JPH0233144A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproducibility and developability and to reduce rise of stains on unexposed areas by incorporating a 5-pyrazolone coupler having at the coupling position a specified group in the silver halide color photographic sensitive material and specifying an average particle diameter of this emulsified dispersion. CONSTITUTION:The silver halide photosensitive material contains the emulsified dispersion having an average particle diameter regulated to <=0.25mum, and an anionic or nononic surfactant and the like, and the 5-pyrazolone coupler having at the coupling position the releasable group represented by general formula (I) in which each of L1 and L2 is methylene or the like; each of l and m is 0 or 1; R1 is H, alkyl, or the like; R2 is a C or O atom or the like; A is a bonding group, such as a C or S atom; n is 1 or 2 according to A; B is a C or O atom or the like; and X is an atomic group necessary to form a ring.

Description

Detailed Description of the Invention (Technical Field of Application of the Invention) The present invention relates to a silver halide photographic light-sensitive material, which has particularly excellent color reproducibility and color development, and which exhibits no increase in staining in unexposed areas after processing. This relates to a silver halide photographic light-sensitive material with a small amount of silver halide.

(Prior Art) In order to form a color photographic image, photographic couplers of three colors, yellow magenta and cyan, are contained in a photosensitive layer, and after exposure, the layer is processed with a color developing solution containing a color developing agent. In this process, the oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a coloring dye, and the coupling rate at this time is as high as possible to give high color density within a limited development time. It is preferable to use color-developing dyes with good color development properties.Furthermore, the color-developing dyes are all vivid yellow, magenta and cyan dyes with little side absorption, and are required to provide color photographic images with good color reproducibility.

In the above, the coupler plays a major role, and many improvements have been made by changing the coupler structure.In the past, 5-pyrazolone derivatives were mainly used as the magenta coupler, which is important from the viewpoint of visibility. There is.

Examples of 5-pyrazolone derivatives include those described in US Patent No. 3.
419.391, Japanese Patent Publication No. 53-46453, U.S. Patent No. 4.076.533, U.S. Patent No. 4.241.168, U.S. Patent No. 4.220,470, U.S. Pat.
No. 3. 227. No. 554, No. 4.263,
No. 723, Japanese Patent Publication No. 53-34044, U.S. Patent No. 3,
It is described in No. 214.437, No. 4.032.346, etc.

Among these magenta couplers of 5-pyrazolone derivatives, there are those that give high color density within a limited time, so-called excellent color development properties, but they do not cause staining (increase in color density in unexposed areas) due to development processing. It has the disadvantage of causing In particular, the magenta coupler having a leaving group represented by the general formula (1) described in International Application Publication No. WO 38104795 had excellent color development, but the increase in stain was large.

Stain in the unexposed areas of silver halide color photographic materials not only determines the quality of the white areas in the image, but also makes the color stain of the color image worse and impairs visual sharpness, which is undesirable. In the case of materials (for example, color paper), the reflection density of the stain is theoretically enhanced several times as much as the transmission density, and is a very important factor because even a weak stain will impair image quality.

The occurrence of stain in silver halide color photographic materials is roughly classified into four types depending on the cause. One is caused by heat and temperature after the unprocessed photosensitive material is manufactured and before it is processed, two is caused by development fog of silver halide, and third is development processing solution for color couplers. (e.g. air fog), or the developing agent remaining in the emulsion film is oxidized by the subsequent bleaching bath or oxygen in the air, reacts with the coupler, and becomes a dye (e.g. bleaching The stain caused by the development process of the 2-equivalent magenta coupler related to the present invention is as follows:
It means 3 and 4 sting.

An even more difficult point is that the developing solution is rarely newly prepared for each developing process, and in reality, the developing solution is replenished according to the amount of development process. However, the liquid composition cannot be maintained only by replenishing the water lost during development.

That is, the processing solution usually consists of a color developing solution, a stop solution, a bleach solution, a fixing solution, a bleach-fixing solution (Blix), etc., but in order to maintain the processing temperature at a high temperature such as 31 to 43 ° C. , the developing agent may decompose over a long period of time, oxidize due to contact with air, eluates from the photosensitive material may accumulate during processing, and processing liquid may adhere to the material. The composition of the processing liquid changes due to factors such as being carried into the next bath, and becomes what is called a running liquid. For this reason, efforts are being made to replenish the missing chemicals by adding additional chemicals and regenerating by removing unnecessary materials, but this is not perfect.Sensitive materials containing 2-equivalent magenta couplers are prone to staining with such running fluids, and conventional No technology could prevent this phenomenon at all.

