H, His-(N,N-dialkyldithiocarbamado)nickel complexes.

The light-sensitive material of the present invention may be used in combination with an ultraviolet absorber such as benzo)IJ azoles, typical examples of which are described in Research Disclosure 24239 (June 1984). The light-sensitive material of the present invention may also contain a water-soluble dye in the hydrophilic colloid layer for filter dyes, irradiation or antihalation purposes, and other purposes.

Gelatin, modified gelatin, synthetic hydrophilic polymers, etc. can be used as the binder for the photographic light-sensitive layer or back layer of the present invention. Further, a hardening agent such as a vinyl sulfone derivative may be contained in any hydrophilic colloid layer.
Additionally, vinyl polymers containing sulfinate salts in their side chains may be used as hardening agents.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, promoting phenomena, increasing contrast, and sensitizing). But that's fine.

In addition to the above-mentioned additives, the light-sensitive material of the present invention further contains various stabilizers, anti-staining agents, phenolic agents or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (19
(November 1976).

The present invention can be preferably applied to a color film for high-sensitivity photography, which has at least two emulsion layers having the same color sensitivity and different sensitivities on a support. The typical layer arrangement order is a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in order from the support side.
It may also be an inverted layer arrangement in which a high-speed layer is sandwiched between emulsion layers having different color sensitivities.

After being processed with a developer containing an aromatic primary amine color developing agent as a main component, the light-sensitive material of the present invention is processed by bleaching and fixing, bleach-fixing, or a combination thereof in order to remove the developed silver. conduct. At this time, bleaching accelerators such as iodine ions, thioureas, thiol compounds, etc. may be used in combination, if necessary.

Washing with water is often performed after bleach-fixing or fixing, but it is convenient to use two or more tanks for countercurrent washing to save water.

Alternatively, a multistage countercurrent stabilization treatment as described in Japanese Patent Application Laid-Open No. 57-8543 may be performed. A pH adjusting buffer or formalin may be added to this treatment. Ammonium salts are preferred additives.

〔Effect of the invention〕

According to the present invention, 1-
By using a specific 2-equivalent coupler, that is, a phenolic cyan dye-forming coupler having an aryl ureido group at the 2-position and a carbonamide group at the 5-position, in combination with a naphthol-based cyan dye-forming coupler, the blue region of the former can be obtained. This has the advantage that a photographic material with excellent color reproducibility can be obtained in which the large sub-absorption in the green region and the large sub-absorption in the green region of the latter are eliminated. In addition to these advantages, silver halide produces cyan images with extremely little loss of cyan color density and excellent color fastness even when using a bleach or bleach-fix solution with a worn-out or degraded bleaching blade. A color photographic material is provided.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 Photosensitive materials Samples 101 to 110 were prepared on a cellulose triacetate support, each layer having the composition shown below.

The couplers contained in the first red-sensitive emulsion layer are shown in Table 1.

In addition, when emulsifying and dispersing the coupler, the high-boiling point solvent is dibutyl phthalate, and the amount used is twice the weight of the coupler.

1st layer: Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.5 μm) Silver coating amount 1.8 g / m2 Sensitizing dye I 4.5 Xl0 per 1 mol of silver -'molar sensitizing dye■ L5 It is a mole. However, 2
When seeds are used in combination, the amount of each added is 0.08 mol. ) Second layer: Protective layer polymethyl methacrylate particles (diameter approximately 1.5 μm)
Gelatin layer containing gelatin coating amount 1.1 g/m'' In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

Compound enhancer dye r used to prepare the sample: Anhydro-5,5'-dichloro-3,3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(T-sulfopropyl)-4,5,4 "-5"-dibenzo'thiacarbocyanine hydroxide triethylamine salt X-1 α X-2 (CH2=C)lsOzcLcONHcL) 2-(C
H2=CH302CH2CONHCH2) 2-After exposing the obtained samples 101 to 110 to light for sensitometry, the following development treatment [A] was performed at 38°C.

1. Color development 3 minutes 15 seconds 2.
Bleach 6 minutes 30 seconds 3, wash with water
3 minutes 15 seconds 4, fixed
4 minutes 20 seconds 5, water washing 3 minutes 15 seconds 6, stability 1 minute 5 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0 g potassium bromide
1.4g salt
Add 4.5g water
1! 1 white liquid ammonium bromide 160.08 liters ammonium bromide water (28%) 25.0 cc glacial acetic acid
Add 14.0cc water
1 β fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium biphosphite 4.6g Add water
11 Stabilizing liquid formalin Add 8.0 cc of water 1 β1 Regarding the developed sample, evaluate the spectral absorption of the developed color image, the relative cyan color density when processed with a tired bleach-fix solution, and the color image survival rate in the fading test. It was measured by the following method.

