JPS63313154A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a multilayered silver halide color photographic material having satisfactory color developing property and picture image preservability by incorporating a coupler expressed by the specified formula into a blue sensitive photosensitive layer. CONSTITUTION:A coupler expressed by formula I and compds. expressed by formulas II and III are incorporated into a blue sensitive photosensitive layer. In the formula for expressing the coupler, R11 is an alkyl group; R12 is H or an alkyl group; R13 is H, alkoxy, or alkyl group wherein R13 is alkoxy or alkyl when R12 is H; R14 is Cl or alkoxy; X11 is a nonmetal atom group necessary for forming a 5- or 6-membered ring. In formula II expressing a compd. to be used in combination with the coupler, R50 is H, alkyl, aryl, heterocyclic, or trialkylsilyl group; each R51-R55 is H, alkyl, aryl, alkoxy, alkoxycarbonyl, hydroxyl, amino, imino, or acylamino group. In formula III, each R61-R64 is H or alkyl; X61 is H, alkyl, acyl, oxy radical, hydroxyl; A61 is a nonmetal atom group necessary for forming a 5- or 6-membered ring. This photosensitive material does not cause discoloration even if it is preserved under severe condition of exposure.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a multilayer halogenated color light-sensitive material, and more specifically, a novel material that has good color development, improved image storage stability, and does not disrupt color balance. The present invention relates to a multilayer silver halide color light-sensitive material (hereinafter referred to as a light-sensitive material) containing a combination of couplers.

(Background Art) A silver halide color sensitive material has a multilayer structure consisting of three types of silver halide emulsion layers that are selectively sensitized to have sensitivity to blue light, green light, and red light. is coated on the support. For example, in so-called color photographic paper (hereinafter referred to as color paper), a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in order from the side that is normally exposed, and between each light-sensitive layer. etc., are provided with an intermediate layer that prevents color mixing, a UV absorbing layer, a protective layer, etc.
In a so-called color positive film, a green-sensitive emulsion layer, a red-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in order from the side that strays from the support, that is, the side that is to be repaired. Color negative films have a wide variety of layer arrangements, and generally they are coated in the order of blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer from the side to which light is spread. In light-sensitive materials having two or more emulsion layers with different sensitivities, there are also some light-sensitive materials in which emulsion layers with different color sensitivities are arranged between the emulsion layers, and one layer of yellow filter that can be whitened, an intermediate layer, A protective layer etc. is inserted.

To form color photographic images, photographic couplers gold-sensitive III# of yellow, magenta and cyan are used.
The photosensitive material, which has been exposed to light, is then processed for color development using a so-called color developing agent. The N-type aromatic primary amine gives a color-forming element through a coupling reaction with a coupler, and the coupling rate at this time is as high as possible to give a high color density within a limited development time. , those with good color development are preferred. Furthermore, the color-developing dyes are all required to be bright cyan, maze/yellow, and yellow dyes with little side absorption and to provide color photographic images with good color reproducibility.

On the other hand, the nine-color JIC images formed are required to have good storage stability under stable conditions. In order to meet this requirement, it is necessary to have a slow rate of fading or discoloration of the color lines of different hues, and to have a uniform rate of fading over the entire range of image density. It is important that the balance does not change.

(Problems to be Solved by the Invention) Conventional photosensitive materials, especially color paper, suffer from large reductions in yellow dye images due to long-term fading due to the influence of humidity and heat, and tend to change color balance, which requires improvement. Strongly Desired: Traditionally, if the color does not easily fade, the color development is poor, so there is a demand for a new combination of couplers that have good color development and image preservation properties.

In order to partially solve this problem, various couplers, particularly yellow couplers, and combinations thereof have been proposed.

For example, JP-A-57-20037, JP-A-59-572
No. 38, JP-A-58-208745, JP-A-60-2
No. 05446, t# Publication No. 60-117249, Japanese Patent Publication No. 60-229029, Japanese Patent Publication No. 60-222852,
JP-A-61-50136, JP-A-59-160143
No., JP-A-61-120147, JP-A-61-404
An example thereof is described in No. 7 and Japanese Patent Publication No. 52-7344.

However, with these couplers and combinations, the color development of the yellow coupler is insufficient, and furthermore, the yellow pigment part is prone to fading due to -& or heat, so the color balance fluctuates and the overall quality is poor. K to resolve
has not yet been reached.

The present invention (11) is an attempt to solve the above problems at the same time.More specifically, the object of the present invention is to provide good color development and improved image storage stability, and in particular, to provide a dark image for a long period of time. An object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material whose color balance does not change either in place or under light exposure. In particular, it is an object of the present invention to provide a multilayer silver halide color photographic light-sensitive material whose color images do not fade even when stored under severe conditions such as exposure to light.

(Means for solving the problem) The above-mentioned objects of the present invention are to provide a halogenated color photographic light-sensitive material having blue-sensitive, green-sensitive and red-sensitive light-sensitive layers on a support. at least one crosspiece of the coupler represented by the following general formula (1) and the following general formula (V
) and (Vl), the silver halide color photographic material is characterized in that at least 15f11 of the compounds contained in (Vl) is reduced to 7. I found out that it can be done.

General formula (1) ”xll (In the formula, R11 represents an alkyl group.

R1□ represents a hydrogen atom or an alkyl group.

R13 represents a hydrogen atom, an alkoxy group or an alkyl group, and when R□2 is a hydrogen atom, R13 represents an alkoxy group or an alkyl group.

R14 represents a chlorine atom or an alkoxy group, and X1□ represents a nonmetallic atom group necessary to form a 5- or 6-membered ring. ) General formula (V) (wherein R3° is a hydrogen atom, an alkyl group, an aryl group,
Represents a heterocyclic group or trialkylsilyl group.

穐□・R52・R53・Rs4 and R55 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an amino group, an imino group or an acylamino group, ) General formula (Vl) (In the formula, R0□, R6□, R63 and R64 may be the same or different and each represents a hydrogen atom or an alkyl group.

X61 represents a hydrogen atom, an alkyl group, an acyl group, an oxy radical group or a hydroxyl group.

A61 represents a nonmetallic atomic group necessary for forming a 5- or 6-membered ring. ) General formula (1) will be explained in detail.

In the formula, R□1 includes unsubstituted alkyl groups (eg, methyl group, ethyl group, n-butyl group, n-octyl group, t-butyl group, etc.) and substituted alkyl groups.

As a substituent, a halogen atom (?Ij is a chlorine atom,'
fluorine atom, etc.), alkoxy group (e.g. methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g. phenoxy group), sulfony A4
(For example, methylsulfonyl group, phenylsulfonyl group, etc.), amide group (for example, acetamide 9 group, methanesulfonamide group, benzenesulfonamide group, etc.),
Alkoxycarbonyl groups (for example, methoxycarbonyl groups, etc.), sulfamoyl groups (for example, ethylsulfamoyl groups, etc.), hydroxy groups, cyano groups, carboxyl groups, 7-enyl groups, and the groups listed in 1 above can be used.

The alkyl group represented by R82 is preferably an unsubstituted alkyl group (for example, methyl M, t-acyl group, t-octyl group, etc. >1).

The alkyl group represented by R13 preferably has 1 carbon number.
-8 unsubstituted alkyl groups (for example, methyl group, ethyl group, n-propyl group, t-butyl group, t-octyl group, etc.).

The alkoxy group represented by R13 is an unsubstituted alkyl group (
For example, methoxy groups, ethoxy groups, n-butoxy groups, etc.) and substituted alkoxy groups.

