JPH075647A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness and color reproduction performance and color image storage stability and to enhance color development density and sensitivity and processing stability by incorporating a specified compound and a specified coupler. CONSTITUTION:The color photographic sensitive material contains the compound represented by the formula; A1-(TIME)a-DI or A2-(TIME)a-DI and the acylacetamide type coupler represented by formula I and and/or the coupler represented by formula II or the like, and in the formulae, each of A1 and A2 is an atomic group to be allowed to release (TIME)a-DI by reaction with the oxidation product of an aromatic primary amine color developing agent and A1 has a diffusion-resistant group and A2 has not such a group; TIME is a timing group releasing DI after its release; DI is to be made a development inhibitor by its release, a is 1 or 2; R1 is a substituent; Q is a nonmetallic atomic group necessary to form a 3-, 4-, or 5-membered hydrocarbon ring or the like; each of X1 and X2 is alkyl, aryl, or the like; Y is an aryl or heterocyclic group; and Z is a group to be released when this coupler reacts with the oxidation product of a developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More particularly, it relates to a silver halide color photographic light-sensitive material having improved image quality, color image storability, color developability and processability.

[0002]

2. Description of the Related Art For silver halide color photographic light-sensitive materials, especially for color photographic light-sensitive materials for photography, research on high sensitivity, improvement of image quality such as graininess, sharpness, color reproducibility, improvement of color image storability, Development is progressing day and night, and user demand is high. With regard to image quality improvement, it is well known to use a development inhibitor releasing compound (DIR compound) as one of the methods, and it has been put to practical use. These compounds are, for example,
Research Disclosure,
Hereinafter, R. Abbreviated as D) No. VII-F of 307105
It is described in the section. Further, similar compounds according to the present invention are presented in, for example, U.S. Pat. No. 4,782,012, JP-B-63-776, and JP-A-4-204940.

Regarding the acylacetamide type coupler having a specific acyl group, European Patent No. 447,969A is disclosed.
And U.S. Pat. No. 5,118,599. The other coupler of the present invention is disclosed in European Patent Nos. 447,920A and 482,552A. Further, the coupler according to the present invention and the DIR
Regarding the combined use of compounds, European Patent No. 503658A
No. 5,134,96A.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The use of the DIR compound disclosed in 4940 in combination with the coupler described in the said patent, and European Patent Nos. 447,969A, 447,920A, 482,552A and US Pat. When the DIR compound described therein is used in combination with the coupler disclosed in 5,118,599, the image quality is improved, the color image fastness is improved,
Higher sensitivity is still unsatisfactory, and further improvement has been desired. Therefore, an object of the present invention is to improve the image quality such as sharpness and color reproducibility, to provide excellent color image storability, high color density and sensitivity, and to be excellent in processing stability. To provide the material.

[0005]

As a result of repeated studies for solving the above problems, the present inventors have found that the objects of the present invention can be achieved by the silver halide color photographic light-sensitive material described below. It was

(1) A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a compound represented by the following formula (I) or (II), And an acylacetamide-type coupler having an acyl group represented by the general formula (YI) shown in the following chemical formula 4 and / or a general formula (1) shown in the following chemical formula 5 or a general formula (2) shown in the following chemical formula 6 A silver halide color photographic light-sensitive material containing a coupler represented by: Formula (I) A _1- (TIME) _a -DI Formula (II) A _2- (TIME) _a -DI In the formula, A ₁ has a nondiffusible group and oxidizes an aromatic primary amine developer. Represents a group capable of leaving (TIME) _a -DI upon reaction with _a derivative, A ₂ has no diffusion-resistant group, and reacts with an oxidant of an aromatic primary amine developing agent to give (TIM
E) represents a group that leaves _a- DI, TIME represents a timing group that cleaves DI after leaving from A, DI represents a development inhibitor that is substantially deactivated after flowing out into a developer, and a represents Represents 1 or 2. two a when a is 2
IME represents the same or different.

General formula (YI)

[0008]

[Chemical 4]

In the formula, R ₁ represents a substituent, Q is a 3- to 5-membered hydrocarbon ring together with C, or 3 to 5 having at least one hetero atom selected from N, O, S and P in the ring.
It represents a group of non-metal atoms necessary for forming a 6-membered heterocycle.

General formula (1)

[0011]

[Chemical 5]

General formula (2)

[0013]

[Chemical 6]

In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, and Y represents an aryl group. Alternatively, Z represents a heterocyclic group, and Z represents a group which is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent.

(2) The photosensitive silver halide emulsion layer and /
Alternatively, the silver halide color photographic light-sensitive material according to (1), characterized in that the adjacent layer on the side closer to the support of the layer contains substantially non-photosensitive fine grain silver halide grains.

(3) The photosensitive silver halide emulsion layer has two or more red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers having different sensitivities, and the following (a) to (d) The silver halide color photographic light-sensitive material as described in (1), which satisfies all the conditions. (A) The photosensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (b) the most sensitive green-sensitive halogen. The silver halide emulsion layer (GH) and the most sensitive red-sensitive silver halide emulsion layer (RH) are the same as the above BH and B.
It is provided between the blue-sensitive silver halide emulsion layer (Bh) having a lower sensitivity than H, and (c) with respect to the Bh, on the side farther from the support, the red-sensitive, green-sensitive and blue having the lowest sensitivity. Sensitive silver halide emulsion layers (RL, GL and B, respectively)
L) is absent, and (d) a fine-grain halogen having a non-photosensitive layer adjacent to the side of the BH close to the support and being substantially non-photosensitive to the BH and / or the non-photosensitive layer. Contains silver halide grains.

The present invention will be described in detail below. First, the compounds represented by formula (I) and formula (II) will be described in detail.

When A ₁ and A ₂ represent a yellow image coupler residue, for example, pivaloyl acetanilide type,
Examples thereof include benzoylacetanilide type, malon ester type, carbamoylacetamide type, malon ester monoamide type, benzimidazolyl acetamide type or cycloalkanoyl acetamide type coupler residues. Further, US Pat. Nos. 5021332 and 50213.
It may be a coupler residue described in No. 30 or European Patent No. 421221A. When A ₁ and A ₂ represent magenta color image-forming coupler residues, examples thereof include 5-pyrazolone type, pyrazolobenzimidazole type, pyrazolotriazole type, pyrazoloimidazole type or cyanoacetophenone type coupler residues. When A ₁ and A ₂ represent a cyan image-forming coupler residue, examples include phenol type or naphthol type. Further, it may be a coupler residue described in US Pat. No. 4,746,602 and European Patent 249453A. Further, A ₁ and A ₂ may be coupler residues that leave substantially no color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and elution type coupler residues described in European Patent Nos. 443530A and 444501A.

Preferred examples of A ₁ and A _{2 in} the formulas (I) and (II) are the following formulas (Cp-1) and (Cp-
2), (Cp-3), (Cp-4), (Cp-5),
(Cp-6), (Cp-7), (Cp-8), (Cp-
9) or a coupler residue represented by (Cp-10). These couplers are preferred because of their high coupling speed.

[0020]

[Chemical 7]

[0021]

[Chemical 8]

The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group. In the above formula, when the coupler residue is A ₁ ,
R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R
_At least one of ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a nondiffusible group having a total number of carbon atoms of 8 to 40,
It is preferably selected to be 10 to 30, and in other cases, the total number of carbon atoms is preferably 15 or less. In the case of a bis-type, telomer-type or polymer-type coupler, any of the above substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon number may be out of regulation. The diffusion resistant group is a group which has a sufficiently large molecular weight in order to immobilize it in the layer to which the molecule is added.

In the above formula, when the coupler residue is A ₂ , R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ ,
The total number of carbon atoms contained in R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ and R ₆₃ is selected to be 0 to 15, preferably 0 to 10. Below, R _{51 to} R ₆₃ , b, d, e
And f will be described in detail. In the following, R ₄₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅
Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₃ . b is 0 or 1
Represents R ₅₄ represents a group having the same meaning as R _41, R ₄₁ CO
(R ₄₃ ) N-group, R ₄₁ SO ₂ (R ₄₃ ) N-group, R
₄₁ (R ₄₃ ) N-group, R ₄₁ S-group, R ₄₃ O-group, or R
_{45 (R 43) NCON (R} 44) - represents a group. R ₅₅ is R ₄₁
Represents a group having the same meaning as. R ₅₆ and R ₅₇ are each a group having the same meaning as R ₄₃ , R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CO (R
₄₃ ) N-group or R ₄₁ SO ₂ (R ₄₃ ) N-group.
R ₅₈ has the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CO (R} 43) N- group, R ₄₁ OCO
(R ₄₃ ) N-group, R ₄₁ SO ₂ (R ₄₃ ) N-group, R
₄₃ (R ₄₄ ) NCO (R ₄₅ ) N-group, R ₄₁ O-group, R ₄₁ S
Represents a -group, a halogen atom, or an R ₄₁ (R ₄₃ ) N-group. d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents. R ₆₀ represents a group having the same meaning as R ₄₃ . R ₆₁ represents a group having the same meaning as R ₄₃ . R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH-
Group, R ₄₁ OCONH- group, R ₄₁ SO ₂ NH- group, R
₄₃ (R ₄₄ ) NCONH-group, R ₄₃ (R ₄₄ ) NSO ₂ NH
-Group, R ₄₃ O- group, R ₄₁ S- group, halogen atom or R
₄₁ represents an NH-group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃
CO (R ₄₄ ) N-group, R ₄₃ (R ₄₄ ) NCO-group, R ₄₁ S
O ₂ (R ₄₃ ) N-group, R ₄₁ (R ₄₃ ) NSO ₂ -group, R ₄₁ S
O ₂ - group, R ₄₃ OCO- group, a halogen atom, a nitro group,
A cyano group, or R ₄₃ CO- group. e is 0 to 4
Represents the integer. When a plurality of R ₆₂ or R ₆₃ are present, they represent the same or different. f is 0 to 3
Represents the integer. When there are a plurality of R ₆₃ 's, they represent the same or different ones.

The definitions of an alkyl group, an aryl group and a heterocyclic group when the coupler residue is A ₁ are described above. The alkyl group has 1 to 32 carbon atoms, preferably 1
To 22 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Representative examples are methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, cyclohexyl, 2-ethylhexyl, 1,1,
Examples include 3,3-tetramethylbutyl, n-dodecyl, n-hexadecyl, or n-octadecyl. The aryl group is preferably substituted or unsubstituted phenyl having 6 to 20 carbon atoms, or substituted or unsubstituted naphthyl. The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to
The heterocyclic atom of 7 is a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring, preferably selected from a nitrogen atom, an oxygen atom or a sulfur atom. Representative examples of the heterocyclic group include 2-imidazolyl, 2-benzimidazolyl, morpholino, pyrrolidino, 1,2,4-triazol-2-yl group or 1-indolinyl.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CO (R ₄₈ ).
N-group, R ₄₇ (R ₄₈ ) NCO-group, R ₄₆ SO ₂ (R ₄₇ ) N
-Group, R ₄₇ (R ₄₈ ) NSO ₂ -group, R ₄₆ SO ₂ -group, R ₄₇
OCO- group, R ₄₇ CONHSO ₂ - group, R ₄₇ (R ₄₈₎ N
CONHSO ₂ — group, group having the same meaning as R ₄₆ , R
₄₇ (R ₄₈ ) N-group, R ₄₆ COO-group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined.

The definition of an alkyl group, an aryl group and a heterocyclic group when the coupler residue is A ₂ is described above. The alkyl group has 1 to 12 carbon atoms, preferably 1
~ 8 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. Typical examples are methyl, cyclopropyl, isopropyl,
n-butyl, t-butyl, i-butyl, t-amyl, cyclohexyl, 2-ethylhexyl, or 1,1,
3,3-tetramethylbutyl may be mentioned. The aryl group is phenyl having 6 to 10 carbon atoms, preferably substituted or unsubstituted. The heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms, preferably selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, preferably a 3-membered to 8-membered ring. is there. Representative examples of the heterocyclic group include 2-imidazolyl, 2-benzimidazolyl, morpholino, pyrrolidino, 1,2,4-triazol-2-yl group or 1-indolinyl.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CO (R ₄₈ ).
N-group, R ₄₇ (R ₄₈ ) NCO-group, R ₄₅ SO ₂ (R ₄₇ ) N
-Group, R ₄₇ (R ₄₈ ) NSO ₂ -group, R ₄₆ SO ₂ -group, R ₄₇
OCO- group, R ₄₇ CONHSO ₂ - group, R ₄₇ (R ₄₈₎ N
CONHSO ₂ — group, group having the same meaning as R ₄₆ , R
₄₇ (R ₄₈ ) N-group, R ₄₆ COO-group, cyano group or nitro group can be mentioned. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined. In the present invention,
Compounds of formula (II) are preferred.