Spectral absorption measurement of the developed color image The spectral absorption of the developed color image was measured for the following points. The results are summarized in Table-1.

of the concentration at 450nm (blue subabsorption) of 550n
Measurement of the cyan coloring density relative to the density (green side absorption) at 450 nm and the density at 550 nm. For samples 101 to 110 exposed in the same manner as above, the processing solution of the bleaching treatment in the development treatment [A] Development processing CB] was carried out in the same manner as development processing [A] except that the following processing solution formulation was used. This bleaching solution simulates the state in which a large amount of photosensitive material has been processed and has become fatigued.

Treatment step CB] Bleach solution composition (B-1) Ammonium bromide 160.0 g Ammonia water (28%) 7.1 mf Ethylenediamine-tetraacetic acid Lithium iron acetate salt 117 g Glacial acetic acid 14 ml Add 1 water
900ml! (B-2) Diamine-tetraacetic acid sodium iron salt 13G g Add water, put steel wool into 1 β (B-2), close the stopper, leave it to dissolve Fe (I[I
) - After changing EDTA to Fe (I[) -60TA, this 100 mj! The treatment was carried out in the same manner as in treatment step [A], except that (B-1) was added to prepare the bleaching solution for treatment step [B].

Treatment step [A] and sample 101 treated with CBI
110 sensitometry was carried out, and the cyan color density obtained in the fatigued process [B] was divided by 1.5 at the exposure amount at which a cyan color density of 1.5 was obtained in the non-fatigued process [A]. The values are summarized in Table-1.

Measurement of residual rate of zero color image Using a developed sample similar to that used for measuring the developed color image, (1) Store in the dark at 100°C for 14 days (2) Canon photofading tester (100,000 lux) A color image fastness test was conducted under two conditions of 7 days of light exposure.

Table 1 summarizes the color image survival rate at a cyan initial density of 1.5.

From the results in Table 1, when the ureido type phenol coupler according to the present invention is used alone (sample 101), the side absorption in the green region is especially large. When the naphthol couplers were used alone (Samples 109 and 110), the sub-absorption in the blue region was particularly large, but in the samples according to the present invention in which they were used in combination (Samples 102 to 104), these sub-absorptions were significantly reduced. I can see that you are there. In addition, E which is a coupler outside the present invention
When X-2 is used in combination (sample 106), it can be seen that the sub-absorption is small in both the green and blue regions, but the relative cyan coloring density decreases greatly and the color image retention rate is also poor.
This does not meet the purpose of the present invention.

On the other hand, in the products of the present invention, almost no decrease in density is observed during processing using a tired bleaching solution, and the color image retention rate is also good.

From the above results, it is clear that silver halide which has excellent spectral absorption characteristics of cyan color images, which has a small density loss during processing using a tired bleaching solution, and which has excellent color image fastness, which is the object of the present invention, has been developed. In order to realize a color photographic light-sensitive material, it is necessary to use a 1-naphthol cyan coupler having a monosubstituted amino group at the 5-position according to the present invention, and a 1-naphthol cyan coupler having an aryl ureido group at the 2-position and having an aryl ureido group at the 5-position according to the present invention. It is clear that it is better to use a phenolic cyan coupler having a carbonamide group in combination.

Example 2 Multilayer color photosensitive materials 201 to 207 each having the composition shown below were prepared on a cellulose triacetate support.

The coating amount of silver halide is expressed in silver equivalent g/m2, the coating amount of ceratin and the coating amount of oil for coupler dispersion are expressed in g/m2, and the sensitizing dye and coupler are expressed in moles per mol of silver halide in the same layer. Expressed in units.