For example, methods for preventing such staining include the use of reducing agents, particularly alkylhydroquinones (e.g., U.S. Pat.
35.016, US Pat. No. 3,960.570, etc.) in the sensitive material, and especially in the emulsion layer where stain occurs, it has been known to be effective. Also, chromans, coumarans (for example, U.S. Patent 2
, 360゜290), phenolic compounds (Japanese Unexamined Patent Publication No. 1973
1-9449) etc. were also considered effective. Furthermore, sulfinic acid polymers are also known to be effective (Japanese Patent Application No. 55,085/1985). However, although these conventional techniques have some effect on stains treated with 5-pyrazolone magenta couplers, particularly stains treated with fatigue liquids, they have not been able to achieve the necessary and sufficient effects.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a silver 10-genide photographic light-sensitive material that has excellent color reproducibility, excellent color development, and less increase in staining in unexposed areas after processing. Our goal is to provide the following.

(Means for Solving the Problems) As a result of extensive research, the inventors have found that the above purpose has been achieved.
In a silver halide photographic material having a small number of light-sensitive silver halide emulsion layers on a support, the silver halide photographic material has a leaving group represented by the following general formula (2) at the coupling position. This is effectively achieved by a silver halide photographic light-sensitive material containing a 5-pyrazolone coupler having the following properties, and wherein the average particle diameter of an emulsified dispersion containing the coupler is 0.25 μm or less. I found out.

(Detailed Description) Each substituent in general formula (1) will be described in detail below.

L, Tori, represents a substituted or unsubstituted methylene or ethylene group. Substituents include halogen atoms, alkyl groups (straight chain and branched chain alkyl groups having 1 to 22 carbon atoms, etc.), alkoxy groups (methoxy, ethoxy , cyclohexyloxy, etc.), aryloxy groups (phenoxy, p-methoxyphenoxy, p-methylphenoxy, etc.), alkylamino groups (dimethylamino, dibutylamino, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), carbamoyl groups (such as N, N-dimethylcarbamoyl), sulfamoyl (such as N, N-diethylsulfamoyl), alkylsulfonyl groups (such as N, N-dimethylsulfamoyl),
methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl groups (phenylsulfonyl, tolylsulfonyl, p-methoxyphenylsulfonyl, etc.), acyl groups (
(acetyl, benzoyl, etc.), hydroxyl group, cyano group, etc., and is preferably an unsubstituted methylene or ethylene group. l and m represent 0 or 1, preferably 0.

R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; specifically, a hydrogen atom, an alkyl group such as a straight chain or branched alkyl group having 1 to 22 carbon atoms, or an aryl group such as a phenyl group or a naphthyl group. or heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyrimidinyl and 4-pyridyl groups, which may further bear substituents as defined in Lt, Lx, preferably R6 is They are a hydrogen atom and an alkyl group.

R2 represents a group connected through a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom; specifically, an alkyl group, an aryl group, a heterocyclic group (connected through carbon), an acyl group, an alkoxycarbonyl group, a carbamoyl group, etc. Groups linked via carbon atoms; groups linked via oxygen atoms such as alkoxy, aryloxy; alkylamino group, anilino group, acylamino group, ureido group, sulfamoylamino group,
Represents a group linked via a nitrogen atom such as an alkoxycarbonylamino group or a sulfonamide group, and a group linked via a sulfur atom such as an alkylthio group or an arylthio group.

Similar to Rt, these may further have the substituents defined for Lt and Lt, and other rings may be condensed to the ring containing X.

Rt and R, may be combined with each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring, and the substituents defined in LllLm may be added to these rings. It may further have a group.

When B is a carbon atom or a nitrogen atom, B and R2 may be combined with each other to form a ring (preferably a 5- or 6-membered saturated or unsaturated ring, more preferably a 5- or 6-membered saturated or unsaturated ring). is 5
Alternatively, a 6-membered saturated ring may be formed, and these rings may further have a substituent defined in L1%Lx.

A first preferred pyrazolone coupler can be represented by the following general formula.