Examples of substituents include halogen atoms (e.g., chlorine atom, fluorine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenoxy group, etc.), sulfonyl groups (e.g., methylsulfonyl group, etc.)
, amide group (e.g., acetamide group, meta/sulfo/amide group, etc.), alkoxycarbonyl group (e.g., methquine carbonyl group), sulfamoyl group (e.g., ethylsulfamoyl group, etc.), human 90oxy group , cyano group, -h lupoxy? 5. Phenyl group, etc. can be mentioned.

The alkoxy group represented by R14 preferably represents an unsubstituted alkoxy group (eg, methoxy group, ethoxy group, etc.).

X11 represents two nonmetallic atomic groups necessary to form a 5- or 6-membered ring.

Preferred specific examples of the 5- or 6-membered ring are the following general formula %, where R71, R72, R8□, and R8゜ are respectively a leaf atom, a halogen atom, a carbonyl ester group, an amino group, an alkyl oxidation group, an alkylthio group, Alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group,
It represents a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.

Nonmetallic atoms required to form a ring or a 6-membered ring t-
represent.

A more preferable specific example of general 5r, (■) is the following formula <X>
It is represented by ~(Xll).

In the formula, R101' R1°2 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and R1o3. R1゜4 and R
105 each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group, and Wlol represents an oxygen or sulfur atom.

A more preferred yellow coupler of general formula (1) is represented by the following general formula (1-A).

General Formula (1-A) In the formula, R15 represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms.

R16 represents a tertiary unsubstituted alkyl group having 4 to 8 carbon atoms.

x1□ represents a group of nonmetallic atoms necessary to form a 5-membered ring.

The unsubstituted alkyl group represented by R15 may be either a straight-chain or branched alkyl group, but especially a straight-chain alkyl group (such as a methyl group, an ethyl group,
n-hexyl group, n-octyl group, n-decyl group, etc.) are preferred. Substituents for the tlt-substituted alkyl group include alkoxy groups (e.g., methoxy group, ethoxy group, n-butoxy group, etc.), amido-S (e.g., acetamide group, methanesulfonamide group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group). , ethoxycarbonyl group (Nato), sulfamoyl group (eg, EVA, ethylsulfamoyl group, diethylsulfamoyl group, etc.), hydroxyl group, carboxy group, phenyl group (also includes ft-substituted phenyl group).

Alk as f substituent group, halogen atom, alkoxy group, etc. ) is mentioned, but alkoxy in % Groups are preferred.

A specific example of the 5-membered ring formed by X12 is the general formula (X
), (Xl) and (X11), with general formulas (X) and (XI) being particularly preferred.

Next, specific examples of the compound represented by the general formula (1) will be shown, but the compounds of the present invention are not limited thereto.

k13 2H5 General formulas (■) and (■) will be explained in detail.

Rso is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, propyl group, 2-methoxyethyl group, 2-cyanopropyl group, benzyl group, phenethyl group, etc.), an aryl group (e.g. phenyl group, p-chlorophenyl X, O-
methoxyphenyl group, p-methoxycarbonylphenyl group, etc.), a heterocyclic group (eg, pyridyl group, etc.), or a trialkylsilyl group (eg, trimethylsilyl group, etc.).

R5□l R52"531 R54 and Rss may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, t-butyl group, t-acyl group, t-octyl group, methoxycarbonylethyl group) group, n-octadecyloxycarbonylethyl group),
Aryl 1i (e.g., tij: phenyl 1k, P-chlorophenyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, n-butoxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), hydroxyl group, It represents an amino group (eg, diethylamino group, pyrisilylamino group, etc.), an imino group, or an acylamino group (eg, acetamido group, methanesulfonamide group, etc.).

R61' R6□, R63 and '64 may be the same or different, and each represents a hydrogen atom or an alkyl group (
For example, it represents a methyl group, ethyl M, t-butyl group, t-acyl group, t-octyl group, etc.).

X6□ is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, I n-propyl group, allyl group, t-butyl group, etc.), an acyl group (e.g. acetyl group, n-decanoyl group, propinoyl group, butanoyl group, (benzoyl group, methanesulfonyl group, etc.), oxy radical group, or human 90xyl group.

A6□ represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. Specific examples of the 5- or 6-membered ring include a pyrrolidine ring, a pirazine ring, a morpholine ring, an imidazolidine ring, and a pyrrolidine ring.

More preferred color image stabilizers of general formulas (V) and (vl) are represented by the following general formulas (VA) and (Vl-A).

General formula (VA) H In the formula, R36"5□ each represents a hydrogen atom or an alkyl group, and at least one of R56 and R5
represents a class alkyl group.

R58 represents an alkyl group, an alkoxy group or an amino group, which may contain a substitutable group. Specific examples of the substituent include an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, and an aryl group.

General formula (Vl-A) In the formula, X6□ represents a hydrogen atom, an alkyl group, an acyl group, or an oxy radical group.

R6! S, R66, R6□, and R68 represent a hydrogen atom or an alkyl group, and at least two of these represent an alkyl group.

R69 is a hydrogen atom, an alkyl group, or an acyloxy group'
kWwasu. Alkyl groups and 7-syloxy groups are substitutable groups! may have been replaced.

Next, specific examples of compounds represented by general formulas (V) and (M) will be shown.

(V-1) (V-2) (V-3) Yes. h, (t) (V-4) (V-5) (V-6) (V-7) (V-S) (V-9) (V-10) (v-1i) t) (V-12) (■t-1) (M-2) (Vl-3) (Vl-4) (Vl-5) (Vl-6) (Vl-7) (Vl-8) (Vl -9) (■-10) Synthesis method of compounds corresponding to general formula (V) or (Vl)K or examples of compounds other than decontamination are described in British Patent No. 1326888.
No. 1354313, No. 1410846, U.S. Patent No. 3336135, U.S. Pat.
-1420, 52-6623, JP-A-Sho -58-
No. 114036 and No. 59-5246.

Two or more of the compounds represented by formulas (V) and (Vl) may be used in combination, and may also be used in combination with a conventionally known anti-fading agent.

The amount of the compounds represented by formulas (V) and (Vl) to be used varies depending on the type of yellow coupler used in combination, but is 0.5 to 200 parts heavier than the yellow coupler, preferably 2 to 150 parts heavier than the yellow coupler. It can be used within a range to achieve the desired purpose. Preferably, it is co-emulsified with the yellow coupler of general formula (1).

In the present invention, 5-pyrazolones, pyrazoleazoles, pyrazolo nottriazoles and cyanoacetyl compounds can be used as magenta couplers, and phenols and naphthols τ can be used as cyan couplers. When the magenta coupler i represented by formulas (n) and (m>) and the cyan coupler represented by the following general formula (■) are combined with the yellow coupler of general formula (1) of the present invention, color image storage properties are improved. This is advantageous in that the image quality can be kept at the same level and the image quality will not deteriorate over time.

General formula (n) (wherein R2□ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group.

R2□ represents an aryl group.

Z2□ represents a hydrogen atom or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine 7 color developing agent. ) General formula <m> (In the formula, R3□ represents a hydrogen atom or a substitutable group.

z31 represents a hydrogen atom or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent.

z32, z33 and z34 represent -C=, -N- or 擢H-, and z34-233
One of the bonds is a double bond, and the other is a single bond. The case where z33-Z3□ is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. ) General formula (■) 0H 24, (wherein R4 represents an alkyl group, an aryl group, an amino group or a heterocyclic group.

R4□ represents an acylamino group or an alkyl group.

R43 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amide group. R4° and R43 may be combined to form a 5J or 6-membered ring.◇ Z4□ represents a hydrogen atom or a group that can be separated upon reaction with an oxidized product of an aromatic primary amine color developing agent. ) General formulas (U) and (ill) will be explained in detail.