Next, the development inhibitor represented by DI will be described. Examples of the development inhibitor represented by DI include US Pat. Nos. 4,477,563, 5,021,331 and 4,
937179, 5,400,677, European Published Patent (EP) 336411A, 436109A,
No. 440466A, No. 446863A, No. 4479
21A, 451526A, 458315A,
Development inhibitors such as those described in U.S. Pat. Nos. 4,842,422A or 4,883,10A are included. Particularly preferably tetrazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-thiadiazolylthio, 1- (or 2
-) Benzotriazolyl, 1,2,4-triazole-
1- (or 4-) yl, 1,2,3-triazole-
1-yl, 1- (or 2-) tetrazolyl, 2-benzothiazolylthio, 2-benzimidazolylthio and derivatives thereof are included. DI has an inhibitory effect on development after cleavage from (TIME) _a , and a part of it flows out from the photographic layer into the developing solution. DI that has flowed into the developing solution is decomposed and the development inhibiting effect is substantially lost. The half-life of decomposition is 30 seconds to 2
The time is preferably 2 minutes to 1 hour. The decomposition reaction is alkali hydrolysis, decomposition by reaction with a chemical species (such as hydroxylamine) contained in the developer, or an adsorption group (D
Deactivation by a substitution reaction of a mercapto group contained in I) is typical. Particularly preferably, at least one of the substituents contained in DI has an ester bond.
Examples of DI include the following.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

Next, the group represented by TIME will be described. The group represented by TIME is A ₁ or A ₂ during development processing.
Any linking group capable of cleaving DI after further cleavage may be used. For example, US Pat.
Group utilizing the cleavage reaction of hemiacetal described in No. 96, No. 4652516 or No. 4698297,
Timing groups for causing a cleavage reaction utilizing the intramolecular nucleophilic substitution reaction described in U.S. Pat. Nos. 4,248,962, 4,847,185, 4,912,028 or 4,857,440, U.S. Pat. Nos. 4,409,323, 503.
No. 4311, No. 5055385 or No. 44218.
No. 45, a timing group for causing a cleavage reaction by utilizing an electron transfer reaction, a group for causing a cleavage reaction by utilizing an iminoketal hydrolysis reaction as described in US Pat. No. 4,546,073, or West German Patent 262
Examples thereof include a group capable of causing a cleavage reaction by utilizing the hydrolysis reaction of an ester described in No. 6317. Two TI
Examples of when MEs are connected (when a is 2) are U.S. Pat. Nos. 4,861,701, 5,026,628 and 50,
21322, European Published Patent (EP) No. 4992
79A and 438129A. TIME may also be a timing group that releases two DIs, examples of which include the timing groups described in EP-A-464612A. TIME binds to A ₁ or A _{2 at} a heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom. In the present invention,
The group represented by TIME is preferably a timing group which causes a cleavage reaction utilizing an electron transfer reaction along a conjugated system.

It is a preferred example that at least one TIME used in the formula (II) contains a diffusion resistant group. Total carbon number 8 to 40, preferably 10 to 22
Substituents are included. Preferred TIME includes the following formulas (T-1), (T-2) or (T-3). Formula (T-1) * -W- ( X = Y) j -C (R 21) R 22
-** Formula (T-2) * -W-CO-** Formula (T-3) * -W-LINK-E-** In the formula, * represents A ₁ in Formula (I) or Formula (II). Or represents a position to be bonded to A _2, and ** is DI or TIME
W represents an oxygen atom, a sulfur atom or> N—R ₂₃ , X and Y each represent a methine or nitrogen atom, and j represents 0, 1 or 2
And R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a substituent. Here, when X and Y represent a substituted methine, any substituent of each of the substituents, R ₂₁ , R ₂₂ and R ₂₃
It may be either a case where two substituents are linked to each other to form a cyclic structure (for example, a benzene ring or a pyrazole ring) or a case where no ring structure is formed. In Formula (T-3), E represents an electrophilic group, and LINK represents a linking group that sterically relates W and E so that they can undergo an intramolecular nucleophilic substitution reaction. The following are specific examples of TIME.

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

Specific representative examples of the compounds represented by formula (I) and formula (II) used in the present invention are shown below, but the invention is not limited thereto.

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

[0053]

[Chemical 29]

[0054]

[Chemical 30]

[0055]

[Chemical 31]

The compounds represented by the formula (I) or (II) of the present invention are described in US Pat.
7-151944, 58-162949, 60
-128444, 63-037350, JP-A-3.
-198048, 3-228048, 4-25
No. 1843, No. 4-278942, No. 4-279994
No. 3, No. 4-280247 and No. 4-313750, and the method described in the patents cited as examples of the development inhibitor and the patents cited as examples of the timing group, or similar methods. You can

The compounds represented by formula (I) and formula (II) of the present invention can be used in any of the light-sensitive silver halide emulsion layer and the non-light-sensitive layer. It is preferably a light-sensitive silver halide emulsion layer or a non-light-sensitive layer adjacent to the light-sensitive silver halide emulsion layer. The compound represented by formula (I) is preferably added to the red-sensitive emulsion layer. The portion of A ₁ represented by the formula (I) is represented by the formulas (Cp-6) and (C
Those represented by p-7) and (Cp-8) are preferable, and the formula (Cp-8) is particularly preferable. The compound represented by the formula (II) is preferably used in the green-sensitive emulsion layer and / or the blue-sensitive emulsion layer.

The amount used varies depending on the performance required of the light-sensitive material, but is 1 × 10 ⁻⁸ to 1 × per 1 m ^{2 of} the layer to be added.
It is 10 ^-2 mol. Preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻³
It is in the molar range. The amount is 1 × 10 ^{−6 to} 0.5 mol, and preferably 1 × 10 ⁻⁵ to 1 × 10, per mol of silver halide present in the light-sensitive silver halide emulsion layer to which the compound is added or the layer adjacent thereto. ^-1 mol range.

The compounds represented by the formulas (I) and (II) can be used in combination of two or more kinds in the same layer, or one kind can be used in two or more layers. Further, known DIR compounds can be used in combination depending on the performance required for the light-sensitive material. Examples of known DIR compounds include RD No. 17643, Item VII-F and No. 3071
No. 05, VII-F, Japanese Patent Laid-Open No. 57-15
1944, 57-154234, 60-184.
No. 248, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782,0.
12, European Patent Nos. 464,612A and 482,
Those described in Nos. 552A and 499,279A are preferable.

In the present invention, formula (I) and formula (II)
The compound represented by can be introduced into the light-sensitive material by applying various known dispersion methods described later. further,
It can be used by being mixed with or coexisting with various couplers and additives described later and introduced into the light-sensitive material.

Next, the acylacetamide type yellow coupler having an acyl group represented by the general formula (YI) used in the present invention will be described in more detail.

The acylacetamide type yellow coupler used in the present invention is preferably represented by the following general formula (YII).
Is represented by General formula (YII)

[0063]

[Chemical 32]

In the general formula (YII), R ₁ is a substituent except hydrogen atom, Q is a hydrocarbon ring having 3 to 5 members together with C or at least one hetero atom selected from N, S, O and P. R ₂ is a hydrogen atom, a halogen atom (F, Cl, Br, I), an alkoxy group, an aryloxy group, a non-metal atom group necessary for forming a 3- to 6-membered heterocycle containing An alkyl group or an amino group, R ₃ is a group capable of substituting on the benzene ring, X is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer (hereinafter referred to as a leaving group. , And k represents an integer of 0 to 4, respectively. However, when k is plural, plural R ₃ may be the same or different. R ₁ is preferably an organic residue containing no metal atom, and more preferably a hydrocarbon group which may have a substituent. In the following description of the acylacetamide type yellow coupler of the present invention, the halogen atom means F, Cl, Br or I.

Here, as an example of R ₃ , a halogen atom,
Alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, aryloxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a heterocyclic group. There are ring thio groups and halogen atoms.

In formula (YII), when the substituent is an alkyl group or contains an alkyl group, the alkyl group is linear, branched or cyclic, unless otherwise specified. Or an alkyl group which may contain an unsaturated bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl,
2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl,
Hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

In the general formula (YII), when the substituent is an aryl group or includes an aryl group, the aryl group may be a monocyclic or compound ring aryl group (which may be substituted) unless otherwise specified. For example, phenyl, 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl,
4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4-di-t-pentylphenyl, p-
Methanesulfonamidophenyl, 3,4-dichlorophenyl).

In the general formula (YII), when the substituent is a heterocyclic group or contains a heterocyclic ring, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. A 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom in the ring (for example, 2-furyl, 2-pyridyl, 4-pyridyl,
1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-2,4-imidazolidindione-3-yl) is meant.

The substituents preferably used in formula (YII) are described below.

In the general formula (YII), R ₁ is preferably a halogen atom, a cyano group, or a monovalent group having 1 to 30 total carbon atoms (hereinafter abbreviated as C number) which may be substituted (for example, C number). , An alkyl group, an alkoxy group, an alkylthio group) or a monovalent group having a C number of 6 to 30 (for example, an aryl group, an aryloxy group, an arylthio group), and the substituent thereof is, for example, a halogen atom, There are alkyl groups, alkoxy groups, nitro groups, amino groups, carbonamide groups, sulfonamide groups, and acyl groups. R ₁ may be a so-called ballast group. When Q together with C forms a heterocycle having at least one heteroatom selected from N, O, S and P in the ring, R ₁ is Q
May combine with to form a bicyclo ring.

In the general formula (YII), Q is preferably C together with C which may be substituted with any of 3 to 5 members.
A hydrocarbon ring of the number 3 to 30 or at least one N, S,
C number 2-3 containing a hetero atom selected from O and P in the ring
Represents a group of non-metal atoms necessary to form a 0 heterocycle. The ring formed by Q together with C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, oxane ring, 1,3-dioxolane ring, dioxane ( 1,3- or 1,4-) ring, thietane ring, thiolane ring, thiane ring, 1,3-dithiolane ring, dithiane (1,3- or 1,4-) ring, 1,4-
There are oxathian ring and pyrrolidine ring. Examples of the substituent are the same as those described for R ₃ , but they may be further substituted with an oxo group (═O), or the substituents may be bonded to each other to form a ring.

In the general formula (YII), R ₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 C atoms, an aryloxy group having 6 to 30 C atoms, or 1 to C atoms. It represents an alkyl group of 30 or an amino group having a C number of 0 to 30, and the substituent thereof is, for example, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group.

In the general formula (YII), R ₃ is preferably a halogen atom, which may have a C number of 1-3.
0 alkyl group, 6-30 C aryl group, 1-C number
30 alkoxy groups, C2-30 alkoxycarbonyl groups, C7-30 aryloxycarbonyl groups,
Carboxamide group having 1 to 30 C number, sulfonamide group having 1 to 30 C number, carbamoyl group having 1 to 30 C number, 0 number of C
To 30 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C
An ureido group having a number of 1 to 30, a sulfamoylamino group having a C number of 0 to 30, an alkoxycarbonylamino group having a C number of 2 to 30, a heterocyclic group having a C number of 1 to 30, an acyl group having a C number of 1 to 30, It represents an alkylsulfonyloxy group having a C number of 1 to 30, an arylsulfonyloxy group having a C number of 6 to 30, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group. , Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoyl Amino group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, Lumpur aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the general formula (YII), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is preferably meta or para to the acylacetamide group.