In this catalytic formula, Yl represents R, or Z, R,
R represents a substituted or unsubstituted allyl or heterocyclic group, and R represents an oxygen atom, a sulfur atom, or NR,
Rb represents a substituted or unsubstituted alkyl, aryl, or heterocyclic group * Re % Ra is a halogen atom, R1
and eRa represents a group selected from the groups 2 and R1, and represents a hydrogen atom, or a group defined by Rc, R, R
f represents a hydrogen atom and a group defined by R5, or represents an oxygen atom, a sulfur atom, or N Rb, R9 is R
Represents a group defined by e. Rh represents the group defined for R1, Rc may be combined with at least one of R4 and Ro to form one or two carbocycles or heterocycles, which further have a substituent. -R+,
and These groups preferably contain an oil-solubilizing group.

R4 is a substituted or unsubstituted 7-aryl group, preferably a substituted phenyl group, and more preferably a 24.6-dolychlorophenyl group.

A more preferred pyrazolone coupler of this type can be represented by the following general formula. In this - pattern hole R1+ R2, R4, Rc, R,.

R, , X and B have the same meanings as the above substituents.

A second preferred pyrazolone coupler can be represented by the following general formula.

1.He/ShiN NHR% In this crest, R3 represents a substituted or unsubstituted alkyl, aryl, or heterocyclic group eRI+R*, Ra,
X and B have the same meanings as the substituents, atomic groups, and atoms described above. Preferably, R1 is a group represented by -NHYm, and R4 is a 24.6-)lichlorophenyl group.

Yt represents a substituted or unsubstituted aryl, arylcarbonyl or arylaminocarbonyl group.

A third preferred pyrazolone coupler can be represented by the following general formula. In this hole, Ri, R
s, Ra and X are the same as the above substituents and atomic groups; a YS represents substituted or unsubstituted methylene, ethylene and >NR; Rt is the same as the above substituents. A more preferable pyrazolone coupler of R4 can be represented by the following general formula. In this hole, R+, Rs and R4 have the same meanings as the above substituents *Rh, R? represents an alkyl group or an aryl group, Re represents a substituent defined for L+ and Lx above, D represents a methylene group, an oxygen atom, a nitrogen atom or a sulfur atom, n is 0 in the case of a methylene group.
p represents an integer from 0 to 2, otherwise it represents 1, and p represents an integer from 0 to 4.

In the following, the term "coupler part" refers to the part excluding the coupling-off group, and the term "coupler" refers to the whole including both the coupler part and the coupling-off group.

"Coupler moieties" are commonly used in the photographic industry to react with oxidized color developing agents to form dyes, especially magenta dyes.
It is a known and used pyrazolone coupler. Examples of preferred pyrazolone coupler moieties include, for example, U.S. Pat.
．． 4336325.4199361.4351897.
43851) 12 Japanese Patent Publication No. 60-170854.60-1
94452.60-194451, U.S. Patent 44079
36.3419391.331) 476, British Patent 13
57372, U.S. Patent 2600788.2908573
．． 3062653.3519429.3152896.
231) 082.2343703.2369489 or the inventions cited in these patents. In these patents, when a portion of the pyrazolone coupler is substituted with a coupling-off group, they can be replaced with a coupling-off group represented by the general formula N> of the present invention.

The pyrazolone couplers of the present invention can also be used in combination with other pyrazolone couplers such as those described in the above-referenced patents.

An example of a preferred "coupler moiety" can be represented by the following general formula. In this maximum, QRl (1 represents the coupling-off group of the invention. R1 represents anilino, acylamino, ureido, carbamoyl, alkoxy, allyloxycarbonyl, alkoxycarbonyl or N-heterocyclic group.

R1° is a substituted or unsubstituted allyl group, preferably a phenyl group having at least one substituent selected from a halogen atom, alkyl, alkoxy, alkoxycarbonyl, acylamino, sulfamide, sulfonamide, and cyano group. The carbon and nitrogen atoms of these substituents may be unsubstituted or substituted with a group that does not reduce the effect of the coupler. is preferably an anilino group, more preferably an anilino group represented by the following general formula. In this pattern, R1) is an alkoxy group having 1 to 30 carbon atoms, an allyloxy group, or a halogen atom (preferably a chlorine atom).