In general formula (If), R2□ and R2□ may each further have a substituent 1&:. For example, the alkyl group for R2□ is an alkyl group having 1 to 42 carbon atoms, such as a methyl group, a butyl group, an octadecyl group, or a 2-(2
, 4-di-tert-amylphenoxy)ethyl group, and the like group includes, for example, phenyl, 11
．． 2-10 lophenyl i, 2-chloro-5-tetradecylaminophenyl group, 2-chloro-5-(3-ophtatecenyl-N-succinimide) phenyl group, 2-chloro-5(2-(2,4-di -t-amylphenoxy)butanamide 9) Phenyl 5.2.4-Cyclo-5-dodecyloxyphenyl group or 2-chloro-5-octadecylthiophenyl group, etc., and examples of the acyl group include acetyl group, 2- Ethylhexanoyl group, α'-(2
, 4-di-tert-inchylphenoxy)acetyl group, α-(2,4-di-tert-inchylphenoxy)
Examples of the carbamoyl group include N-methylcarbamoyl H1N, N-t Methylcarbamoyl group, N-hexatecylcarbamoyl group, N
-methyl-N-phenylcarbamoyl group or N-(3
-(α-(2,4-di-tert-d-butylphenoxy)butyramide]) phenyl group, and the like.

As R2□, for example, phenyl group, 2,4.6-)dichlorophenyl i, 2.5--, 'chlorophenyl group,
2.4-dimethyl-6-medoxyphenyl group, 2.6-
Cycloro 4-me)-? diphenyl group, z, s-9 chloro-4-ethoxycarbonylphenyl group, ma or Z, 6
-S) chloro-4-cyanophenyl group, or 4-(α
-(2,4-di-tert-amylphenoxy)butylami-P)phenyl group, and the like.

Z21 represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., dodecyloxy group, dodecyloxycarbonylmethoxy group, methoxycarmemoylmethoxy group, carboxypropyloxy group, methanesulfonyloxy group), aryloxy group (e.g. 4-methylphenoxy group, 4-methylphenoxy group,
-tert-butylphenoxy group, 4-methoxyphenoxy group, 4-methanesulfonylphenoxy group, 4-(4
-benzyloxyphersulfonyl) phenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazokayloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group,
toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, methanesulfonylamino group, triphonylphosphonamide group), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, potassium oxycarbonyloxy group) ), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy groups), aliphatic or aromatic thio groups (e.g. phenylthio group, dodecylthio group, benzylthio group, 2-butoxy-5-tert-octylphenylthio group) , 2.5-di-octyloxyphenylthio group, 2-(2-ethoxyethoxy)-5-tert-octylphenylthio group, tetrazolylthio group, etc.), imide group (e.g., succinimide group, hydantoinyl i
, 2.4-dioxoxazolidin-3-yl group, 3-
N-heterocycle (e.g., 1-pyrazolyl group, 1-enzotriazolyl group, 5-chloro-1,2,4-triazol-1-yl group, etc.) , aromatic azo groups (eg, phenylazo group, etc.). These leaving groups may include photographically useful groups.

R21, R2□, and Z2□ of general formula (II) may form a dimer or a multimer of more than that.

, In the general formula (II), R3□ represents a mineral water atom or substituent, z3□ represents a hydrogen atom or a group that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent, z3□, z33 and z34 are −C=, −
N=t7'cu-NH-efi, z34-233
One of the bonds and the z3s-232M bond is a double bond, and the other is a single bond. If z33-23□ is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. General formula (
In II), R3□ is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, or a silyloxy group. , sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sul7amoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide represents a carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group or aryloxycarbonyl group.

To explain these R substituents in more detail, R3□ represents a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group (e.g., methyl group, propyl group, t-
Butyl group, trifluoromethyl group, tridecyl group, 3-
(2,4-di-t-amylphenoxy)propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-5xylsulfonyl-ethyl group, cyclo2notel group, benzyl group, etc.) , an aryl group (e.g. l
! , 7z Nil! L4-1-butylphenyl group, 2.4-
di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group,
2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, 2-
dodecyloxyethoxy group, 2-methanesulfonylethoxy7 group, etc.), aryloxy group (e.g., 7ethoxy7 group, etc.)
Group, 2-methylphenoxy! , 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g.,
acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (1'lJ, t, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group,
etc.), silyloxy groups (e.g., trimethyl7lyloxy group, etc.), sulfonyloxy groups (e.g., to9-defursulfonyloxy group, etc.), acylamino groups (e.g.,
Acetamide group, benzamyl group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, r-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4- (4-hydroxyphenylsulfonyl)phenoxy)decanamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxy Carbonylanilino group, N-acetylanilino group, 2-chloro-5
-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N, N
- dibutylfreido group, etc.), imide group (e.g. N-
Succinimide group, 3-penzylhydantoinyl i, 4
-(2-ethylhexanoylamino)phthalimide group,
), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio groups (e.g., methylthio group, octylthio group, tetradecyl thio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-5-t-octyl group) phenylthio group, 3-bentadecyl phenylthio group, 2-carboxyphenylthio group, 4-tetradecanamyl phenylthio group, etc.), heterocyclic thio group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonyl Amino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino group,
2.4-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide &, P-)luenesulfonamide group,
Octadecanesulfonamide group, 2-methyloxy-5
-t-butylbenze/sulfonyl group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl, N, N
-dibutylcarbamoyl group, N-(2-)'7'siloquinethyl)carbamoyl group, N-methyl-N-to'decylcarbamoyl group, N-(3-(2,4-di-tar)
t-7mil7z/*'s/)propyl)carbamoyl group, etc.), acyl group (e.g. 1.acetyl group,
(2,4-di-tert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl f = (e.g., t
For example, N-ethylsulfamoyl%, N,N-dipropylsulfamoyl group, N-(2-)";F'syloxyethyl)sulfamoyl group, N-ethyl-N-)"decylsulfamoyl group , N, N-9 ethylsulfamoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group,
Octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, 2-butoxy-5-tart-octylphenylsulfonyl 1%), sulfinyl group (fFI
J, ttf, octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group (1%), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, 1- or 4-aryloxycarbonyl group (e.g. , phenylox7carbonyl Z, a--Z-tadecyloxy-carbonyl group, etc.).

Z31 represents a hydrogen atom that can be separated in a reaction with an oxidized product of an aromatic primary amine color developing agent;
Details a of 3□ are the same as those explained in 221 of general formula (II).

R3□ and Z31 of general formula (Ill) may form a dimer or a multimer of more than that.

The general formula (■) will be explained in detail.

In the general formula (IV), R4 is an alkyl group having 1 to 32 carbon atoms, such as an alkyl group having 1 to 32 carbon atoms, such as a methyl group, a methyl group, a tridecyl group, a nclohexyl group,
Examples of the aryl group include:
Examples include phenyl group and naphthyl group, and examples of heterocyclic groups include 2-pyridyl group and 2-furyl group.

When R41 is an amino group, special Kff! Preferred are phenyl-substituted amino groups which may have convertible groups).

R41 further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, a methoxy group, a tridecyloxy group, a methoxyethoxy group, a phenyloxy group, a 2,4-di-tert-amylphenox group, a 3-
tert-butyl-4-hydroxyphenyl, oxy, naphthyloxy, etc.), carboxy group, alkyl or arylcarbonyl group (eg, acetyl, tetradecanoyl, benzoyl, etc.), alkyl or aryloxy Carbonyl group (e.g., methoxycarbonyl group, phenoxycarbonyl group, etc.), acyloxy group (e.g., acetyl group, penzoyl group, etc.)
, sulfamoyl group (e.g., N-ethylsulfamoyl group, N-octadecylsulfamoyl group, etc.), carbamoyl group (e.g., fl, N-ethylcarbamoyl i N
-methyl-rdecylcarbamoyl group, etc.), sulfonamide group (e.g., methanesulfonamide group, be/zene sulfonamide group, etc.), acylamino group (e.g., acetylamino group, hanzuamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group, etc.), imide group (e.g., succinimide group, hydantoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, etc.), human90xy group, cyano group, nitro group, and halogen atom. It may be substituted with a group.