In the general formula (YII), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents a heterocyclic group, X is preferably an optionally substituted 5- to 7-membered monocyclic or condensed-ring heterocyclic group, for example, succinimide,
Maleinimide, phthalimide, diglycolimide,
Pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-
Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidin-4-one, these heterocycles being optionally substituted.

Examples of the substituents of these heterocycles include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group and arylthio group. Group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, There is a sulfamoylamino group.

When X represents an aryloxy group, X preferably represents an aryloxy group having a C number of 6 to 30,
It may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. The substituent of the aryloxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group,
An arylsulfonyl group or a cyano group is preferable.

Next, the substituents particularly preferably used in formula (YII) will be described.

R ₁ is particularly preferably an alkyl group having a C number of 1 to 30 (eg methyl, ethyl, n-propyl, n-).
(Butyl, isobutyl, n-octyl, n-dodecyl, phenoxymethyl, phenylthiomethyl, p-toluenesulfonylmethyl, benzyl, cyclohexylmethyl, methoxyethyl), most preferably an alkyl group having 1 to 4 C atoms. .

Q is particularly preferably a group of non-metal atoms whose ring formed with C forms a 3- to 5-membered hydrocarbon ring,
For example, it is an ethylene group, a trimethylene group, or a tetramethylene group, both of which may be substituted. Here, as the substituent, for example, an alkyl group, an alkoxy group,
There are aryl groups and halogen atoms.

Q is most preferably a substituted or unsubstituted ethylene group.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having a C number of 1 to 30. (For example, methoxy, ethoxy, methoxyethoxy, butoxy, hexadecyloxy), or an aryloxy group having a C number of 6 to 24 (for example, phenoxy group, p-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom. , A methoxy group or a trifluoromethyl group.

R ₃ is particularly preferably a halogen atom,
Cyano group, trifluoromethyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group or sulfamoyl group, most preferably chlorine atom, alkoxy group, alkoxycarbonyl group, sulfamoyl A group, a carbonamido group, or a sulfonamide group.

X is particularly preferably the following formula (Y-
1), (Y-2), or (Y-3).

[0086]

[Chemical 33]

In the formula (Y-1), Z is --O--CR _{4
(R 5) -, - S} -CR 4 (R 5) -, - NR 6 -CR
_{4 (R 5) -, -} NR 6 -NR 7 -, - NR 6 -C (= O)
_{-, - CR 4 (R 5} ) -CR 8 (R 9) - or -CR ₁₀ =
Represents CR ₁₁ −.

Here, R ₄ , R ₅ , R ₈ and R ₉ are hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or amino group. R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁
Represents a hydrogen atom, an alkyl group or an aryl group. R
₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). .

Among the heterocyclic groups represented by the formula (Y-1), particularly preferable ones are those in which Z in the formula (Y-1) is-.
_{O-CR 4 (R 5)} -, - NR 6 -CR 4 (R 5) - or -NR ₆ -NR ₇ - is a heterocyclic group which is. Formula (Y-1)
The C number of the heterocyclic group represented by is 2 to 30, preferably 4
-20, more preferably 5-16.

In the formula (Y-2), at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group,
A group selected from a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other is a hydrogen atom or an alkyl group. It may be a group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0-2. The C number of the aryloxy group represented by the formula (Y-2) is 6 to.
30, preferably 6 to 24, more preferably 6 to 15
Is.

In the formula (Y-3), W represents a nonmetallic atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N.
Here, the ring represented by formula (Y-3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group and an aryl group. , An amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (Y-3) is 2 to 30, preferably 2 to 24, more preferably 2 to 16.

X is most preferably a group represented by the formula (Y-1).

The coupler represented by the general formula (YII) is
The substituents R ₁ , R ₂ , R ₃ , Q or X may form a dimer or a multimer which is bonded to each other through a bond or a divalent or higher valent group. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

Specific examples of the yellow coupler represented by formula (YII) are shown below.

[0095]

[Chemical 34]

[0096]

[Chemical 35]

[0097]

[Chemical 36]

[0098]

[Chemical 37]

[0099]

[Chemical 38]

[0100]

[Chemical Formula 39]

[0101]

[Chemical 40]

[0102]

[Chemical 41]

[0103]

[Chemical 42]

[0104]

[Chemical 43]

[0105]

[Chemical 44]

[0106]

[Chemical formula 45]

[0107]

[Chemical formula 46]

[0108]

[Chemical 47]

The yellow coupler represented by the general formula (YII) can be synthesized by a conventionally known synthesis method, for example, a European patent application (E
P) 447969A, US Pat. No. 5,118,59
It can be synthesized by the method described in No. 9.

The coupler represented by formula (YII) can be used in any layer in the light-sensitive material. That is, any of a photosensitive layer (blue-sensitive emulsion layer, green-sensitive emulsion layer, red-sensitive emulsion layer) and a non-photosensitive layer (for example, protective layer, yellow filter layer, intermediate layer, antihalation layer) can be used. In particular, it is preferably used in a blue-sensitive emulsion layer or a non-light-sensitive layer adjacent thereto.

[0111] The preferred amount of the coupler represented by Formula (YII) is 0.05 to 5.0 mmol / m ^2, more preferably from 0.1 to 2.0 mmol / m ^2.

When the coupler represented by formula (YII) is used in the photosensitive layer, the preferable molar ratio of the coupler to silver halide is in the range of 1: 0.1 to 1: 200, more preferably. It is 1: 2-1: 150. Also,
When used in the non-photosensitive layer, the molar ratio of the adjacent silver halide emulsion layers to the silver halide is preferably 1: 2 to 2.
It is 1: 200.

The coupler represented by the general formula (YII) is
Of course, they may be used alone or in combination with other yellow couplers (for example, benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers).

In the present invention, the coupler represented by the general formula (YII) exhibits high color-forming property and excellent color image fastness, but has excellent spectral absorption characteristics, in particular, small spectral absorption on the long wavelength side (green light region). Shows that excellent color reproducibility is provided and further sharpness is improved.

Further, in the present invention, the coupler represented by the general formula (YII) is prepared by applying an oil-in-water dispersion method to prepare a fine emulsified dispersion using a high-boiling point organic solvent described below and introducing it into a light-sensitive material. At this time, even if the amount of the high boiling point organic solvent with respect to the coupler is reduced, it has excellent performance of exhibiting high color development. Therefore, this coupler is preferably on the side farther from the support of the color photosensitive material for photographing (the side closer to the incident light).
Is used for the blue-sensitive layer, which contributes to the reduction of the film thickness and advantageously acts on the sharpness of the photosensitive layer on the side closer to the support.

Next, the general formula (1) shown in the above "Chemical formula 2" and the general formula (2) shown in the above "Chemical formula 3" of the present invention.
The coupler represented by will be described in detail.

When X ₁ and X ₂ represent an alkyl group, it is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl,
Examples thereof include i-butyl, dodecyl, and 2-hexyldecyl.

When X ₁ and X ₂ represent a heterocyclic group, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. It is a 3- to 12-, preferably 5- or 6-membered, saturated or unsaturated, substituted or unsubstituted, or monocyclic or condensed-ring heterocyclic group containing at least one or more. Examples of the heterocyclic group include 3-pyrrolidinyl,
1,2,4-triazol-3-yl, 2-pyridyl,
4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl,
2,4-dioxo-1,3-imidazolidin-5-yl or pyranyl can be mentioned.

When X ₁ and X ₂ represent an aryl group, they represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl.

When X ₃ represents a nitrogen-containing heterocyclic group formed with> N-, the heterocyclic group has 1 to 20 carbon atoms,
It is preferably 1 to 15, and may be, for example, an oxygen atom or a sulfur atom in addition to a nitrogen atom as a hetero atom, and is a substituted or unsubstituted, saturated or unsaturated 3- to 12-membered ring, preferably 5- or 6-membered ring. It is a saturated or monocyclic or condensed-ring heterocyclic group. Examples of this heterocyclic group are pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinolin-1-yl, 1-imidazolidinyl, 1
-Pyrazolyl, 1-pyrrolinyl, 1-pyrazolidinyl,
2,3-dihydro-1-indazoline, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl are mentioned.

When X ₁ and X ₂ each represent an alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ with> N- has a substituent, The following are mentioned as an example of those substituents. Halogen atom (for example, fluorine, chlorine), alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, methoxycarbonyl, hexadecyloxycarbonyl), acylamino group (having 2 to 2 carbon atoms).
30, preferably 2-20. For example, acetamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonamide, hexadecylsulfonamide) , Benzenesulfonamide), carbamoyl group (having 1 to 3 carbon atoms)
0, preferably 1-20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 2 carbon atoms).
0. For example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 0 to 10 carbon atoms)
30, preferably 1-20. For example, N-butylsulfamoyl, N-hexadecylsulfamoyl, N-3-
(2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfamoyl), an alkoxy group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, methoxy, hexadecyloxy, iso Propoxy), aryloxy groups (C6-20, preferably 6-10.
For example, phenoxy, 4-methoxyphenoxy, 3-t-
Butyl-4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (C7-21, preferably 7-11. For example, phenoxycarbonyl), N-acylsulfamoyl group (C2-30, preferably 2-2).
20. For example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxycarbonyl. Amino group (2 carbon atoms
-30, preferably 2-20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 1 carbon atoms).
30, preferably 1-20. For example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), and ureido group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, N-
Phenyl ureido, N-hexadecyl ureido), aryl group (C6-20, preferably 6-10. For example, phenyl, naphthyl, 4-methoxyphenyl), heterocyclic group (C1-20, preferably 1-). 10. As a hetero atom, for example, at least one or more of nitrogen, oxygen or sulfur is contained and has 3 to 12, preferably 5 or 6 membered ring,
Single ring or fused ring. For example, 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl group (having 1 to 30 carbon atoms) ,
Preferably 1 to 20 straight chain, branched or cyclic, and saturated or unsaturated alkyl, such as methyl, isopropyl, cyclopropyl, t-octyl, cyclopentyl, s-butyl, 2-hexyldecyl), acyl group (number of carbon atoms) 2 to 30, preferably 2 to 20. For example, acetyl, benzoyl), an acyloxy group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (having 6 to 20 carbon atoms, Preferably 6 to 10. For example, phenylthio, naphthylthio, a sulfamoylamino group (having 0 to 30 carbon atoms, preferably 0 to 20. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenyl. Sulfamoylamino) or N-sulfonylsulfamoyl group (having 1 carbon atom 30, preferably from 1 to 20. For example N- mesyl sulfamoyl, N- ethane acylsulfamoyl, N- dodecane acylsulfamoyl, N- hexadecane sulfonylsulfamoyl) is Ageraru. The above substituents may further have a substituent.
Examples of the substituent include the substituents mentioned here.

Preferred substituents among the above are an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group. Is mentioned.

When Y represents an aryl group in the general formulas (1) and (2), Y has 6 to 20 carbon atoms, preferably 6 carbon atoms.
10 to 10 substituted or unsubstituted aryl groups. Phenyl and naphthyl groups are typical examples.

In formulas (1) and (2), when Y represents a heterocyclic group, Y has the same meaning as described above when X ₁ or X ₂ represents a heterocyclic group.

When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include, for example, X ₁
The examples of the substituents having a substituent include the substituents listed above. Preferred examples of the substituent of Y include:
One of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino group, N-
This is when it is a sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

A particularly preferred example of Y is a phenyl group in which at least one substituent is in the ortho position.

The group represented by Z in the general formulas (1) and (2) may be any conventionally known coupling-off group. Preferable Z is a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or a halogen atom. Can be mentioned. These leaving groups are non-photographic useful groups or photographically useful groups or precursors thereof (eg, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, developing agent oxidation agents). Body scavenger, fluorescent dye, developing agent or electron transfer agent).