R+g and R13 are hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom, fluorine atom), alkyl group (
For example, alkyl groups having 1 to 30 carbon atoms), alkoxy groups (
For example, alkoxy groups having 1 to 30 carbon atoms), acylamino groups, sulfonamide groups, sulfamoyl groups, sulfamide groups, carbamoyl groups, diacylamino groups, allyloxycarbonyl groups, alkoxycarbonyl groups, alkoxysulfonyl groups, allyloxysulfonyl groups, alkanes A sulfonyl group, an allenesulfonyl group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an alkylureido group, an acyl group, a nitro group, and a carboxy group.For example, R1) and R13 may each be a hydrogen atom or a ballast group. good.

R1) is preferably a substituted phenyl group. Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), alkyl groups having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, propyl group/t-butyl group, tetradecyl group), and 1 to 22 carbon atoms. -22 alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy), carbon number 1-2
3, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tetradecyloxycarbonyl group), an acylamino group (for example, an α-[3-pentadecylphenoxybutyramide group) and/or a cyano group. R5° is more preferably 2,4.6-)
It is a lychlorophenyl group.

RI! , R13 in more detail, these are hydrogen atoms, halogen atoms (e.g. chlorine atoms, bromine atoms,
fluorine atom), a linear or branched alkyl group having 1 to 30 carbon atoms (e.g. methyl group, trifluoromethyl group, ethyl group, t-butyl group, tetradecyl group), 1 to 30 carbon atoms
alkoxy group (e.g. methoxy group, ethoxy group, 2-
ethylhexyloxy group, tetradecyloxy group), acylamino group (e.g. acetamido group, benzamide group, butyramide group, tetradecaneamide group, α-(2,
4-di-t-pentylphenoxy)acetamido group, α
-(2,4-di-t-pentylphenoxy)butyramide group), α-<4-hydroxy-3-t-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2-oxy- 5-tetradecyl-pyrrolin-1-yl group, N-methyltetradecanamide group, t
-butylcarbonamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyltetradecylsulfonamide group, hexadecanesulfonamide group group), sulfamoyl group (e.g. N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N,N-dimethylsulfamoyl group, N-(3-(dodecyloxy)propyl))
Sulfamoyl group, N-(4-(2,4-di-1-pentylphenoxy)butyl)sulfamoyl, N-methyl-N-tetradecylsulfamoyl group, N-dodecylsulfamoyl group), sulfamide group (e.g. N-methylsulfamide group, N-octadecylsulfamide group)
, carbamoyl group (e.g. N-methylcarbamoyl group,
N-octadecylcarbamoyl group, N-(4-(2,4
-di-t-pentylphenoxy)butyl)carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, N
, N-dioctylcarbamoyl group), diacylamino group (e.g. N-succinimide group, N-phthalimide group,
2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, N-acetyl-N-dodecylamino group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-dodecyloxyphenoxy carbonyl group), alkoxycarbonyl group having 2 to 30 carbon atoms (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarbonyl group), alkoxysulfonyl group having 1 to 30 carbon atoms (
For example, methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, 2-ethylhexyloxysulfonyl group), oryloxysulfonyl group (e.g. phenoxysulfonyl group, 2゜4-di-t
-pentylphenoxysulfonyl group), carbon number 1-30
alkanesulfonyl group (e.g. methanesulfonyl group,
octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group), arenesulfonyl i (e.g. benzenesulfonyl group, 4-nonylbenzenesulfonyl group, p-)luenesulfonyl group), carbon f
&1 to 22 alkylthio groups (e.g. ethylthio group, octylthio group, benzylthio group, tetradecylthio group,
2-(2,4-di-t-pentylphenoxy)ethylthio group), arylthio group (e.g. phenylthio group, p-
tolylthio group), alkoxycarbonylamino group (e.g. ethoxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group), alkylureido group (e.g. N-methylureido group, N,N-dimethylureido group, N- Methyl-N-dodecylureido group, N-hexadecylureido group, N, N
-Dioctadecylureido group, N, N-dioctyl-
N'-ethylureido group), acyl group (e.g. acetyl group, benzoyl group, octadecanoyl group, p-dodecanamidobenzoyl group, cyclohexanecarbonyl group),
They are a nitro group, a cyano group, and a carboxy group.

To explain in more detail the alkoxy group and allyloxy group of R1), the alkoxy group includes methoxy group, ethoxy group, propoxy group, butoxy group, 2-methoxyethoxy group, 5ec-butoxy group, hexyloxy group, 2-ethylhexyloxy group. group, 2-(2,4-';-t-pentylphenoxy)ethoxy group, 2-dodecyloxyethoxy group, and the aryloxy group is phenoxy group, α- or β-naphthyloxy group, 4-tolyloxy group. .