R4□ represents an acylamino group or an alkyl group.

Acylamino groups include unsubstituted acylamino groups (eg, acetamido group, n-tetradecanamide group, ?-tridecanamide group, etc.) and substituted acylamino groups. As a specific example of the substituent of the substituted acylamino group, a phenoxy group is preferred, but the phenoxy group may be substituted.

Specific examples of substituents for the substituted phenoxy group include alkyl groups (e.g., methyl group, ethyl group, n-hexadecyl group, t-amyl group, etc.), halogen atoms (e.g., chlorine atom, fluorine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), cyano group, aryloxy group (e.g., phenoxy group, etc.), acylamino group (e.g., methanesulfonamide group, acetamide group, etc.), imide group (e.g., succinimide l n-octadecylsuccinimide group, etc.), sulfamoyl group ( (e.g. 1-jN-ethylsulfamoyl group, n-octadecylsulfamoyl group, etc.)
Examples include an alkoxycarbonyl group (eg, ethoxycarbonyl group), a sulfonyl group (eg, methylsulfonyl group, etc.), and a hydroxyl group.

The alkyl group is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group,
(t-butyl group, t-octyl group, etc.) t-represented.

R43 is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group (e.g., methyl group, ethyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), or an amide group (e.g. (acetamide group, methanesulfonamide group, etc.).

R4□ and R43 may be combined to form a 5t or 6-membered ring.

z4□ represents a hydrogen atom or a coupling-off group, examples of which include a norogen atom (e.g., heptad atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., dodenyloxy group, methoxycarbamoylmethoxy group) group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy7 group, 4-methoxyphenoxyx7 group, etc.), acyloxy group (e.g., acetoxy group, tetrazokayloxy group, etc.) group, benzoyloxy group), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy a [etc.), amide group (e.g., dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group) ), alkoxycarbonyloxy groups (e.g., ethoxycaponyloxy groups, hydroxycarbonyloxy groups, etc.), aryl-dicarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), aliphatic or aromatic thio groups (e.g.
phenylthio group, tetrazolylthio group, etc.), imide 9
groups (e.g., succinimide group, hydantoinyl group, etc.), N-heterocycles (e.g., l-pyrazolyl group, l-penztriazolyl group, etc.), aromatic azo groups (e.g., phenylazo group, etc.), etc. . These leaving groups may include photographically useful groups.

R4□ or R4□ in the general formula (■) may form a dimer or a multimer of more than that.

More preferable magenta couplers of general formulas (II) and ([1) are the following general formulas C, u-A) and (ill
-A), a more preferable cyan coupler of general formula (fV) is represented by the following general formula (fV-A) or (iV-B).

General formula (n-A) In the formula, R23 is a phenyl group having at least one chlorine atom? ◇ R24 represents an acylamino group or an imide group.

Z2□ represents a hydrogen atom or a phenylthio group.

At least one chlorine atom represented by R23? The phenyl group may have other substituents. Specific examples of the substituent include alkoxy groups (e.g., methoxy group, ethoxy group, etc.), amide groups (e.g., acetamide group, methanesulfonamido group, etc.), and alkyl groups (e.g., methyl group, ethyl group, etc.). 2.4.6-Dolichlorophenyl group is preferred.

The acylamino group represented by R24 is particularly preferably an unsubstituted acylamino group such as n-) lysokalylamino n-decanoylamino group or 2-ethylhexanoylamino group, or a phenoxy-substituted acylamino group. The phenyl group of the phenoxy-substituted acylamino group may have a substituent group. The substituents include halogen atoms (e.g., chlorine atoms, etc.), alkyl groups (e.g., t is methyl group, t-amyl group, t-octyl group, n-
methyl group, etc.), alkoxy groups (eg, methoxy 4, n-tridecyloxy group, nato)amide group (eg, n-)lysosylsulfonamide group, acetamide 9 group, etc.).

The imide group is preferably 9% succinimide group (for example, 3-octadecenyl-N-succinimide group).

The phenylthio group represented by z2□ may have a substituent, such as a halogen atom (such as a chlorine atom), an alkyl group (such as a methyl group, n-butyl i, n-octyl group, or t-butyl group). , t-amyl group, t-octyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, t-butoxy group, t-octyloxy group, etc.).

9 has alkoxy fund in 2nd place and 5 7-enzyme having a tertiary alkyl group in position A ruthio group is preferred.

General formula (Iu-A) In the formula, Z35 represents a hydrogen atom, a halogen atom, or an arylthio group.

R3□ represents an alkyl group, an alkoxy group or an aryloxy group.

x3□μ Represented as alkylene group, arylene group or aralkylene group.

R33 represents an aryl group or an alkyl group.

The alkyl group represented by R3° includes unsubstituted alkyl groups (eg, methyl group, ethyl group, t-butyl group, etc.) and substituted alkyl groups. Examples of #L-substituted alkyl group substituents include alkoxy groups (eg, methoxy group, ethoxy group, etc.) and aryl groups (eg, phenyl M, p-chlorophenyl, m-tridecanamidophenyl group, etc.). The alkoxy group includes unsubstituted alkoxy groups (eg, methoxy group, ethoxy group, etc.) and substituted alkoxy groups. Examples of the substituent for the substituted alkoxy group include the substituents listed above for the alkyl group.

The aryl group of the aryloxy group is left unplaced. Replaced aryloxy group (for example, phenoxy) ) and substituted aryloxy Contains groups. Specific examples of the substituents are Alkyl group (e.g. methyl group) Lucoxy group (for example, methoxy group, etc.) Halogen atoms (for example, chlorine atoms, etc.) Amide group (e.g. acetamide group, methane group) 9 groups of tansulfonamide, etc.).

R3□ is particularly preferably a methyl group or an ethyl group.

X3□ is an alkylene group (ethylene group, 2-methylpropylene group, etc.), an arylene group (such as Vi phenylene group, 2-chlorophenylene g, 2
-t-butylphenylene group, etc.), aralkylene groups (phenythyle/group, etc.).

The aryl group represented by R8 includes a phenyl group and a substituted phenyl group. Examples of the substituent include substitutable groups such as an alkyl group, an alkoxy group, a halogen atom, a sulfonamide group, a sulfamoyl group, an acylamide group, an alkoxycarbonyl group, a hydroxyl group, and a cyano group. Preferably, it contains at least one acylamide group. Examples include 2-ethoxy-5-t-octylbenzenesulfonamide V group, 9 groups of 2-n-butoxy-5-t-octylbenzenesulfonamide, and 9 groups of 2,5-di-t-acylphenoxyacetamide. It will be done.

General formula (IV-A) In the formula, R44 represents an alkyl group having 1 to 15 carbon atoms.

R45 represents an unsubstituted alkyl group having 1 to 32 carbon atoms or an aryloximit-substituted alkyl group having 7 to 32 carbon atoms.

The alkyl group having 1 to 15 carbon atoms represented by R44 may be either a straight chain or a branched alkyl group, and specific examples thereof include methyl group, ethyl group, n-propyl group, t-butyl group, n-decyl group, etc. It will be done.