1st layer: Antihalation layer Black gelatin containing colloidal silver Seratin coating amount 1.1 2nd layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-sheet t-hentadecylhydroquinone and coupler EX-3 and silver iodobromide (silver iodide 1 mol %, average particle size 0.07 μm) Gelatin coating amount 1.4 force puller dispersion Oil ■0.2 〃■0゜02 3rd layer: 1st red-sensitive emulsion layer Silver coating ■1.5 Sensitizing dye I 4.5X10-'〃
II 1.5X10-' coupler As shown in Table 2 Gelatin coating amount 1.2 Power puller dispersion oil 0.3 4th layer: 2nd red-sensitive emulsion layer Silver coating amount 2.0 Sensitizing dye r
3.0X10-'//II
1.0X10-' coupler Described in Table 3 Gelatin coating amount 1.3 Power puller dispersion oil I O,15In 0.30 5th layer: Intermediate layer gelatin layer Gelatin coating amount 0.9 6th layer: 1st green Sensitizing emulsion layer silver coating amount 0.6 Sensitizing dye III
4.5X10-'” IV
1.8X10-'Cub5-EX-
70,078 〃 EX-80,019 〃 EX-90,006 Gelatin coating amount 0.5 Power puller dispersion oil I O, 18 7th layer: 2nd green emulsion layer Silver coating amount 1.5 Sensitizing dye III
4.0XlO-'tt ■
1.6xlO-' coupler EX-1
00,018 〃 EX-80,002 〃 EX-90,001 Gelatin coating amount 1.8 Force puller dispersion oil IO, 50” I[0,
12 8th layer: 3rd R-sensitive emulsion layer Silver coating amount 2.0 Sensitizing dye I [3
,0X10-' 〃rV 1. :) Yellow colloidal silver and 2,5-di-t-
Gelatin layer containing emulsified dispersion of pentadecyl hydroquinone Gelatin coating amount 0.9 10th layer: 1st
Blue-sensitive emulsion layer silver coating amount 0.5 coupler EX-
110,25 〃 EX-120,003 Gelatin coating amount 1.3 Power puller dispersion oil 10.3 11th layer: 2nd blue-sensitive emulsion layer Silver coating amount 0.6 coupler EX-
110,047 Gelatin coating amount 0.5 Coupler dispersion oil I O,05 12th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 10 mol% Average grain size: 1.8 μm) Silver coating Amount 1.0 sensitizing dye V
2.1X10-'Coupler EX-1
10,035 Gelatin coating amount 0.4 Force puller dispersion oil I O, 15 13th layer: 1st protective layer: Gelatin layer Gelatin coating amount 0.7 14th layer: 2nd
Protective layer silver iodobromide (silver iodide 1 mol%, average grain size 0.07 μm) J
and polymethyl methacrylate particles (approximately 1.5μ in diameter)
Gelatin layer gelatin coating amount including m)
0.8 In addition to the above composition, each layer contains a gelatin hardening agent H-
1 and H-2 and a surfactant were added.

Table-2 Third layer coupler *The amount added represents the amount added per 1 mole of silver.

Table-3 Compound sensitizing color sm used to prepare the fourth layer coupler sample: Anhydro-9-ethyl-5,5゜-dichloro-3,3''-di<r-sulfopropyl)oxacarbocyanine sodium Salt-sensitizing dye ■: Anhydro 5.6.5',6'-tetrachloro-1,1'-diethyl-3,3'-di(β-[β-(γ-sulfopropoxy)ethoxy]ethylimidazolo Carbocyanine hydroxide sodium salt sensitizing dye ■: Anhydro-5,5°-dichloro-3,3
'-di(δ-sulfobutyl)thiacyanine triethylammonium salt coupler EX-4 Coupler EX-5 Coupler EX-6 Coupler EX-7 -(CH2-CH, CH2-CH, CH2-CID-.

1 1] Coupler E
X-10 Coupler EX-12 CH2=CH302fl:H2C0NH-C112□ CH2 Tortoise CH2=[:H3O2, CH2C0NH-CH2 Coupler dispersion oil I Coupler dispersion oil■ Coupler dispersion oil■ (C6H,,0→Cing PO Obtained Samples 201 to 207 were tested in the same manner as in Example 1. Color image fastness tests were also carried out using (1) 80
Store in the dark at ℃ for 14 days (2) Fluorescent light fading tester (1)
The test was carried out under two conditions: 1,000,000 lux) and 7 days of light exposure. The above results are summarized in Table 4.

When the ureido type phenol coupler according to the present invention is used in both red-sensitive emulsion layers (sample 202), the decrease in cyan color density is small when treated with fatigue bleaching solution, and the color image fastness is also excellent. However, the subabsorption is large on the short wavelength side, especially in the green region. Furthermore, when the 1-naphthol coupler having a monosubstituted amino group at the 5-position according to the present invention was used in both layers (sample +206), the cyan coloring density decreased when treated with fatigue bleaching solution, similar to sample 202. Although it is small and has excellent color image fastness, it has large sub-absorption on the short wavelength side, especially in the blue region.

In contrast, samples according to the invention (sample 203.205
), the sub-absorption on the short wavelength side is reduced in both the green and blue regions, and the decrease in cyan coloring density is small when treated with fatigue bleaching solution, and the color image fastness is also excellent. Further, Document 205 has high sensitivity, and it can be seen that this combination is suitable for a high-sensitivity photosensitive material. In contrast, when a ureido-type phenol coupler according to the present invention and a naphthol coupler other than the present invention were used together (Sample 201), and when a 1-naphthol coupler having a monosubstituted amino group at the 5-position according to the present invention was used together. In case (sample 204), although the sub-absorption on the short wavelength side is small, the color density decreases greatly when treated with a fatigue bleaching solution, and the fastness of the color image is also poor, which is not suitable for the purpose of the present invention.

From the above results, it is clear that the sample based on the present invention has excellent spectral absorption characteristics, less decrease in color density when treated with fatigue bleaching solution, and excellent color image fastness. .

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, 5
at least one 1-naphthol cyan dye-forming coupler having a monosubstituted amino group in the 2-position and at least one phenolic cyan dye-forming coupler having an arylureido group in the 2-position and a carbonamide group in the 5-position; A silver halide color photographic material characterized by containing.