A monomer containing a pyrazolone coupler having a leaving group represented by formula (1) is a copolymer with a non-chromogenic ethylene-like monomer that does not couple with the oxidation product of an aromatic-grade amine developer. You can make it.

Acrylic acid, α
- chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate)
, acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether) ), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-
pyrrolidone, N-vinylpyridine, and 2- and 4
-Vinylpyridine, etc. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more. For example, butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate. and diacetone acrylamide.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Next is the general ceremony [! ] is a coupling-off group (Q
), but the invention is not limited to these.

Q-1) Q-2) Q-3) Q-7) Q-20) Q-21) Q-22) Q-31) Q-32) Q-26) -m Q-28) Q-29) Q-30) Q - stamen) Q-40) Q-41) Q- Minoru) Q-43) Q-44) Q-45) Q-52) Q-46) c*　H.

1)゜shiall+? (i) Q-56) QCs H+t(n) Next, specific examples of the coupler of the present invention will be shown, but the coupler is not limited thereto.

(M-1) CM-2) (M-5) (M-6) Hs (M-3) L;z (M-4) Hs (M-7) Hs Shil Hs Hs Hs Hs (M-9) (M-10) (M (M-14) Hs H3 (M-1)) CM-12) (M-1ri) (M-16) CM H3 (M-17) (M-18) (M (M-22) C gHs (M-19) (M-20) (M-23) (M-24) Cz　Hs Cz)Is (M-26) (M-29) CM-30) (M-27) (M-31) (M-32) CM-33) (M-34) (M-37) H3 (M-36) CM-39) (M-40) ShiL CM-41) (M-42) (M-45) death! (M-43) (M-44) CM-47) (M-48) CH3 CH3 CH3 Cβ OCH.

(M-49) CM-50) I (M-51) (M-52) CM-56) (M-57) I (M-58) The treatment stain prevention effect of the present invention is achieved by Further improvement can be achieved by using a combination of at least one selected from anionic surfactants, nonionic surfactants, and betaine surfactants and a fluorine-based surfactant as the surfactant used. Further, by using these surfactants in combination, the maximum color density of the magenta color image can also be further increased.

These surfactants are preferably used together when emulsifying and dispersing the magenta coupler having a leaving group represented by the general formula (1) of the present invention.

Examples of the anionic surfactant according to the present invention include those represented by the following symbols [A-1] to [A-Vll].

General formula [A-IF [wherein R and R1 each have 1 to 1B carbon atoms]
represents an alkyl group, M represents a hydrogen atom or a cation, rnl is an integer of 0 to 50, and n is 0
represents an integer of ~4, ll represents 0 or 1] General formula [A-IIF R3(C), 0(CHxClbQhu (CHt+
-1) tsOJ [wherein R1 represents an alkyl group or alkenyl group having 6 to 20 carbon atoms, M represents a hydrogen atom or a cation, ml is an integer of 0 to 50, n
, represents an integer of 0 to 4, and a represents an integer of 0 or 1. ] General formula [A-I1)] [In the formula, R4 and R6 each have 6 to 18 carbon atoms
represents an alkyl group, and M represents a hydrogen atom or a cation.] General formula [A-IV] OR? R6-CN*CHt), sX [wherein, R6 represents an alkyl group having 6 to 20 carbon atoms, R9 represents an alkyl group having 1 to 4 carbon atoms,
represents 1000M or 13OzM, M represents a hydrogen atom or a cation, and n represents an integer from 1 to 4. ] General formula [AV] I R@ -0-C-CH! R* 0-CCHS()+M [In the formula, R1 and R each have 6 to 20 carbon atoms
1 represents an alkyl group having the general formula [A-Vll K++ )3M [wherein R16, Ro and R+g each represent an alkyl group having 1 to 16 carbon atoms, and M represents a hydrogen atom or kachen; M represents a hydrogen atom or a cation.] Examples of the alkyl group having 1 to 18 carbon atoms represented by R3 and R1 include methyl group, ethyl group, butyl group, octyl group, decyl group, dodecyl group, octadecyl group, etc. can be mentioned.

6 carbon atoms represented by R3, R4, R. and R9
-20 alkyl groups include, for example, hexyl, heptyl, octyl, dodecyl, octadecyl, eicosyl, and the like.