The unsubstituted alkyl group having 1 to 32 carbon atoms represented by R45 may be either a straight chain or branched alkyl group, and specific examples thereof include methyl group, ethyl group, n-decyl group, n-tridecyl group, 2-ethylhexyl group, etc. The aryl group of the aryloxy-substituted alkyl group includes a phenyl group and a substituted phenyl group, and specific examples of the substituent include a halogen atom (e.g., chlorine atom, etc.), an alkyl group (e.g., a methoxy group, etc.), an amide group ( Examples include acetamido group, methanesulfonamide group, etc.) cyano group, hydroxy group, etc.

General formula (IV-B) In the formula, R46tR4□ is an open collar with R45 of general formula (fV-A).

R48 is an 8-deaf nonmetallic atom group that forms a 5- or 6-membered ring with a hydrogen atom, an alkyl group, R4□, or a carbon atom of a carbonyl group.

Examples of the nonmetallic atom group represented by R48 include an alkylene group and an amino group. When forming a 5- or 6-membered ring, R4□ is not present.

Next, specific examples of compounds of general formulas (11) to (IV) will be listed.

(II-1) Shini (it-16) ShiL (II-19) Cdan (ll1-1) (iff-2) Ji8M□7(t) (Ill-3) (Ill-5) (Ill -6) CIll-7) CIll-8) (Ill-t+) (Ill-10) (Ill-11) U-12) (Ill-14) CII+-15) (■-1) (IV-2) ( IV-3) H (IV-4) Shidan (IV-5) (1 yen-6) (IV-7) (!V-8) (IV-9) (■-11) Shini (fV-12 ) (to'-13) (IV-1=S) ([V-15) (1\-16) (fV-17) (~'-18) (IV-19) LA;i-13 (t) 08H17 ft) C5H11 (1'v'-27) (IV-29) (IV-30) The above general formula (S, further general formula (11) or (Il
The couplers represented by l) and (■) are usually present in the silver halide emulsion layer constituting the photosensitive layer in an amount of 90.1 to 1.0 mol, preferably 0.1 to 0.0, per 1 mol of silver halide. .5
Contains moles. Also, when comparing the amounts of each coupler represented by general formula (1), (II) or (lit), (IV), the molar ratio is usually about 1:0.2 to 1.5:0.5 to 1.
Although it is often in the range of 5, it is possible to design sensitive materials outside this range.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, for example, dibutyl phthalate,
After dissolving in a single or mixed solvent of a phthalate ester such as dioctyl phthalate, a high boiling point organic solvent such as a phosphate ester such as tricresyl phosphate and trinonyl phosphate, or a low boiling point organic solvent such as ethyl acetate, the interface Emulsify and disperse in an aqueous gelatin solution containing an activator. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. The low-boiling organic solvent may be removed from the coupler dispersion by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

In order to introduce the yellow coupler, magenta coupler, or cyan coupler of the present invention into the emulsion layer, for example, phthalic acid alkyl esters (dibutyl 7-thalerate, dioctyl-7
tallate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl 7),
male 7ate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl triztyl citrate), benzoic acid esters (e.g. octyl benzoate),
Alkyl amyl (e.g. diethyl laurylamide 3)
, fatty acid esters (e.g., diptoxyate, tylsuccioate, dioctyl azelate-containing 7-ethers (e.g., 2,4-di(1)amylphenol), etc. with a boiling point of 16
High boiling point organic solvents above 0°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, propio/ethyl acetate, 2, butyl alcohol, methyl in butyl ketone, β-ethoxyethyl acetate, methylseron lupus acetate, etc. Low-boiling organic solvents having a boiling point of 30°C to 150°C can be used alone or in combination as required.

General formula (1); (II) and (lit); (I
Two or more couplers can be selected from the group of same-hue couplers shown in V) and used in combination. In this case, the linear coupler can be co-emulsified or separately emulsified and mixed, and furthermore, the coupler can be used in combination with an anti-fading agent which will be described later.

The coupler represented by the general formula (IV) may be mixed with other known cyan couplers, but the coupler represented by the general formula (fV)
It is preferred that the mixing molar ratio of the cyan coupler is 30 or more, preferably 50 or more.

A preferred combination coupler is a phenolic cyan coupler described in Japanese Patent Publication No. 11572/1983.

In order to achieve object 1 of the present invention, the total weight ratio of the high boiling point organic solvent and the yellow coupler of the present invention is 1.0 or less, especially 0.
．． It is preferable to adjust it to 1 to 0.8.

It is preferable to optimize the amount of the high-boiling point solvent for the magenta coupler and cyan coupler, taking into consideration aspects such as the solubility of the coupler and the developability of the light-sensitive material.
It is set in the range of 10% to 300ch.

The photosensitive material of the present invention may contain a special coupler other than the coupler represented by the above general formula, if necessary. For example, a colored magenta coupler can be included in the green-sensitive emulsion layer to provide a masking effect. In addition, a development inhibitor-releasing coupler (DIR coupler) is contained in each color-sensitive emulsion layer or in its adjacent layer.
A development inhibitor-releasing hyperquinone or the like can also be used in combination. The development inhibitors released from these compounds during development bring about interlayer effects such as improvement of image sharpness, finer grains of images, and monochromaticity.

In the photographic emulsion layer of the present invention or its adjacent layer, a coupler that releases a development accelerator or nucleating agent upon silver development is added to improve photographic sensitivity, improve graininess of color images, and improve gradation. It is also possible to obtain effects such as increasing the contrast of images.

In the present invention, an ultraviolet absorber can be added to any layer.

Specific examples thereof include JP-B-44-29620, JP-A-50-151149, JP-A-54-95233, U.S. Patent No. 3.766,205, and EPOO57.
No. 160, Research Died-osure
225 19 (1983, /g225), etc. Also, JP-A-58-1119
42, Patent Application No. 57-61937, No. 57-63602,
It is also possible to use the high molecular weight ultraviolet absorbers described in Japanese Patent No. 57-129780 and No. 57i33371, and it is also possible to use a combination of low-molecular and high-molecular ultraviolet absorbers.

The above-mentioned ultraviolet absorber, like the coupler, is dissolved in a single or mixed solvent of a high-boiling point organic solvent and a low-boiling point organic solvent, and is dispersed in a hydrophilic colloid.

Although there are no particular limitations regarding the high-boiling organic solvent and the ultraviolet absorber, the high-boiling organic bath medium is usually used in an OI% range of 300% to the weight of the ultraviolet absorber.

It is preferable to use compounds that are liquid at room temperature alone or in combination.

When the coupler of the present invention is used in combination with the ultraviolet absorber gold,
It is possible to improve the storage stability, especially the color fastness, of color development images, especially cyan images. This ultraviolet absorber and cyan coupler may be co-emulsified.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is applied, it may cause yellowing of the white background of the color photographic material. Usually, it is preferably 1×10 mol/
n? 〜2×10 mol/d, especially 5×10 mol/d〜
It is set in the range of 1.5×10 mol/2.

In the light-sensitive material layer structure of normal color paper, either side adjacent to the cyan coupler-containing red-sensitive emulsion layer. -,
Preferably, both layers contain an infrared absorber.

When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a cord absorbent is added to the protective I-shield, another layer of protection may be applied as the outermost layer. This purulent storage layer can contain a matting agent of any particle size.

Each dye storage stabilizer for the magenta coloring dye of the coupler represented by the above general formulas (I1) and (ill),
Stain inhibitors or antioxidants are effective in improving storage stability.

These compounds are described in US Pat. Nos. 3,336,135 and 343.
No. 2300, No. 3573050, No. 3574627, No. 3700455, No. 3764337, No. 393
No. 5016, No. 3982944, No. 4254216, No. 4279990, British Patent No. 1347556, No. 2062888, No. 2066975, No. 20774
No. 55, % Application No. 58-205278, JP-A No. 52-1
No. 52225, No. 53-17729, No. 53-203
No. 27, No. 54-145530, No. 55-6321, No. 55-21004, No. 58-24141, No. 5
Synthesis methods and examples of compounds other than those listed above are described in Japanese Patent Publication No. 9-10539, Japanese Patent Publication No. 48-31625, and Japanese Patent Publication No. 54-12337.