When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat. No. 4,24
8,962, 4,409,323, 4,43
8,193, 4,421,845, 4,61
8,571, 4,652,516, 4,86
1,701, 4,782,012, 4,85
7,440, 4,847,185, 4,47
7,563, 4,438,193, 4,62
8,024, 4,618,571, 4,74
1,994, European Published Patent No. 193389A
No. 348139A or No. 272573A, the photographically useful group or a leaving group for releasing the group (for example, a timing group) is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, the nitrogen-containing heterocyclic group has 5 to 6 members and has 1 to 15, preferably 1 to 10 carbon atoms. It is preferably a cyclic, substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino, 1,2,4-triazol-2-yl,
1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-2,4-
Dione-3-yl, oxazolidin-2,4-dione-
3-yl, 1,2,4-triazolidine-3,5-dione-4-yl, imidazolidin-2,4,5-trion-3-yl, 2-imidazolinone-1-yl, 3,5-
Examples include dioxomorpholino or 1-yldazoline. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Preferred substituents include one alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group, acylamino group, sulfonamide group, aryl group, nitro group,
This is when it is a carbamoyl group, a cyano group or a sulfonyl group.

When Z represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group,
Examples thereof include a halogen atom, a carbamoyl group, a nitro group, a cyano group and an acyl group.

When Z represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, preferred substituents are when at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group.

When Z represents a heterocyclic oxy group, the heterocyclic group moiety has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group containing 3 to 12 or more, preferably 5 or 6-membered rings. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, or a furyloxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, preferable substituents include one alkyl group, aryl group, carboxyl group, alkoxy group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group,
Alkylthio group, acylamino group, sulfonamide group,
When it is a nitro group, a carbamoyl group, or a sulfonyl group.

When Z represents a heterocyclic thio group, the heterocyclic group moiety has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having 3 to 12, preferably 5 or 6 membered rings. Examples of the heterocyclic thio group include tetrazolylthio group, 1,3,4-thiadiazolylthio group, 1,3,4-
Examples thereof include an oxadiazolylthio group, a 1,3,4-triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, and a 2-pyridylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is at least one of an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylthio group, acylamino group, sulfonamide group,
When it is a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z represents an acyloxy group, the acyloxy group preferably has 6 to 10 carbon atoms and is a monocyclic ring or a condensed ring. It is a substituted or unsubstituted arylacyloxy group or a substituted or unsubstituted alkylacyloxy group having 2 to 30, preferably 2 to 20 carbon atoms. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

When Z represents a carbamoyloxy group, this carbamoyloxy group is an alkyl, aryl, heterocycle, substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example N,
Mention may be made of N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

When Z represents an alkylthio group, the alkylthio group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Which are linear, branched or cyclic, saturated or unsaturated, and substituted or unsubstituted alkylthio groups. When it has a substituent, examples of the substituent include the above-mentioned X.
Examples thereof include the substituents enumerated as the substituents which the group represented by ₁ may have.

Next, a particularly preferable range of the couplers represented by the general formulas (1) and (2) will be described below.

The group represented by X ₁ in the general formula (1) is preferably an alkyl group. Particularly preferably, it is an alkyl group having 1 to 10 carbon atoms.

The group represented by Y in the general formulas (1) and (2) is preferably an aryl group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. As the explanation of the substituent, those enumerated as the substituents which may be possessed when Y is an aryl group can be mentioned.
The example of a preferable substituent is also the same.

The group represented by Z in the general formulas (1) and (2) is preferably a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aryloxy group,
A 5- or 6-membered heterocyclic oxy group or a 5- or 6-membered heterocyclic thio group can be mentioned.

In the coupler represented by the general formula (1) or (2), the preferred coupler is the following general formula (3),
It is a coupler represented by (4) or (5).

[0142]

[Chemical 48]

In the formula, Z has the same meaning as described in the general formula (1), X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aryl group, and Ar represents at least one substituent at the ortho position. Represents a phenyl group having, X ₆ is -C
(R ₁ R ₂₎ represents an organic residue forming a -N <with a nitrogen-containing Hajime Tamaki (monocyclic or condensed), X ₇ is -C (R ₃₎
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocycle or condensed ring) together with ═C (R ₄ ) —N <, and R ₁ , R ₂ , R ₃
And R ₄ represents a hydrogen atom or a substituent.

Detailed description and preferable ranges of the groups represented by X _{4 to} X ₇ and Z in the general formulas (3) to (5) can be found in the explanations given in the general formulas (1) and (2). It has the same meaning as the description of the corresponding group. When R _{1 to} R ₄ represent a substituent, the examples of the substituent that X ₁ may have are listed.

Particularly preferred couplers in the above general formula are the couplers represented by the general formula (4) or (5).

The couplers represented by the general formulas (1) to (5) are represented by X _{1 to} X ₇ , Y, Ar, R _{1 to} R ₄ and Z, and are bis or divalent or higher groups. Dimers or higher multimers (eg telomers or polymers) may be formed which are linked together via In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

The couplers represented by the general formulas (1) to (5) are preferably diffusion resistant couplers. The diffusion-resistant coupler is a coupler having a group (diffusion-resistant group) in the molecule that increases the molecular weight sufficiently in order to immobilize the molecule in the added layer. As the diffusion resistant group, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is usually used. These diffusion resistant groups may be substituted in any of the molecules, or may have a hetero group.

Specific examples of the couplers and yellow couplers represented by the general formulas (1) to (5) are shown below, but the invention is not limited thereto.

[0149]

[Chemical 49]

[0150]

[Chemical 50]

[0151]

[Chemical 51]

[0152]

[Chemical 52]

[0153]

[Chemical 53]

[0154]

[Chemical 54]

[0155]

[Chemical 55]

[0156]

[Chemical 56]

[0157]

[Chemical 57]

[0158]

[Chemical 58]

[0159]

[Chemical 59]

The chemical formula YB-24 and the chemical formula 57
YB-25 in Chemical formula 58, YB-29 and YB-30 in Chemical formula 58 and YB-31, YB-3 in Chemical formula 59
In 2 and YB-33, “}” indicates that the substituent is substituted at the 5- or 6-position of the benzotriazolyl group.

The yellow couplers represented by the general formulas (1) to (5) used in the present invention are described in European Patent 447,
It can be synthesized according to the method described in No. 920A and No. 482,552A.

In the present invention, the yellow couplers represented by the general formulas (1) to (5) are 1.0 to 1.0 × 1 per 1 mol of the photosensitive silver halide coated on the photosensitive material.
It can be used in the range of 0 ^-3 mol. Preferably,
It is 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol.

In the present invention, when the yellow couplers represented by the general formulas (1) to (5) are used as the main coupler, it is preferably added to the blue-sensitive silver halide emulsion layer or the adjacent non-photosensitive layer. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

In the present invention, the yellow couplers represented by the general formulas (1) to (5) may be used in combination of two or more kinds, or may be used in combination with other known couplers.

In the present invention, the couplers represented by the general formulas (1) to (5) can be prepared by various known dispersion methods.
It can be incorporated into a color light-sensitive material.

In the oil-in-water dispersion method, which is one of the known dispersion methods, a low-boiling organic solvent (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol) is used to coat a fine dispersion and dry it. A method in which the low boiling point organic solvent does not substantially remain in the film can be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used. The ratio of the couplers represented by the general formulas (1) to (5) to these high boiling point organic solvents can be in a wide range, but 1 g of the coupler can be used.
The range is 5.0 or less per weight ratio. Preferably 0
To 2.0, and more preferably 0.01 to 1.0.

The latex dispersion method described below can also be applied.

Further, various couplers and compounds described later can be mixed or used together.

In using the acylacetamide type coupler having an acyl group represented by the above general formula (YI) and / or the coupler represented by the general formula (1) or the general formula (2) of the present invention, the following general formula is used. It is preferable to use the compound represented by (B) in combination.

General formula (B) A- (L ₁ ) _k -Z A represents a group which cleaves (L ₁ ) _k -Z by reacting with an oxidized product of a developing agent, and L ₁ is a bond with A. Represents a group capable of cleaving Z, and k represents 0 or 1, and Z represents a mercapto compound residue.

Next, the general formula (B) will be described.

In the general formula (B), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (eg, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (eg 5-pyrazolone type, pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
No. 4,001, such as a pyrazolopyrimidine type coupler residue) and a colorless coupler residue (for example, an indanone type or acetophenone type coupler residue). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-2.
30135, 62-251746, 61-27.
8852, U.S. Pat. Nos. 3,364,022 and 3,
379,529, 3,639,417, 4,6
84,604 or J.Org.Chem., 29,588 (1
964).

In the general formula (B), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A of the compound represented by the general formula (B), and the ** mark represents the position of bonding with Z. General formula (T
-1) * - (W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, the R ₁₁ and R ₁₂ is a hydrogen atom or a substituent R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups represented by the following "Chemical Formula 60".

[0176]

[Chemical 60]

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, * mark and ** mark represent the same meaning as described for general formula (T-1), and Nu represents a nucleophilic group. Represents an example of a nucleophilic species such as an oxygen atom or a sulfur atom, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu and cleaving the bond with the ** mark. Represents a linking group that is sterically related so that it can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) include those represented by the following "Chemical formula 61" and "Chemical formula 62".

[0178]

[Chemical formula 61]

[0179]

[Chemical formula 62]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
9737, 58-209738 and the like,
It is a group represented by the general formula (T-3) represented by the following "Chemical Formula 63".

[0181]

[Chemical formula 63]

In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). However, R ₁₁ and R ₁₂ may be bonded to each other to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1.
When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Further, t represents 1 or 2, t is two when the 2 - _{[Z 1 (R 11) x =} Z 2 (R 12) y ] - may be the same or different. Also, -CH ₂ adjacent to ** mark
The -group may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.

The following "Chemical 64" to "Chemical 67" (T-
Specific examples of 3) will be given.

[0184]

[Chemical 64]

[0185]

[Chemical 65]

[0186]

[Chemical formula 66]

[0187]

[Chemical formula 67]

(4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, the following groups are the linking groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General formula (T-4) * -OCO-** General formula (T-5) * -SCS-** (5) Group utilizing cleavage reaction of imino ketal For example, described in U.S. Pat. No. 4,546,073. It is a certain linking group, and is represented by the general formula (T-
It is a group represented by 6).

[0189]

[Chemical 68]

In the formula, *, ** and W represent the general formula (T
-1) has the same meaning as described above, and R ₁₄ is R
Has the same meaning as ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following "Chemical Formula 69".

[0191]

[Chemical 69]

(6) A compound that becomes a coupler residue or a redox group after being cleaved from A. For example, those represented by B in the general formula (I) of JP-A No. 63-214752, more preferably a redox group. In the general formula (B), L ₁ is preferably one represented by (T-1) to (T-5), particularly preferably (T-1) (T-3) and (T-4). is there.

The group represented by Z in the general formula (B) is, for example, US Pat. No. 3,893,858,
British Patent No. 1138842, JP-A-53-14
Various mercapto compounds described in JP-A No. 1623, compounds having a disulfide bond as described in JP-A No. 53-95630, JP-B No. 53-
A thiazolidine derivative as described in JP-A-9854, an isothiourea derivative as described in JP-A-53-94927, and JP-B-45-8506.
Thiourea derivatives as described in JP-B-49-26586, thioamide compounds as described in JP-A-49-42349, JP-A-55-2650
No. 6, dithiocarbamate salts, and arylene diamine compounds as described in US Pat. No. 4,552,834. These compounds, in substitutable hetero atom contained in the molecule of the general formula A- in _{(B) (L 1) k} - as preferred examples for binding.

The group represented by Z is preferably a group represented by the following general formula (V), (VI) or (VII).