Examples of the alkyl group having 6 to 18 carbon atoms represented by R4 and R3 include hexyl group, heptyl group, dodecyl group, pentadecyl group, and octadecyl group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R1 include atomic methyl group, ethyl group, propyl group, butyl group, and the like.

R1 Ro and R1! 1 to 1 carbon atoms represented by
Examples of the alkyl group of 6 include methyl group, ethyl group,
Examples include butyl group, decyl group, dodecyl group, hexadecyl group, and the like.

Each alkyl group represented by R1 to R1 includes those having a substituent, and in this case, the number of carbon atoms does not include the substituent.
Among those represented by the general formula [A
-IF, [A-■] and [A-Vl.

A specific example is shown next.

C+tHzs O(CHi CHt O)-a (C
Hgto3 SOS KC+iH. s-0-(CHz C
HtOfs-(CHs)-a 303 NaC
+zHtsOSOs Na C+iHzs C) (CHz CH wealth O) -s So
w NaC++Hts C-C) (CHz CHg
O)-m SOs NaC+zHgsC O(CHi
CHt Otos (CHx) s 301 Na
I C9 H+* O C CHt C9 Hl? O-C CH SO3 NaCs
HIIOCOCH SO3 NaC,. Hx+OC
OCHi C寞H.

Ca H* CHCHt OCOCH SOs Na
Ca H* CHCHt OCOCH! tHs CH3 C1gH33CONCHg CHg SO3 NaA-
17 General formula [N-l1F C1sHslCONCHt CHz Sow NaCH
.

C1oHuCON (CHi)a SOs NaCHg C9H,,C0NCHx C1(X 303 NaCH
3 C1oHuCON (CH2)3303 NaC! R
5 C,H+tCON (CHg)s SO+ Na The nonionic surfactant according to the present invention has the following general formula [:
N-1, [N-II], [N-! III and [N-
IV].

General formula [N-1] R□-A -(CHx CHg O) 1) u H General formula [N-ml General formula [N-1! /] CHt 0Rsa CHI 0R34 In the formula, Rt+ represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, an alkenyl group, or an aryol group, and each of these groups includes those having a substituent. R2,
is preferably an alkyl group, alkenyl group, or aryl group having 4 to 24 carbon atoms, particularly preferably a hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, or 2,4-di-t- butylphenyl group, 2.
These include 4-di-1-pentylphenyl group, p-dodecylphenyl group, n-pentadecaffenyl group, t-octylphenyl L2,4-dinonylphenyl group, octylnaphthyl group, and the like.

A is -o--s--coo--oco--N-R3゜,
CON-R5° or -SO□N R3° (where R1° represents a hydrogen atom or an alkyl group including one having a substituent).

R2! , R23, R2'r and R19 represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group; Those each having a substituent are also included.

R1 and Ro represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group, and each of these groups includes those having a substituent. It will be done.

Rt & and R1) 1 is preferably an alkyl group having 1 to 20 carbon atoms, a phenyl group, a p-chlorophenyl group, etc., -0Rss (here, RlS is an alkyl group having 1 to 20 carbon atoms)
represents an alkyl group or an aryl group, including those having a substituent. The same applies below. ), alkoxy groups and aryloxy groups, halogen atoms such as chlorine and bromine atoms, acyl groups represented by -CORss, NRsthCOR3s (where R3&
represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
The same applies below. ), and a sulfonamidoyl group represented by NR3bSOz RlS. Among these, R2 and R2 are more preferably an alkyl group or a norylogen atom,
Most preferred are tertiary alkyl groups such as [-butyl group, t-amyl group, and t-octyl group.

RlS, Ro, R1'l and R1 are preferably hydrogen atoms or the groups listed above as preferred examples of R1 and R2°. Among these, Rat and R2
, is particularly preferably a hydrogen atom.

Rza and Rts represent a hydrogen atom, an alkyl group, or an aryl group, and these groups include those having a substituent. Especially preferred as R24 and R2 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a furyl group, and the like.

R24 and R□, Ro and R, and R2 and Rzt may be linked to each other to form a ring, for example, a cyclohexyl ring, and the substituents on the phenyl ring are asymmetric at -maximum [N-III] But that's fine.

R□ represents a hydrogen atom or an alkyl group, and this alkyl group includes those having a substituent.

Ro represents a hydrogen atom or an alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 30 carbon atoms;
Each group represented by R31) includes those having a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, a thioether group, a polyoxyalkyl ether group, etc. .