These antifade agents are 2 to 2
00 molti is added. Preferably, these compounds are co-emulsified with magenta couplers.

The silver halide emulsion used in the present invention may be any of silver monide, silver bromide, and silver iodide, but silver chlorobromide, which does not substantially contain silver iodide, is particularly preferred. Substantially free of silver iodide means that the content of silver iodide is 3% of the total amount of silver halide.
It should be less than 1 mole, preferably less than 1 mole. More preferably it is 0.5 molar or less, and most preferably it does not contain any silver iodide. Containing silver iodide has many useful benefits in terms of photosensitivity, such as increasing the yield of the original plate, strengthening the adsorption of spectral sensitizing dyes, or weakening the desensitization caused by spectral sensitizing dyes. There are cases in which it is preferable to contain silver iodide, for example, in an amount of 1 molar or less, especially 0.2 molar or less, as compared to not containing it. Even in such a case, the fact remains that silver iodide itself delays the development of grains containing it, compared to silver chloride or silver bromide. Therefore, in the present invention, the company
Although it is basically preferable to use a silver halide emulsion that does not contain silver iodide, in cases where the above-mentioned problems occur, it may be advantageous to include a trace amount of silver iodide.

In the present invention, when silver chlorobromide is used, any composition ratio can be used, and it may be pure silver chloride, pure silver bromide, or an intermediate composition. They may also contain trace amounts of silver iodide as described above.

Silver chlorobromide emulsions having a silver bromide content of 10 moles or more are preferably used in the present invention. To obtain an emulsion with sufficient sensitivity without increasing the capri, the pure silver content should be 20
It is preferable to use molti or more, but if rapidity is required, it is also preferable to use 20 molti or less, or 10 molti or less.

In systems using the technology of the present invention, when particularly rapid speed is required, the silver bromide content is 3 molar or less, more preferably 1 molar.
It is more preferable to use a chlorinated metal containing substantially no silver bromide below the molar ratio.

Reducing the silver bromide content not only improves the speed of development, but also reduces the equilibrium accumulation in the developing solution, which is determined by the relationship with the amount of replenishment, when a light-sensitive material containing silver bromide is run in a processing solution. amount of bromide ion will be present in low concentration,
This is preferable because the rapid developability of the developer itself can be set high.

It is preferable that the silver bromide content of the emulsion be further increased, preferably 50 mole or more, for K to obtain a light-sensitive material that does not easily cause capri and exhibits stable gradations using the technique of the present invention. Furthermore, if it is 65 molt or more, a very stable emulsion can be obtained.
preferable. If the silver bromide content exceeds 95 molt, the rapid developability will decrease slightly, but V with a changed crystal grain shape (e.g. tabular grains, etc.), development accelerators (e.g. 3-pyrazolito, etc.), etc. Onythyls, hydrazines, etc.) can be used in combination to obtain a photosensitive material with high sensitivity and stable storage and processability without any interruption.

Developability of silver halide grains is determined not only by the halogen composition of the entire lamp grain, but also by the halogen distribution within the grain.

Therefore, in the present invention, the silver halide emulsion can have a distribution or structure regarding the halogen composition in its grains. A typical example thereof is a core-shell type particle or a double structure type particle, in which the interior and surface layers of the particle have different halogen compositions.

In such particles, the core shape and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the particle with the shell attached may be cubic or octahedral. On the other hand, the core may be octahedral and the shelled particle may be cubic or octahedral in shape. Further, although the core part is a clearly shaped grain, the shape of the shelled grain may be slightly distorted or irregular. Furthermore, it is possible to have not only a simple double structure but also a triple structure or a more multiple structure, or to apply a thin layer of silver halide having a different composition to the surface of a core-shell double structure grain.

In order to provide a structure inside a particle, it is possible to create a particle having not only the enveloping structure as described above but also a so-called bonding structure. The crystal to be bonded can have a composition different from that of the host crystal, and can be formed by bonding to an edge, part of a corner, or surface of the host crystal. Such a bonded crystal can be formed even if the host crystal is uniform with respect to the halogen group gK or has a structure such as a core-shell type. For example, particles with these structures may have a high silver bromide content in the core part and a low silver bromide content in the shell part in a core-shell type particle, or vice versa. It may be a particle with a low shell portion and a high shell portion. Similarly, for particles with a bonded structure, even if the host crystal has a high silver bromide content and the bonded crystal has a relatively low silver bromide content,
The opposite particles may be used.

However, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the shape of mixed crystals due to composition differences. It may also be one with continuous structural changes.

In the present invention, it is preferable to use an emulsion consisting of grains having some structure rather than one having a uniform halogen composition within the grains. In particular, particles having a halogen composition in which the steel bromide content is lower on the particle surface than on the inside of the particle are preferably used. A typical example is a core-shell emulsion in which the core contains a higher content of silver bromide than the shell. The constituent molar ratio of the core part and the shell part is between O:100 and 100:0, and n can be any ratio, but in order to make the structure clearly different from that of particles with a uniform structure, it is 3:97 to 98. :2 is preferable. When the shell part is formed by the solubility difference depending on the species of silver halogenide, 1 when the shell part is formed by the chloride conversion, especially when the chloride conversion is carried out using a water-soluble compound such as chloride. It is preferable that the ratio is less than 98:2.It is especially preferable that the ratio is less than 99:1.
In practice, it is difficult to uniformly cover the particle surface by logen conversion, and it tends to adhere unevenly to some corners and edges. In such halogen-converted particles, the halogen distribution becomes uniform due to, for example, Ostwald ripening, but even particles whose distribution has become uniform in this way and particles whose shape immediately after halogen conversion remains can be applied to the present invention. It is preferable as an emulsion to be used.

When core-shell type silver halide grains are used in a filter system using the technology of the present invention, the ratio of core to shell is more preferably between 5:95 and 95:5, and even more preferably between 7:93 and 95:5. It is between 90:10. Most preferably it is between 1s:85 and 80:20.

The difference in silver bromide content between the core part and the shell part varies depending on the molar ratio of the core part and the shell part, but it is preferably 3 molar or more and 95 molar or less.

More preferably, it is 5 molar or more and 80 molar or less. Most preferably it is between 10 and 70 moles. If the silver bromide content is not much different between the core and shell,
If the composition is not much different from particles with a uniform structure and the difference in composition is large, this is undesirable because it tends to cause performance problems. The appropriate composition difference depends on the composition ratio of the core part and the shell part, and is 0:
It is preferable that the closer the composition ratio is to 100 or 100:0, the larger the composition difference is, and the closer the composition ratio is to 1=1, the smaller the composition difference is.

The shape of silver chlorobromide used in the present invention is cubic as described above.
It may be a dodecahedron or a rhombic dodecahedron other than an octahedron, or it may have other shapes. In particular, in the case of bonded particles, bonded crystals may be formed uniformly on the corners, edges, or surfaces of the host crystal, and may have a regular particle shape, although they are not irregularly shaped. It may also be in its original state. In the present invention, octahedral particles are preferably used. Moreover, cubic particles are particularly preferably used. Tabular grains can also be used, but emulsions in which tabular grains with a ratio of yen-equivalent grain diameter to grain thickness of 5 or more and 8 or less occupy more than 50 mmoles of the total grain projected area have excellent rapid developability. . Even for such tabular grains, it is more advantageous to have a structure as described by Ail.