[0195]

[Chemical 70]

In the formula, * indicates A- (L₁)_kPosition to connect with
And R₃₁Is 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms
Represents a valent aliphatic group, R₃₂Is R₃₁Charcoal, which has the same meaning as
Divalent aromatic group having a prime number of 6 to 10 or 3 to 8 members
A ring, preferably a 5- or 6-membered divalent heterocyclic group
Represent, X₁Is -O-, -S-, -COO-, -SO
₂-, -NR₃₃-, -NR₃₃-CO-, -NR₃₃-SO₂
-, -S-CO-, -CO-, -NR₃₃-COO-,-
N = CR₃₃-, -NR₃₃CO-NR₃₄-Or-NR
₃₃SO₂NR₃₄Represents a group, X₂Is an aromatic with 6 to 10 carbon atoms
Represents an aromatic group, X ₃Is at least one bound to S
A 3- to 8-membered ring having carbon atoms in the ring, preferably
Represents a 5- or 6-membered heterocyclic group, Y₁Is carbo
Xyl group or its salt, sulfo group or its salt,
Droxyl group, phosphonic acid group or its salt, amino group
(May be substituted with an aliphatic group having 1 to 4 carbon atoms), -N
HSO₂-R₃₅Or-SO₂NH-R₃₅Represents a group
(Here, salt means sodium salt, potassium salt or anion.
Means a monium salt, etc.), Y₂Is Y₁As explained in
Represents a group having the same meaning or a hydrogen atom, and r is 0 or
1 represents, i represents an integer of 0 to 4, and j represents 1
Represents an integer of 4, and k represents an integer of 0 to 4.
You However, j Y₁Is R₃₁-{(X₁)_r-R₃₂}_iAnd
And X₂-{(X₁)_r-R₃₂}_iAt the replaceable position of
Combine, k Y₁Is X₃-{(X₁)_r-R₃₂}_iCan be replaced
When the number of k and j is two or more,
k and j Y₁Represent the same or different
, And when i is plural, i (X₁)_r-R₃₂Are the same
Or represents something different. Where R₃₃, R₃₄And R₃₅
Are each a hydrogen atom or 1 to 8 carbon atoms, preferably 1 to 5
Represents an aliphatic group of. R₃₁Through R₃₅Represents an aliphatic group
When it is chained or cyclic, linear or branched, saturated
It may be unsaturated, substituted or unsubstituted
Yes. Unsubstituted is preferable, but examples of the substituent include halogen.
Atom, an alkoxy group (eg, methoxy, ethoxy)
A), an alkylthio group (eg, methylthio, ethylthio)
E).

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. Examples of the substituent include those enumerated above as the aliphatic group substituents.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₃₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. For example, pyridine, imidazole, piperidine, oxirane,
Mention may be made of sulfolane, imidazolidine, thiazepine or pyrazole. Examples of the substituent include those enumerated above as the aliphatic group substituents.

Specific examples of the group represented by the general formula (V) include the followings.

[0200]

[Chemical 71]

[0201]

[Chemical 72]

Specific examples of the group represented by the general formula (VI) include the followings.

[0203]

[Chemical formula 73]

Specific examples of the group represented by the general formula (VII) include the following.

[0205]

[Chemical 74]

[0206]

[Chemical 75]

The specific examples of the compounds represented by formula (B) preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0208]

[Chemical 76]

[0209]

[Chemical 77]

[0210]

[Chemical 78]

[0211]

[Chemical 79]

[0212]

[Chemical 80]

[0213]

[Chemical 81]

[0214]

[Chemical formula 82]

[0215]

[Chemical 83]

[0216]

[Chemical 84]

[0217]

[Chemical 85]

[0218]

[Chemical 86]

[0219]

[Chemical 87]

Others, Research Disclosure I
tem No. 24241, No. 11449, JP-A-61-
201247, 63-106749, 63-121843, 63-121844, 63-2144752 and 2-93.
The compounds described in Japanese Patent No. 454 are also used in the same manner.

The compound represented by the general formula (B) used in the present invention can be easily synthesized based on the description in the above patent specifications.

The compound of formula (B) may be added to any layer, but it is preferably added to the light-sensitive silver halide emulsion layer or a layer adjacent thereto. In the present invention, it is particularly preferable to use the acylacetamide coupler having an acyl group represented by the general formula (YI) and / or the coupler represented by the general formula (1) or (2). The addition amount of the compound of the general formula (B) varies depending on the structure of the compound, but is in the range of 1 × 10 ^{−4 to} 1.0 g / m ² . It is preferably in the range of 5 × 10 ⁻⁴ to 1 × 10 ⁻¹ g / m ² , and particularly preferably in the range of 1 × 10 ^{−3 to} 5 × 10 ⁻² g / m ² .

The acylacetamide type coupler having an acyl group represented by the general formula (YI) and / or the coupler represented by the general formula (1) or (2) and the compound represented by the general formula (B) of the present invention. The effect of suppressing the variation of photographic properties such as sensitivity and color density in color development processing, particularly continuous (running) processing, is shown not only by improving the color reproducibility of the color image.

Next, the layer structure of the light-sensitive material of the present invention will be described.

The light-sensitive material of the present invention preferably has three light-sensitive layers: a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer. Further, for example, a yellow filter layer for reducing the blue sensitivity of the green-sensitive emulsion layer and the red-sensitive emulsion layer, or a same-color-sensitive layer for reducing color mixture during development between photosensitive layers having different color sensitivities. It may have a non-photosensitive layer such as an intermediate layer provided between the layers and an antihalation layer for preventing halation, and for improving color reproducibility, for example, US Pat. No. 4,663,271. , No. 4,70
5,744, 4,707,436, JP-A-62.
-160448 and 63-89850, a donor layer having a multi-layer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer is adjacent to the main photosensitive layer. Alternatively, they may be arranged close to each other.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541 and No. 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the farthest side from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H.

Further, as described in JP-B-55-34932, blue-sensitive layers / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, JP-A-56-25738 and 62-63.
As described in Japanese Patent No. 936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a middle layer in the lower layer. A silver halide emulsion layer having a lower photosensitivity than that of the silver halide emulsion layer may be disposed, and the photosensitivity may be sequentially decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In the present invention, various layer structures and layer arrangements can be selected as described above according to the purpose of each light-sensitive material.

The light-sensitive material of the present invention preferably has at least one of the above various layer structures and layer arrangements.
In a layer on the side close to the support adjacent to the photosensitive silver halide emulsion layer and / or the photosensitive silver halide emulsion layer,
It contains substantially non-photosensitive fine grain silver halide grains. This will be described in more detail.

Of the various layer configurations and layer arrangements described above,
Representative basic preferred examples are listed in Table-A below.

[0234]

[Table 1]

Typical basic layer structure shown in Table-A
In the layer arrangement, each color-sensitive layer is shown as a high-sensitivity and low-sensitivity two-layer structure, but three layers (for example, high sensitivity,
(Medium sensitivity, low sensitivity) or higher. In this case, for example, RH may be RH-1 and RH-2, and RL may be RL-1 and RL-2.
At this time, the low sensitivity layer, the medium sensitivity layer,
It is preferably arranged with the high-sensitivity layer. RH-1 and RH-
2, an intermediate layer M may be provided between RL-1 and RL-2, if necessary. Also, RL and R in Example 1 in Table-A
An intermediate layer M may be provided between H, GL and GH, and BL and BH. Furthermore, an intermediate layer may be provided between AH and RL or on the side of the YF close to the support or on the side far from the support, and these non-photosensitive layers including the protective layer may be two layers if necessary. The above can be provided adjacent to each other.

Explaining in accordance with the representative basic layer constitution / layer arrangement shown above, the photosensitive silver halide emulsion layer is B
H, BL, GH, GL, RH, RL, at least one of these photosensitive silver halide emulsion layers and / or a layer adjacent to the photosensitive silver halide emulsion layer and close to the support. It is preferable to contain substantially non-photosensitive fine grain silver halide grains.

The layers adjacent to the support, which are adjacent to the light-sensitive silver halide emulsion layer, including the layers adjacent to the support shown in Table A, are provided as necessary as described above. It also includes a non-photosensitive layer such as an intermediate layer capable of

In the present invention, the light-sensitive silver halide emulsion layer containing substantially non-light-sensitive fine silver halide grains is preferably a blue-sensitive emulsion layer (BH and BL in Table A) or a green-sensitive emulsion layer. It is the most sensitive layer (GH in Table-A) and the most sensitive layer (RH in Table-A) of the red-sensitive emulsion layers.
More preferably, it is a blue-sensitive emulsion layer (BH and B in Table-A).
L). Most preferred is the most sensitive layer of the blue-sensitive emulsion layers.

Further, the layer adjacent to the support adjacent to the photosensitive silver halide emulsion layer is preferably a non-photosensitive layer. The intermediate layer described above is more preferable, and the hydrophilic colloid layer containing no coupler or other compound is most preferable.

Next, the substantially non-photosensitive fine grain silver halide grains will be described.

In the present invention, substantially non-photosensitive fine grain silver halide grains have a substantial non-photosensitivity, which is 0.5 or more in log unit lower than the sensitivity of the lowest sensitive layer of the adjacent photosensitive silver halide layers. Means that. More preferably, it is lower than 1.0.

The substantially non-photosensitive fine grain silver halide grain in the present invention may be pure silver chloride, pure silver bromide, pure silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide. But,
Since it is preferable that these silver halide grains are not dissolved during development, it is desirable that the silver chloride content is low.
It is preferably 0 mol% or less. On the other hand, it is desirable that the content of silver bromide is high, and it is preferably 60 mol% or more. The silver iodide content is 40 mol% or less, preferably 10 mol% or less. Particularly, silver iodobromide grains having a silver iodide content of 10 mol% or less are preferable.

The particle size is not particularly limited, but is preferably 0.6 μm or less. More preferably 0.0
It is in the range of 4 to 0.4 μm. When the layer containing the substantially light-insensitive fine grain silver halide grains is a blue-sensitive emulsion layer, a blue-sensitive emulsion layer or a layer of the lowest sensitivity blue-sensitive emulsion layer, which is closer to the support, it is preferably 0. It is in the range of 0.08 to 0.25 μm. When the layer containing the substantially non-photosensitive fine grain silver halide grains is a green-sensitive emulsion layer, a green-sensitive emulsion layer or a layer of the lowest-sensitivity green-sensitive emulsion layer closer to the support, it is preferably 0.1 to When the content layer is in the range of 0.3 μm and the layer is on the side closer to the support of the red-sensitive emulsion layer, the red-sensitive emulsion layer or the red-sensitive emulsion layer having the lowest sensitivity, it is preferably 0.1 to 0. Four
It is in the range of μm. The substantially non-photosensitive fine grain silver halide grains used in the present invention can have a relatively wide grain size distribution, but it is preferable that they have a narrow grain size distribution, especially with respect to the weight or number of silver halide grains. It is preferable that the size of particles occupying 90% is within ± 40% of the average particle size.

The coating amount of the substantially non-photosensitive fine grain silver halide grain of the present invention is 0.03 to 5.0 g, and preferably 0.05 to 1.0 g per 1 m ³ . When the layer containing the substantially non-photosensitive fine grain silver halide grains is a non-photosensitive layer other than the photosensitive emulsion layer, the binder of this layer may be any hydrophilic polymer, but gelatin is particularly preferable. The binder amount is preferably less than 250 g per 1 mol of fine grain silver halide.

The substantially non-photosensitive fine grain silver halide grain used in the present invention can be prepared by a known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . As one of the simultaneous mixing methods, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Since this method has a narrow grain size distribution, it is preferable as a method for preparing substantially non-photosensitive fine grain silver halide grains used in the present invention.

The substantially non-photosensitive fine grain silver halide grain used in the present invention may have a regular crystal form such as a cube, an octahedron, a dodecahedron and a tetradecahedron, and may have a spherical or tabular shape. Particles having a crystal form such as Tabular grains having an aspect ratio of 2 or more are preferred.

The aspect ratio of the substantially non-photosensitive tabular fine grain silver halide grain used in the present invention means the ratio of the diameter to the thickness of the silver halide grain. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with an electron microscope. Therefore, an aspect ratio of 2 or more means that the diameter of this circle is twice or more the thickness of the particles.

The tabular silver halide grains used in the present invention have a grain size of not less than twice the grain thickness, more preferably 2 to 15 times, more preferably 3 to 10 times, particularly preferably 4 times. ~ 8 times. The proportion of tabular grains in the projected area of all substantially non-photosensitive silver halide grains is preferably 50% or more, more preferably 70% or more, and particularly preferably 85% or more.

The tabular silver halide emulsion used in the present invention can be prepared according to the reports of Cgnac and Chateau, and Duf.
Fin “Photographic Emulsio”
nChemistry ”(published by Focal Press,
New York 1966) pp. 66-72, and A. P. H. Trivelli, W.C. F. Smith edited "Phot. Journal" 80 (1940) 28
Although it is described on page 5, for example, JP-A-58-113
927, 58-113928, 58-1279.
It can be easily prepared by referring to the method described in No. 21.