The average size of the grains of the silver halide emulsion used in the present invention (average diameter by volume equivalent method) is 0.1μ or less than 2μ.
The above is preferable. Particularly preferred is 1.4μ or less.0.
It is 15μ or more.

The grain size distribution may be narrow or broad, but monodisperse emulsions are preferred. In particular, monodisperse emulsions of regular or tabular grains are preferred for the present invention. Number of particles or '1L
85 of the total particles within ±20% of the average particle size at jJk
Emulsions containing 90% or more are preferred, especially emulsions containing 90% or more.

Particularly favorable results can be obtained by using two or more of such monodispersed emulsions, including cubic, octahedral and tetradecahedral monodispersed emulsions, in a mixture or in a multilayer coating.

The silver chlorobromide emulsion used in the present invention is P, G1afkides.
'f5 Chimie at Physique Ph
o℃ographique (Pau1Monte1, 1967), G, F', Pho by Guffin
tographic Emulsion Chem
istr7 (FocaIPress, 1966
), V, L, Zslikma eta1 Author Maki
ng and coating photography
It can be prepared using the method described in icEmulsion (published by Focal Press, 1964) and the like.

That is, the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. good. A method in which particles are formed under conditions of excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the silver ion concentration in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondral double jet method can also be used. According to this method, a monodisperse halogenated steel emulsion with a regular crystal shape and a narrow grain size distribution can be obtained.The above-mentioned grains preferably used in the present invention are prepared based on the simultaneous mixing method. This is desirable.

During the grain formation or physical ripening process Kb of silver halide, even if cadmium salts, curved lead salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or their complex salts, etc. coexist. good.

In particular, the iridium salt or its complex salt is 10 to 10 mol per mol, more preferably 10 to 10 mol per mol of silver halide.
1 mole is used. Compared to emulsions prepared without using iridium salts or their complex salts, this shows that
It is particularly useful for obtaining rapid developability and stability at high or low illuminance outside the t@ degree range.

Known silver halide solvents (such as salt, ammonia, potassium thiocyanate, or U.S. Pat.
No. 408, JP-A-53-144319, JP-A-54-
When physical ripening is carried out in the presence of thioethers and thione compounds described in JP-A No. 100717 or JP-A No. 54-155828 (isobaric), monodisperse chloride with a regular crystal shape and a narrow particle size distribution is produced. A silver emulsion is obtained.

In order to remove soluble salts from the emulsion after physical ripening, washing with water, Flokie sedimentation, ultrafiltration, or the like can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin, a sulfur sensitization method using a sulfur-containing compound that can react with silver ions (such as thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.), or a sulfur sensitization method using a reducing substance (
For example, reduction sensitization using stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.), and metal compounds (for example, total complex salts, Pt, hydrazine derivatives, P(1, Rh, Fe, etc.). A noble metal sensitization method using complex salts of metals of group Ⅰ of the periodic table, etc.) can be used alone or in combination.In the silver chlorobromide of the present invention, sulfur sensitization or selenium sensitization can be used. is preferably used, and it is also preferable to have a human 90-xiazaindene compound present during this sensitization.

In addition to the silver halide emulsion layer, retention layer, and intermediate layer, the light-sensitive material according to the present invention may optionally be provided with auxiliary layers such as a filter layer, an antihalation layer, and a backing layer.

Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
It is advantageous to use gelatin, but other hydrophilic colloids may also be used.

Preferred supports for the light-sensitive material of the present invention are reflective supports, such as baryta paper, polyethylene V-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective layer, For example, there are glass plates, polyester aluminum such as vinyl chloride resin, cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide 4 film, polycarbonate film, polystyrene film, etc., and these supports are used for each purpose of the photosensitive material. It is selected accordingly.

The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

A preferred example is a p-phenylenediamine fatty conductor, and representative examples are shown below, but the invention is not limited thereto.

(D-1) N,N-diethyl-p-phenyl diamine (D-2) 2-amino-5-diethylaminotoluene (D-3) 2-amino-5-(N-ethyl-
N-laurylamino)toluene (D-4) 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline CD-5) 2-methyl-4-[N-ethyl-N-(
β-hydroxyethyl)aminocoaniline (D-6)
4-Amino-3-methyl-N-ethyl-N-[β-(
Methanesulfonamide) ethyl-to-aniline (D-7) N-(2-amino-5-diethylaminophenylethyl) methanesulfonamide (D-8) N,N-dimethyl-p-7 22-diamine (1)- 9) 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline (D-10) 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline (D-11) 4- Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline Among the above p-phenylenediamine salt conductors, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyltoaniline (exemplified compound D-6).

Further, these p-7 22-diamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of nuclear aromatic-grade amine developing agent used is preferably from about 0.19 to about 20.9% per 11 parts of the developer solution.
A concentration of about 0.59 to about 109 is most preferred.

The color developer preferably has an Fi of 9 to 12, more preferably Fi of 9 to 11.0. Preservatives, buffering agents, chelating agents, development accelerators, anti-capri agents that can be added to color developers,
F of fluorescent whitening agent! For details such as type and stock weight, see page 11 of the application specification of patent application (A) dated March 18, 1986 (Fuji Photo Film application; title of invention "Color image forming method")]9 It is written on the page.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds to 5 minutes.
Preferably it is 30 seconds to 2 minutes.

The smaller the amount of replenishment, the better;
0~600ral, good 1t, <h50~300rnl
There is. More preferably 100-200t6! It is.

The desilvering step in the present invention will now be explained.

In general, any process such as a bleaching process, a fixed fixing process, a fixing process-bleach-fixing process, a heading process-bleach-fixing process, an opening-fixing process, etc. may be used for the process of removing the bride. The desilvering step takes 2 minutes or less, more preferably 15 seconds to 90 seconds.

Regarding the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention, as well as additives to these solutions and information thereof, for example, those described on pages 20 to 25 of the application specification mentioned above can be applied. can.

Moreover, the matters described on page 25 to page 29, line 12 of the application specification can also be applied to the filtering water washing and/or stabilization treatment performed after the desilvering treatment.

The method of the present invention includes a process using a color developer,
It can be applied to any processing process. For example, color Eno sign, color reversal Eper, color direct positive photosensitive material,
It can be applied to the processing of color positive films, color negative films, color reversal films, etc., and is particularly preferably applied to color -bar and color reversal papers.

(Example) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution preparation yellow coupler (example coupler: (1-1)) 19.
19 and color image stabilizer (exemplary compound: l-9)) 4.4
9, 27.2 CC of ethyl acetate and solvent (S01v-0
7,70C was added and dissolved, and this solution was emulsified and dispersed into 10 Tigelatin aqueous solution 1850CK containing 8CC of 10% sodium dodecylbenzenesulfonate. On the other hand, in a chlorobromide recording emulsion (containing 80.θ mol of silver bromide, 71/d of Ag), the blue-sensitive sensitizing dye shown below was added at 5.0×1 per mol of silver.
A sample containing 0 mol was prepared.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. From the second layer to the seventh! The coating solution for - was also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1-oxy-
3,5-dichloro-〇-triazine sodium salt was used.

The following explosives were used as spectral sensitizing dyes in each layer.

Blue-sensitive emulsion layer (5.OX]O mol per 1 mol of silver halide) Edge-sensitive emulsion layer (4.0 x 10 mol per mol of silver halide)
and (tarif per mole of halogenated compound, 0X10-5 mole) for the red-sensitive emulsion layer (0.9X10 mole per mole of halogenide) For the red-sensitive emulsion layer, the following compounds are halogenated
2.6 X 10 moles were added per mole.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the non-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole"h was 4.0xlO mol per mol of silver halide, 3.0 ×10 mol, 1.0X1
0 mol was added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added at a concentration of 1.2×lθ per mole of silver chloride, respectively.
Mol, 1. 1×10 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and A (layer structure) The composition of each layer is shown below. The numbers represent coating f (9/m''). Silver halide emulsions represent coating t in terms of silver.