The substantially non-photosensitive fine grain silver halide grain used in the present invention may have a halogen composition in which the inside and the surface of the grain are different, or may have a uniform halogen composition. The substantially non-photosensitive silver halide grains may contain, for example, cadmium ions, lead ions, zinc ions, iridium ions, rhodium ions, thallium ions, and iron ions as impurities.

The substantially non-photosensitive fine grain silver halide grain may be of a surface latent image type or an internal latent image type, and may have a fog nucleus inside.

The substantially non-photosensitive fine grain silver halide grains may be subjected to usual chemical sensitization, that is, sulfur sensitization, gold sensitization and reduction sensitization, but it is desirable to restrain the degree of chemical sensitization as much as possible. . In the present invention, an emulsion that is not chemically sensitized (so-called unripened) is preferable. The preparation method and shape of these silver halide grains will be described in more detail later.

The substantially non-photosensitive fine grain silver halide grain used in the invention may be spectrally sensitized. That is, known dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrene dyes and hemioxonol dyes may be included. Further, a desensitizing dye which has a large desensitization and is not preferable in a normal negative emulsion can be used.

The substantially non-photosensitive fine grain silver halide grains may contain known antifoggants and stabilizers. For example, azoles, heterocyclic mercapto compounds, thioketo compounds,
Antifoggants or stabilizers such as azaindenes, benzenethiosulfonic acids, benzenesulfinic acid can be added.

In the present invention, a dye may be added to the layer containing substantially non-photosensitive fine silver halide grains, or a dispersion of a slightly soluble synthetic polymer may be contained.

Thus, an acylacetamide type coupler having an acyl group represented by the general formula (YI) and /
Alternatively, at least one layer of the silver halide color photographic light-sensitive material of the present invention containing a coupler represented by the general formula (1) or the general formula (2) in at least one of the light-sensitive silver halide emulsion layers is sensitized. High sensitivity by containing substantially non-photosensitive fine grain silver halide grains in the photosensitive silver halide emulsion layer and / or the adjacent layer on the side close to the support which is adjacent to the photosensitive silver halide emulsion layer. Image quality (color reproducibility, sharpness) can be improved. Moreover, in the constitution of the present invention, the processability of the light-sensitive material is high.

The support of the silver halide color photographic light-sensitive material of the present invention may be any known support [for example, a film made of a semi-synthetic or synthetic polymer or a flexible support having a reflective layer provided on these films. Body (cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc.),
Paper laminated with α-olefin polymer or the like, flexible reflective support such as synthetic paper, glass, metal, pottery, etc.] can also be used. In the present invention, a transparent support preferably composed of a fiber-based polymer (eg cellulose acetate) and a polyester-based polymer (eg polyethylene terephthalate). In particular, diols [eg fatty acid diols (ethylene glycol, 1,4
-Butanediol, 1,4-cyclohexanediol, etc.), aromatic diol (hydroquinone, catechol, resorcin, etc.)] and dicarboxylic acid [eg, aliphatic dicarboxylic acid (succinic acid, maleic acid, sebacic acid, 1,4 -Cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic anhydride, etc.)] or a blend thereof, and having an average molecular weight of 1 × 10 ⁴ It is preferable that the glass transition point (Tg) is 90 ° C. or higher and 200 ° C. or lower in the range of up to 5 × 10 ⁵ . Examples of compounds of these polyester-based polymers that can be used as the support are shown below, but the invention is not limited thereto.

(Example of Compound) [(Inside of parentheses represents molar ratio) PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [ Terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. 2,6-NDCA / TPA / EG / BPA (50/50/75 / 25) Tg = 112 ° C. TPA / EG / BPA (100/50/50) Tg = 105 ° C. TPA / EG / BPA (100/25/75) Tg = 135 ° C. TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. Isophthalic acid (IPA) / paraphenylenedicarboxylic acid (PPDC) / TPA / EG (20/50/30/100) Tg = 95 ° C. NDCA / neopentyl glycol (NPG) / EG (100/70/30) Tg = 105 ° C. TPA / EG / biphenol (BP) (100/20/80) Tg = 115 ° C. parahydroxybenzoic acid (PHBA) ) / EG / TPA (200/100/100) Tg = 125 ° C. PEN / PET (60/40) Tg = 95 ° C. PEN / PET (80/20) Tg = 104 ° C. PAr / PEN (50/50) Tg = 142 ° C PAr / PCT (50/50) Tg = 118 ° C PAr / PET (60/40) Tg = 101 PEN / PET / PAr (50/25/25) Tg = 108 ℃

An ultraviolet absorber may be kneaded into these polyester polymer films for the purpose of preventing fluorescence and imparting stability with time. Further, dyes and pigments can be kneaded. Known conventional techniques can be used to provide a photographic layer or a back layer for use as a support. For example, chemical treatment, mechanical treatment, corona discharge treatment,
A surface activating treatment such as glow discharge treatment or a method of forming a photographic layer or a back layer by providing an undercoat layer after or without such surface activating treatment can be performed.
When an undercoat layer or a back layer is provided, known antistatic agents, lubricants, matting agents, surfactants,
Dyes, pigments, etc. can be contained as required.

Further, the silver halide color photographic light-sensitive material of the present invention may have a magnetic recording layer for recording various information. A known ferromagnetic material can be used. The magnetic recording layer is preferably used on the back surface of the support layer and can be provided by coating or printing. . Further, a space for optically recording may be provided in the photosensitive material for recording various information.

The silver halide in the photosensitive silver halide emulsion layer which can be used in the silver halide color photographic light-sensitive material of the present invention, couplers, other photographic additives and the like and their use, and color development treatment and For the treatment method, etc., see page 36, 3 of EP 482,552A.
Lines 0 to 37, 38; 37, 55 to 41, 32; 41, 40 to 45
Those described on page 25, line 25 can be used.

The silver halide color photographic light-sensitive materials of the present invention are described in Japanese Examined Patent Publication No. 2-032615 and Japanese Utility Model Publication No. 03-03978.
It can be applied to the film unit with a lens described in No. 4 or the like.

[0263]

【Example】

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye Coating amount is g / for silver halide and colloidal silver
The amount of silver in m ² units, the amount in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes. Indicated by.

First layer: antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 HBS-1 0.30 HBS-2 1.2 x 10 ^-2

Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, sphere equivalent diameter O.O7 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ⁻² Cpd-3 2.0 × 10 ⁻²

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A Silver coating amount 0.42 Silver iodobromide emulsion B Silver coating amount 0.40 Gelatin 1.90 ExS-1 6.8 × 10 ^-4 mol ExS-2 2.2 × 10 ^-4 mol ExS-3 6.0 × 10 ^-5 mol ExC-1 0.40 ExC-3 0.30 ExC-4 2.3 × 10 ^-2 Comparative coupler (A) 1.5 × 10 ^-2 HBS-
1 0.32

Fourth layer: Medium-sensitive red-sensitive emulsion layer Silver iodobromide emulsion C Silver coating amount 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ⁻⁴ mol ExS-2 1.5 × 10 ⁻⁴ mol ExS-3 4.5 × 10 ^{− 5} mols ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 Comparative coupler (A) 5.0 × 10 ^-3 HBS-1 8.0 × 10 ^-2 HBS- 4 5.0 x 10 ^-2

[0268] Fifth layer: high sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D silver laydown 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ^-4 mol ExS-2 9.0 × 10 ^-5 mol ExS-3 3.0 × 10 ^{- 5} mols ExC-2 8.5 × 10 ^-2 ExC-5 3.6 × 10 ^-2 ExC-6 1.0 × 10 ^-2 B-16 3.7 × 10 ^-2 HBS-1 0.12 HBS-2 6.0 × 10 ^-2 HBS-5 6.0 × 10 ^-2

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 HBS-1 8.0 × 10 ^-2

Layer 7: Low-sensitivity green emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ^-4 mol ExS-5 3.0 × 10 ^-4 mol ExS-6 1.5x10 ^-4 mol ExM-1 0.40 ExM-2 0.15 ExM-5 3.5x10 ^-2 Comparative coupler (B) 1.2x10 ^-2 HBS-1 0.20 HBS-3 2.5x10 ^-2 HBS-4 0.10

[0271] Eighth layer: middle sensitivity green-sensitive emulsion layer Silver iodobromide emulsion G silver laydown 0.57 Gelatin 0.45 ExS-4 5.2 × 10 ^-4 mol ExS-5 2.1 × 10 ^-4 mol ExS-6 1.1 × 10 ^{- 4} mol ExM-1 0.10 ExM-2 3.0 × 10 ^-2 ExM-3 3.5 × 10 ^-2 Comparative coupler (B) 8.5 × 10 ^-3 HBS-1 0.10 HBS-4 5.0 × 10 ^-2 HBS-3 8.0 × 10 ^-3

Ninth layer: intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2

[0273] Tenth layer: High speed green-sensitive emulsion layer Silver iodobromide emulsion H silver laydown 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ^-4 mol ExS-5 1.2 × 10 ^-4 mol ExS-6 1.2 × 10 ^{- 4} mol ExM-4 5.8 × 10 ^-2 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 HBS-1 0.20 HBS-5 5.0 × 10 ^-2

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

Twelfth layer: intermediate layer Gelatin 0.45 Cpd-3 0.10

Thirteenth layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol Comparative coupler (1) 0.60 Comparative coupler (B) 3.0 × 10 ^-2 B-32 5.0 x 10 ^-3 HBS-1 0.15 HBS-5 5.0 x 10 ^-2

14th layer: Medium speed blue sensitive emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ^-4 mol Comparative coupler (1) 0.22 Comparative coupler (B) 1.0 × 10 ^-2 B-26 1.0 x 10 ^-2 HBS-1 7.0 x 10 ^-2 HBS-4 3.0 x 10 ^-2

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, spherical equivalent diameter O.20 μm) Silver coating amount 0.20 Gelatin 0.36

16th layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ^-4 mol Comparative coupler (1) 0.21 B-32 2.0 × 10 ^-2 HBS- 1 7.0 x 10 ^-2 HBS-4 3.0 x 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS-1 1.0 × 10 ^-2 HBS-2 1.0 × 10 ^-2

[0281]

In addition to the above, the samples thus prepared were
1,2-benzisothiazolin-3-one (200 ppm average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. further,
B-4 to B-6, W-2 to W-4, F-1 to F-17, iron salts, lead salts, gold salts, platinum salts, iridium salts, rhodium salts and palladium salts are contained.

[0283]

[Table 2]

In Table-B, (1) Each emulsion was subjected to reduction sensitization at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. There is. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0285]

[Chemical 88]

[0286]

[Chemical 89]

[0287]

[Chemical 90]

[0288]

[Chemical Formula 91]

[0289]

[Chemical Formula 92]

[0290]

[Chemical formula 93]

[0291]

[Chemical 94]

[0292]

[Chemical 95]

[0293]

[Chemical 96]

[0294]

[Chemical 97]

[0295]

[Chemical 98]

[0296]

[Chemical 99]

[0297]

[Chemical 100]

[0298]

[Chemical 101]

[0299]

[Chemical 102]

Next, the comparative coupler (A) used in the third and fourth layers of the sample 101 was used as the comparative coupler (C) and the seventh coupler
Sample 102 was prepared by replacing the comparative coupler (B) used in each of the layers, the eighth layer, the thirteenth layer, and the fourteenth layer with the comparative coupler (D) in an equimolar amount. Sample 103 is sample 10
The comparative coupler (A) used in the third and fourth layers of No. 1 was added to the compound D-11 represented by the formula (I) of the present invention.
The comparative coupler (B) used in the layers and the eighth layer was added to the compound D-16 represented by the formula (II) of the present invention, the thirteenth layer and the first layer.
Samples were prepared by substituting the 4-layer comparative coupler (B) with the compound D-8 represented by the formula (I) of the present invention in equimolar amounts. Sample 104 is the thirteenth layer, the first of Sample 102.
The comparative coupler (1) used in the 4th and 16th layers is the coupler YB- represented by the general formula (2) of the present invention in the 13th layer.
9, a 14th layer was prepared by substituting a 1: 1 molar ratio mixture of YB-9 and a coupler Y-29 represented by the general formula (YI) for the 16th layer, and Y-29 was replaced by equimolar amounts to prepare samples. . Sample 105 is the same as Sample 104 except that the comparison coupler (1) of the thirteenth layer of Sample 103 is applied to YB-10 and the first coupler.
Samples were prepared by replacing the 4-layer comparative coupler (1) with a 1: 1 molar ratio mixture of YB-10 and Y-29 and the 16th layer comparative coupler (1) with Y-29 in equimolar amounts. . Comparative couplers (C) and (D) are shown in Formula 103.

[0301]

[Chemical 103]

Subsequently, the comparative coupler (A) used for the third layer and the fourth layer of Sample 101, the seventh layer, the eighth layer, the thirteenth layer,
The comparative coupler (B) used in the 14th layer and the comparative coupler (1) used in the 13th layer, the 14th layer and the 16th layer are represented by formulas (I), (II) and general formula (YI) of the present invention. Samples 106 to 122 were prepared by substituting the compounds represented by the general formulas (1) and (2), the coupler, and the comparative couplers (H) to (N) in equimolar amounts as shown in Table-C. Comparative couplers (H) to (N) are shown in Chemical formulas 104 and 105.

[0303]

[Table 3]

[0304]

[Table 4]

[0305]

[Table 5]

[0306]

[Table 6]

[0307]

[Chemical 104]

[0308]

[Chemical 105]

The produced samples 101 to 122 were subjected to the color development processing shown below, and the following performances were examined. (1) Photographic properties The samples 101 to 122 were subjected to gradation exposure of white light (4800 ° K) and subjected to color development processing. The treated sample was subjected to density measurement of B, G, and R colors, and its characteristic curve was obtained. From this characteristic curve, the minimum density +
The logarithmic value of the reciprocal of the exposure amount giving a density of 0.2 was calculated, and the relative value was calculated by setting the value of Sample 101 to 100. B
The values of the results of measuring the concentrations are shown in Table-D, where S _{B is} the G concentration, S _{G is} the G concentration, and S _R is the R concentration. Next, B, G, R3 of each sample
As the γ value of the color, the slope of the straight line connecting the two densities at the exposure amount point of log E = 1.5 from the exposure amount point giving the minimum density +0.3 to the high exposure amount side is γ, and these _Was determined as γ _WR , γ _WG , and γ _WB , and the relative γ value was calculated by setting Sample 101 to 1.00. Table-D shows the relative γ values at B concentration, G concentration, and R concentration. further,
Samples 101 to 122 were subjected to color development by exposing them with a B-G-R3 color separation filter, and the densities of these samples were measured, and the γ value was determined from the characteristic curve by the method described above. It was Γ
_R , γ _G , and γ _B are set, and the ratios of γ value, γ _WR , γ _WG , and γ _WB , which are obtained by applying the grayscale exposure of white light, are calculated for each sample, and the color reproducibility is evaluated as 1 The so-called multi-layer effect, which is one of the measures, was investigated, and the γ ratio of B concentration (γ _B /
γ _WB ), G concentration γ ratio (γ _G / γ _WG ) and R concentration γ ratio (γ _R / γ _WR ) are shown in Table-D. When the value is larger than 1.00, the layering effect is largely received and the color reproducibility is excellent.

(2) Color image storability The B, G and R densities of the samples obtained by subjecting the samples to color development processing by gradation exposure of white light were measured, and then these samples were stored at 60 ° C. and relative humidity. After storing at 70% for 5 weeks, perform density measurement again, and read the density after storage of the exposure dose point that gives the minimum density + 2.0 before storage under high temperature and high humidity conditions. , And the difference in concentration was determined. The smaller the density difference, the more robust the color image is, and the more excellent the color image storability is.

(3) Image Quality With respect to the sample which has been subjected to color development processing by gradation exposure with the B-G-R filter attached, the yellow color image portion obtained by exposure with the B filter is subjected to B and G densities. measured as, from the characteristic curve, determine the G density of the exposure points give B concentration 2.0 (G _1), it was subtracted G density of the minimum density portion of the B concentration (G ₂₎ value from the G ₁ values Is calculated as ΔB _G ,
It was used as another measure of color reproducibility. In addition, the magenta color image portion obtained through the G filter is measured as G and R densities, and the R density (R ₁ ) at the exposure amount point giving the G density of 2.0 is obtained from the characteristic curve, and the minimum density of the G density is obtained. The value obtained by subtracting the R concentration (R ₂ ) value of _{each part} from R ₁ is calculated, and
Based on the value of (R ₁ -R ₂ ) obtained in step ₁ , the difference from each sample was obtained, and the color reproducibility was examined. Next, the coating amounts of the respective color-sensitive layers were finely adjusted so that the gradations of B, G, and R of the samples 101 to 122 were the same, and the samples were re-produced. Using the method, the MTF pattern was exposed to white light and developed, and the MTF value of each of the yellow, magenta, and cyan color images at 40 cycles / mm at the density of the minimum density +1.0 was measured to examine the sharpness. .

The treatment steps and treatment liquid compositions are shown below. In addition, the processing was carried out by separately treating the imagewise-exposed sample at a rate of 1 m ² per day, performing a running treatment until the tank was replenished with the color developing solution in an amount three times the tank volume, and then performing the treatment.

(Processing step) Process Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ℃ 23 ml 2 liters Bleach 50 seconds 38.0 ℃ 5 ml 5 liters Bleach fixing 50 seconds 38.0 ℃ -5 liters fixed 50 seconds 38.0 ℃ 16 ml 5 liters Water wash 30 seconds 38.0 ℃ 34 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ -3 liters stability (2) 20 seconds 38.0 ℃ 20 milliliters 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishing amount per 35m width of photosensitive material 1.1m (24E
x. (Equivalent to 1)

The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the washing step were as follows. 2.5 ml, 2.0 ml per 1 m,
It was 2.0 ml and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 130 195 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Hydroxyacetic Acid 50 75 Acetic Acid 40 60 Water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (Adjust with ammonia water and acetic acid) 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The results obtained by carrying out the above (1) to (3) are summarized in Table-D.

[0322]

[Table 7]

[0323]

[Table 8]

[0324]

[Table 9]

[0325]

[Table 10]

From the results of Table-D, regarding the B concentration, the acylacetamide type coupler having an acyl group represented by the formulas (1), (2) and (YI) of the present invention and / or the formula (I) or ( Samples 105-118 of the present invention containing couplers of II) are comparative samples 101-104.
And 119 to 122, high sensitivity and color density are provided, color image fastness is excellent, a large multi-layer effect is provided, color purity of the color image is high, and color reproducibility and sharp image quality are excellent. is there. Regarding the G concentration and the R concentration, the use of the compounds represented by the formulas (1) and (2) of the present invention is
It can be seen that the same excellent effects as in the above photographic properties, color image fastness and image quality improvement are exhibited. In particular, even in the compound represented by the formula of the present invention (I) and (II), a compound represented by having no diffusion-resistant group to the coupler mother nucleus moiety of the formula (II) (A ₂₎ is In comparison with the compound represented by (A ₁ ), which has a diffusion-resistant group in the mother nucleus portion of the coupler represented by the formula (I), it is preferable to improve the above-mentioned photographic properties, color image fastness and various image quality performances. It can be known from the use examples (Samples 113 to 115 and Samples 116 to 118) of the exemplary compounds represented by the formulas (I) and (II) used in Samples 105 to 118. The compound represented by the formula (II) undergoes a coupling reaction with an oxidant of a color developing agent to give (TIME) _a
Although A ₂ produces a dye at the same time as -DI is released, A ₂ has an advantage that it does not flow out from the film of the light-sensitive material and remains on the light-sensitive material because it does not have a diffusion-resistant group. Therefore, the formula (I
The compound represented by I) does not limit the amount used in any color-sensitive layer and impairs color reproducibility regardless of whether A ₂ is a mother nucleus of cyan, magenta or yellow coupler. It has the advantage that it can be used without.

Example 2 The composition of the color developing solution used in Example 1 was changed as shown below, the processing temperature was set to 43.0 ° C., and the replenishment rate was set to 100 ml / m ² . Using Samples 101 to 122, one type of each sample was processed by one automatic processor, and the same performance evaluation as in Example 1 was performed.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 6.0 Potassium carbonate 37.5 39.0 Potassium bromide 5.5-Iodine Potassium iodide 1.3 mg-hydroxylamine sulfate 4.0 6.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 10.0 19.0 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 12.0

As a result of high-temperature low-replenishment amount processing using the above-mentioned color development, Samples 105 to 118 of the present invention were
The results are the same as those obtained in Example 1, and it was found that excellent photographic performance, color image storability and image quality were provided, and stable processability was exhibited. On the other hand, comparative samples 101 to 104, 11
In Nos. 9, 121 and 122, the photographic sensitivity and the gradation were slightly low (-0.0) when compared with the results of Example 1.
5), low γ (-0.08), a slight deterioration in color image storability (-0.02 to -0.01) was observed, and the multilayer effect,
The sharpness is the same or slightly lower (-0.02
However, there was a change in performance due to changes in processing. As a result, it is clear that the DI of the compounds represented by the formulas (I) and (II) of the present invention gives stable photographic properties, color image fastness and image quality during the running process by being deactivated after the process. .

Example 3 PEN having a thickness of 85 μm, which was provided with an undercoat layer and subjected to heat treatment
[2,6-Naphthalenedicarboxylic acid / ethylene glycol (100/100 mol ratio)] A support was used to prepare a multilayer color light-sensitive material having the following composition.

The amount added to the light-sensitive material is shown in grams per m ² , silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is expressed in moles with silver halide. The ratio is shown.

(Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 Ultraviolet absorber UV-I 0.1 Ultraviolet absorber UV-II 0.1 Ultraviolet absorber UV- III 0.1 Dispersion oil Oil-1 0.2 Dispersion oil Oil-2 0.1

Second layer (intermediate layer) Gelatin 1.0 Coupler C-2 0.02 Dispersion oil Oil-1 0.01

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Monodisperse Silver Iodobromide Emulsion 1.8 (3 mol% silver iodide, average grain size 1.0 μm) Gelatin 1.2 Sensitizing dye I 1.4 × 10 ^-4 Sensitizing dye II 7 × 10 ^-5 Coupler C-1 0.5 Coupler C-2 0.05 Comparative coupler (E) 0.04 Compound D 0.1 Dispersion oil Oil-3 0.03 Dispersion oil Oil-4 0.05

Fourth Layer (Intermediate Layer) Gelatin 1.0 Compound A 0.1

Fifth layer (low-sensitivity green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.4 (3 mol% of silver iodide, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.3 ( Silver iodide 3 mol%, average particle size 0.3 μm) Gelatin 0.8 Sensitizing dye III 3 × 10 ^-4 Sensitizing dye IV 1 × 10 ^-4 Sensitizing dye V 1 × 10 ^-4 Coupler C-30 .4 coupler C-4 0.1 coupler C-5 0.1 coupler C-6 0.3 comparative coupler (F) 0.05 coupler C-11 0.08 compound C 0.1 dispersion oil Oil-3 0. 3 Dispersion oil Oil-5 0.2

Sixth Layer (Intermediate Layer) Gelatin 1.0 Compound A 0.1

Seventh layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 0.7 (3 mol% of silver iodide, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.2 ( Silver iodide 3 mol%, average particle size 0.3 μm, cube) Gelatin 1.0 Sensitizing dye VI 2 × 10 ⁻⁴ Sensitizing dye VII 2 × 10 ⁻⁴ Comparative coupler (2) 0.73 Comparative coupler (3 ) 0.38 Comparative coupler (G) 0.05 Dispersion oil Oil-1 0.20 Dispersion oil Oil-5 0.10

Eighth Layer (Intermediate Layer) Gelatin 1.0 Compound B 0.1

Ninth layer (high-sensitivity red-sensitive emulsion layer) Polydisperse silver iodobromide emulsion 2.3 (6 mol% silver iodide, average grain size 2.0 μm) Gelatin 1.2 Sensitizing dye I 7 × 10 ^-5 Sensitizing Dye II 2 × 10 ^-5 Coupler C-8 0.15 Coupler C-1 0.15 Comparative Coupler (E) 0.03 Compound D 0.1 B-32 5.0 × 10 ^-3 Dispersed Oil Oil-4 0.2

10th layer (intermediate layer) Gelatin 1.0 Coupler C-5 0.2 Compound A 0.1

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Polydisperse silver iodobromide emulsion 2.0 (silver iodide 5 mol%, average grain size 2.0 μm) Gelatin 1.0 Sensitizing dye III 1 × 10 ^-4 Sensitizing dye IV 3 × 10 ^-5 Sensitizing dye V 3 × 10 ^-5 Coupler C-6 0.04 Coupler C-9 0.18 Coupler C-10 0.04 Comparative coupler (F) 0.03 B -14 1.0 × 10 ^-2 Compound C 0.1 Dispersion oil Oil-1 0.40 Dispersion oil Oil-5 0.05

Twelfth Layer (Intermediate Layer) Gelatin 1.2 Compound A 0.1

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.8 (3 mol% silver iodide, average grain size 2.1 μm) Monodisperse silver iodobromide emulsion 0.5 ( Silver iodide 3 mol%, average particle size 1.2 μm) Monodisperse silver iodobromide emulsion 0.2 (3 mol% silver iodide, average particle size 0.3 μm, cubic) Gelatin 1.2 Sensitizing dye VI 3 ^X10-4 Sensitizing Dye VII ^1x10-4 Comparative Coupler (2) 0.32 Comparative Coupler (G) 0.02 B-16 ^1.5x10-2 Dispersed Oil Oil-1 0.11.