Support polyethylene laminate paper [white pigment (T10□) and reality dye (contains clusters in polyethylene on first layer side) First layer (blue sensitive layer) Silver halide emulsion (Br: 80%) 0.26
Gelatin 1.83 Yellow coupler (Exemplary coupler (1-1)) 0.83 Color image stabilizer (Exemplary compound (Vl-9)) 0.1
9 Solvent (Solv-1) 0.3
5 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-2) o, os third Jm
# (Green sensitive layer) Silver halide emulsion (Br: 809J) 0.
16 Gelatin 1.79 Macentacap 5- (EXM) 0.3
Two-color image stabilizer (Cpd-3) 0.20 Color image stabilizer (Cpd-4) 0.01 Solvent (5olv-2) 0.65 Fourth layer (ultraviolet absorption) Gelatin 1.58 Ultraviolet absorption Agent (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Sol
v-3) 0.24 Fifth) - (Red-sensitive layer) Silver halide emulsion (Br near 0%) 0.2
3 Gelatin 1,34 Cyan coupler (EXC) 0.34 Color image stabilizer (Cpa-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (S
olv-4) 0.23 6th layer (ultraviolet absorption layer) Gelatin 0.54 ultraviolet i
Absorbent t, tJv-1) 0.21 Solvent (
Solv-3) 0.08 seventh! −
(Retaining film layer) Gelatin 1.33 Polyvinyl alcohol acrylic 0.17
Modified copolymer (degree of modification 17%) Liquid paraffin 0.03 Yellow coupler (Example coupler (1-1)) H3 Magenta coupler (Example coupler (ll-29)) U8
1-11□ta Cyan coupler (Example coupler U-1) 1 (Vl-9) Color image stabilizer (Cpd-2) Color mixture inhibitor H (Cpa-3) Color image stabilizer - (Cpd-4) Color image stabilizer (Cpa-5) Color mixture prevention agent H (Cpa-6) 5:8:9 mixture (weight ratio) of color image stabilizer (Cpd-7) Polymer-(-CH2-CH C0NHC4H8(t) Average molecular weight 80,000 (UII) 2:9:8 mixture of UV absorbers (weight ratio) (5o1v-1) Solvent (5o1v-2) 2:l mixture of solvent (volume ratio) (5olv-3) Solvent 0=P (-0-C,H,, (180) )3(Sol
The sample obtained in this manner was designated as 100.

Next, as shown in <ff-1>, the yellow coupler and color image stabilizer in the first layer, the magenta coupler in the third layer, and the cyan coupler in the fifth layer were changed, and sample 101 was prepared in the same manner.
Friend who adjusted ~130.

size
1-2X Φ-m N
-ζ After passing the light-sensitive material through an optical wedge and exposing it to g light, it was processed in the next step.

Process Temperature Time Color development
38℃ 1 minute 40 seconds white constant 9
30~34℃ 1 minute OO seconds ■ 30~
34℃ 20 minutes■ 30~34
℃ 20cm■ 30~34℃
Dry for 20 seconds at 70-80℃
Rinse for 50 seconds (3-tank countercurrent method from rinsing ■ to ■).

) The composition of each treatment liquid is as follows.

Water 800
W1t diethylenetriaminepentate acid 1. (19]-Hydroxyethylidene-1,]-diphosphonic acid (60%) 2.
0g nitrilotriacetic acid
2.0g triethylenediamine (1,4-diazabicyclo(2,2,2)octane) 5.
09 Potassium bromide 0.59
Potassium carbonate 309N-ethyl-N-(-methanesulfonamidoethyl)-3-
Methyl-4-aminoaniline sulfate
Add 5.5g diethylhydroxylban and 4.09 liters of water.
1000+ILlpH (25℃) 10.25 Bleach-fix water 40
0al ammonium thiosulfate (70%)
20OtJ sodium sulfate
209 Iron (lu) ammonium ethylenediaminetetraacetate 609 Add water
1000aJpi ((25℃)
7.00 Rinse solution with ion-exchanged water (calcium and magnesium are each 34 or less) For each sample with a colored dye image formed by the above method, the maximum concentration of each color and the original storage stability and heat storage stability were determined. Please pray for the 9th prisoner of the trial according to the instructions in (a) and (b) below.

(a) Light storage property Xenon fade meter 8.5X10 lux 10 days in the dark) Insulation storage property 100°C Calorie No. ) - # after testing against 1,0!
The results, expressed as average percentages, are shown in Table 2.

As is clear from Table 2, the sample of the present invention (100
~115) are samples (116~13) using comparative couplers.
0), superior performance in terms of image color balance, original storage stability, and insulation storage stability'? ：I found out that it is lower.

(Effects of the Invention) According to the present invention, a multilayer silver halide color photographic photosensitive material which has good color development properties and improved image storage stability, and in which the color balance does not change even when exposed to light for a long period of time. materials can be obtained.

,−“, (′、′　・ Agent: Patent attorney (8107) Kiyotaka Sasaki;.

(3 others)

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material having blue-sensitive, green-sensitive and red-sensitive photosensitive layers on a support, at least one coupler represented by the following general formula (I) and the following general formula are added to the blue-sensitive photosensitive layer. A silver halide color photographic material containing at least one compound represented by formulas (V) and (VI). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_1 represents an alkyl group. R_1_2 represents a hydrogen atom or an alkyl group. R_1_3 represents a hydrogen atom, an alkoxy group, or an alkyl group. When R_1_2 is a hydrogen atom, R_1_3
represents an alkoxy group or an alkyl group. R_1_4 represents a chlorine atom or an alkoxy group. X_1_1 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. ) General formula (V) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_5_0 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or a trialkylsilyl group. R_5_1, R_5_2, R_5_3, R_5_4 and R_5_5 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an amino group, an imino group or an acylamino group. ) General formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_6_1, R_6_2, R_6_3 and R
_6_4 may be the same or different and each represents a hydrogen atom or an alkyl group. X_6_1 represents a hydrogen atom, an alkyl group, an acyl group, an oxy radical group, or a hydroxyl group. A_6_1 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring. ) (2) The green-sensitive emulsion layer contains at least one coupler represented by the following general formulas (II) and (III), and the red-sensitive emulsion layer contains at least one coupler represented by the following general formula (IV). Claim No. 1 containing seeds
) Silver halide color photographic light-sensitive material described in item 2. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 represents an alkyl group, aryl group, acyl group, or carbamoyl group. R_2_2 represents an aryl group. General formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_3_1 represents a hydrogen atom or a substitutable group. Z_3_1 represents a hydrogen atom or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent. Z_3_2, Z_3_3 and Z_3_4 have ▲numerical formulas, chemical formulas, tables, etc.▼, -N= Or it represents NH-, and the Z_3_4-Z_3_3 bond and Z_3_3-Z_3_
One of the two bonds is a double bond and the other is a single bond. The case where Z_3_3-Z_3_2 is a carbon-carbon double bond includes the case where it is part of an aromatic ring. ) General formula (IV) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4_1 represents an alkyl group, aryl group, amino group, or heterocyclic group. R_4_2 represents an acylamino group or an alkyl group. R_4_3 is hydrogen Represents an atom, a halogen atom, an alkyl group, an alkoxy group, or an amide group. R_4_2 and R_4_3 may be combined to form a 5- or 6-membered ring. Z_4_1 is a hydrogen atom or an oxidized aromatic primary amine color developing agent. (represents a group that can be separated in a reaction with a body)