Fourteenth Layer (First Protective Layer) Coupler C-7 0.1 UV Absorber UV-I 0.05 UV Absorber UV-II 0.05 UV Absorber UV-III 0.05 UV Absorber UV -IV 0.05 UV absorber UV-V 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1

Fifteenth layer (second protective layer) Gelatin 0.5 Polymethylmethacrylate particles 0.2 (diameter 1.5 μm) The compounds used in this Example are shown in Chemical Formulas 106 to 119 below.

[0347]

[Chemical formula 106]

[0348]

[Chemical formula 107]

[0349]

[Chemical 108]

[0350]

[Chemical 109]

[0351]

[Chemical 110]

[0352]

[Chemical 111]

[0353]

[Chemical 112]

[0354]

[Chemical 113]

[0355]

[Chemical 114]

[0356]

[Chemical 115]

[0357]

[Chemical formula 116]

[0358]

[Chemical 117]

[0359]

[Chemical 118]

[0360]

[Chemical formula 119]

In addition to the above components, each layer contains a surfactant WI.
And W-II, hardeners HI and DI-1 were added. Further, ST-1 and AF-1 are contained in the photosensitive emulsion layer.
Was added to the third layer, and AI-2 was added to the fifth layer. Further formalin scavenger 15th
Added to layer. This sample is referred to as sample 301.

Then, using the control double jet method, tabular non-photosensitive fine grain silver halide grains having an average grain size of pure silver bromide of 0.15 μm and an average aspect ratio of 4.0 and silver iodobromide ( Silver iodide (2 mol%) average grain size 0.18
tabular non-photosensitive fine grain silver halide grains having an average aspect ratio of 4.0, respectively, and having a grain size of 0.25 μm in the eighth layer of the intermediate layer of the above multilayer color light-sensitive material. To give a coating amount of 0.30 g / m ² , a particle size of 0.20 μm for the 10th layer to 0.25 g / m ^2, and a particle size of 0.15 μm for the 12th layer. Of 0.20 g / m ² and the cube of the 7th layer, average particle size 0.3 μm
The same weight of the fine grain silver iodobromide of m was replaced with the same weight of tabular grains and coating was conducted to prepare a multilayer color light-sensitive material. This sample is referred to as sample 302.

Subsequently, the sample 303 is the eighth sample of the sample 301.
Samples were prepared by coating non-photosensitive fine grain silver halide grains in the layers, the tenth layer and the twelfth layer with the same average grain size as the sample 302 and applying the cube-shaped grains in the same weight. Sample 304 is the seventh and thirteenth layers of Sample 301.
Monodisperse silver iodobromide emulsion used in the blue-sensitive emulsion layer (silver iodide 3
A sample was prepared by removing 0.2 g (mol%, average particle size 0.3 μm).

Further, the comparative coupler (E) used in the third and ninth layers of Samples 301 to 304 was used as D-11 of the present invention.
And D-30 in a 1: 1 molar ratio mixture; comparative coupler (F) used in the fifth and eleventh layers was used as D-37 of the present invention
Layer, D-17 as the 11th layer; the comparative coupler (G) used in the 7th and 13th layers, the D-42 of the present invention as the 13th layer, and D-15 as the 7th layer. The seven-layer comparative couplers (2) and (3) were added to Y-11 and YB-7 of the present invention, firstly.
Samples 305-3 with the three-layer comparative coupler (2) changed to a 2: 1 molar ratio mixture of Y-29 and comparative coupler (2).
08 was produced.

The samples 301 to 308 thus prepared were exposed to white light, and the color development treatment described in Example 2 was used to carry out separate imagewise exposure before the start of the running treatment and until the replenishment amount of three times the tank capacity of color development was replenished. After a given sample was subjected to a running process, a development process was carried out before the continuous process was started, and a running process was carried out to examine the fluctuation of the sensitivity of the photographic property when the steady process state was reached. This was determined as the sensitivity difference (ΔS). Further, the sensitivity and the γ ratio when the running process was performed and the process reached a steady state were obtained by the same method as in Example 1.
The sensitivity was based on Sample 304. The results for these yellow color images are shown in Table-E. Further, the color image fastness and sharpness were also obtained for the yellow color image. Similarly, they are collectively shown in Table-E.

[0366]

[Table 11]

From the results of Table-E, Samples 305 to 308 using the couplers represented by the formula (I) or (II), the general formula (YI) and the general formula (2) of the present invention used comparative couplers. The sensitivity of the photographic property,
It is clear that the color density is high, the fluctuation of the sensitivity is small even when the low-complement amount processing of the color developer is carried out, and the color image storability and the sharpness are excellent. Further, by using non-photosensitive fine grain silver halide grains in the non-photosensitive layer adjacent to the support of the highly sensitive blue-sensitive, green-sensitive and red-sensitive emulsion layer, the photographic property and sharpness can be improved. It is also possible to improve the samples 304 and 301 to 303 and the samples 308 and 305 to 30.
As can be seen from Sample No. 7, the effect of improving the photographic property and the sharpness is large by using the coupler of the present invention.
It can be seen by comparing the corresponding samples of 1-304 and 305-308, respectively. It can be seen that it is particularly preferable to use non-photosensitive fine grain silver halide grains.

Example 4 A film unit with a lens was prepared from Samples 101, 105 to 118 prepared in Example 1 according to the methods described in JP-B-2-32615 and JP-B-3-39784. These 15 types of film units with lenses capture various subjects under the same conditions, and the automatic processor FP-560B AL
(Fuji Photo Film Co., Ltd.) color development processing, and then Fuji Mini Lab Champion, Printer Processor FA-140 (Fuji Photo Film Co., Ltd.) is used, Fuji Color Paper, Super FA, T
Printing was performed on ypeV (CP-45X was used for color development processing at this time).

When the respective patterns obtained by printing from these 15 kinds of samples were observed, the color prints obtained from Samples 105 to 118 using the coupler of the present invention were compared with those obtained from Sample 101 in the subject. It was confirmed that the delicate parts were excellent in depiction, and the color was particularly yellowish, which improved the image quality. Further, when the color negative was examined for color image fastness under the same conditions as in Example 1, it was confirmed that Samples 105 to 118 using the coupler of the present invention had improved fastness as compared with Sample 101. Although the same procedure was performed for Samples 301 to 308, it was confirmed in the same manner as above that Samples 305 to 308 using the coupler of the present invention had improved image quality and color image fastness as compared to Samples 301 to 304. I was able to. In particular, it was confirmed that the samples 305 to 307 were excellent in photographic property and sharpness.

Example 5 Samples 101 to 122 prepared in Example 1 were used, and the color developing solution used in Example 1 was used.
Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate was added to 2-methyl-4- [N-
Example 1 was carried out by substituting an equimolar amount of ethyl-N- (δ-hydroxybutyl) amino] aniline sulfate to obtain a color developer, and shortening the developing time from 3 minutes 5 seconds to 2 minutes 30 seconds. Performance evaluation was performed by the same method.

As a result, Sample 10 having the constitution of the present invention was obtained.
5 to 118 are comparative samples 101 to 104 and 119 to 1.
Compared with No. 22, it gives high sensitivity and color density even in the processing that changed the color developing agent and shortened the color development time, and it also has excellent color image storability, and it gives a large multi-layer effect and high color purity of color image and color reproducibility. It was also confirmed that the sharpness was excellent and a good image quality was provided.

[0372]

The compound represented by formula (I) or formula (II), the acylacetamide type coupler having an acyl group represented by formula (YI) and / or the formula (1)
Alternatively, by using a coupler represented by the general formula (2), a silver halide color photograph having high sharpness, high color density, excellent color image storability, good multi-layer effect and hue, and excellent sharpness. A photosensitive material can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seijo Nakajo 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a compound represented by the following formula (I) or (II), and , The general formula (Y
I) an acylacetamide type coupler having an acyl group and / or a coupler represented by the general formula (1) represented by the following chemical formula 2 or the general formula (2) represented by the following chemical formula 3 A silver halide color photographic light-sensitive material. Formula (I) A _1- (TIME) _a -DI Formula (II) A _2- (TIME) _a -DI In the formula, A ₁ has a nondiffusible group and oxidizes an aromatic primary amine developer. Represents a group capable of leaving (TIME) _a -DI upon reaction with _a derivative, A ₂ has no diffusion-resistant group, and reacts with an oxidant of an aromatic primary amine developing agent to give (TIM
E) represents a group that leaves _a- DI, TIME represents a timing group that cleaves DI after leaving from A, DI represents a development inhibitor that is substantially deactivated after flowing out into a developer, and a represents Represents 1 or 2. two a when a is 2
IME represents the same or different. General formula (Y
I) [Chemical formula 1] In the formula, R ₁ represents a substituent, Q together with C is a 3- to 5-membered hydrocarbon ring or a 3- to 6-membered hydrocarbon ring having at least one hetero atom selected from N, O, S, and P in the ring. Represents a group of non-metal atoms necessary to form a heterocycle. General formula (1) General formula (2) In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, and Y represents an aryl group or a heterocyclic group. Represents a group, and Z represents a group which leaves when the coupler represented by the general formula reacts with an oxidized product of a developing agent. 2. A light-sensitive silver halide emulsion layer and / or an adjacent layer on the side closer to the support of the layer contains substantially light-insensitive fine grain silver halide grains. Item 1. A silver halide color photographic light-sensitive material according to Item 1. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the light-sensitive silver halide emulsion layer is a blue-sensitive silver halide emulsion layer. 4. The silver halide color photographic light-sensitive material according to claim 2, wherein the layer adjacent to the support of the light-sensitive silver halide emulsion layer is a non-light-sensitive layer. 5. The photosensitive silver halide emulsion layer has two or more red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers each having different sensitivities, and the following conditions (a) to (d) are satisfied. 2. All of the above are satisfied.
A silver halide color photographic light-sensitive material described in 1. (A) The photosensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (b) the most sensitive green-sensitive halogen. Silver halide emulsion layer (G
H) and the most sensitive red-sensitive silver halide emulsion layer (R
H) between the BH and a blue-sensitive silver halide emulsion layer (Bh) having a lower sensitivity than BH, and (c) with respect to the Bh, the side farthest from the support has the highest sensitivity. Low red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers (RL, GL and BL, respectively) are not present, and (d) a non-photosensitive layer is adjacent to the side of the BH close to the support, The BH and / or the non-photosensitive layer contains substantially non-photosensitive fine grain silver halide grains.