R33 represents an alkylene group having 1 to 10 carbon atoms, a polyoxyalkylene group, or a divalent aromatic group (for example, a phenylene group), including those having a substituent.

R34 represents an alkyl group or an aryl group having 1 to 20 carbon atoms. Each group represented by @R14 includes those having a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, Examples include aryloxy groups, thioether groups, polyoxyalkylene ether groups, and the like.

Re0,nl! , n12 and n14 are the average number of added moles of ethylene oxide, and are from 2 to 5, particularly preferably from 5 to 30. onlj and n14 may be the same or different; Similarly, is the average number of added moles of ethylene oxide, and is a number from 1 to 100.

m is an integer of 2 to 50, ml and ml are each 0 to 2
An integer of 0, l is an integer of θ to 30.

These compounds are described, for example, in U.S. Patent No. 2,982°651.
No. 3,428,456, No. 3.457.076, No. 3,454,625, No. 3552.972,
3,655,387, JP 51-9610, JP 53-29715, JP 54-89626,
Japanese Patent Application No. 57-85764, Japanese Patent Application No. 57-90909, “New Surfactant” by Hiroshi Horiguchi (Sankyo Publishing 1975)
It is described in etc.

Next, specific examples of nonionic surfactants preferably used in the present invention will be shown.

Compound example HOfcH. CH. OhH HOfcHz CHI Oho H HOfCH2 CH. Oh. H H O + C H z C ) ( z Oh o.H
C++Hz:+COO(CHz CH2O)-sHCI
SI(31COO fcHz CHz Ohs HC+
+ Hn O'fcHt CHt OhHClzHz
s OfcHz CHz Oho HC+bHx3
0(CHACl(, Oh.l(N-14 Cr+HtsCONfcHt CHtO'r-H(CH
O cHz O? , H a+b=7 CH5 C+3HgtCONfcHm CHt Ohz HCu
HzsN (CHP CHz O)-, H(CHI C
HI 0)-b H a+b=2O Ct*Hts-3-ecHz CHz Ohs HCu
HssCOO+CHz CHP O)'is HC++
+H3sOfcHz CHI O)Ih HC22H,
5OfcH, CH2Ohs HCaH* a+b=15 C1tHtsOfcHcHx Oh (CHz CHz
Ohs HCH.

CHz CHt 0fcHt CHt Oht HN-
38 N-39 -4O -5O N-54 N-58 HO+cHx CHI O)-,1(C)I! CHO
)-,1(CHI cHt O?atHCHgOCHi CHs CHioCIlsj! m
l Ko Seal 1= 7 1 ``-FR1-18CHI ba) C!Its i ``) lower i translation 12 CIl□QC!ll5 T-1,1m7 publication 1-6 CII*OC*1Is j ``17r heel 25 CIhOCJIs ``) 71 Gon 40 Examples of the betaine surfactant according to the present invention include those represented by the following - Monana [B-1].

The most recent model [B-IF 4g Ru (CONH product cHt)-'N (CHzhtC
OO"Hff CIl□0C41)? Bore 1) 5-8 C1!.

"Go'nz-30 [In the formula, R41 represents an alkyl or alkenyl group having 5 to 17 carbon atoms, and R1 and R43 each represent an alkyl group or a hydroxyalkyl group having 4 or less carbon atoms. r is 2 to represents an integer of 8, S represents O or l, and t represents l, 2 or 3.] Examples of the alkyl group or alkenyl group having 5 to 17 carbon atoms represented by R4I include an octyl group and a nonyl group. , decyl group, dodecyl group, hexadecyl group, decenyl group, etc.

Examples of the alkyl group or hydroxyalkyl group having 4 or less carbon atoms represented by R4t and R43 include methyl group, ethyl group, propyl group, and hydroxyethyl group.

Examples of specific compounds will be listed next, but the invention is not limited to these.

CH.

CHIHzzCONH(CHz)z ON CHz
Coo.

CH.

CH.

C9H19CONH(CHt)4”N CHz CH
z CooQCH.

CH.

C,,H□ΦN−CH2Cooθ tHs CH.

Ca　Hu”N　CHz　CooQ CH.

CH.

C+zHts"N CH2Cooe CH.

CH.

CnHzt"N CHzCoo" CH.

CH.

C,lH21'! 'N-CH2 cooeCH.

The fluorine-based surfactant according to the present invention is, for example, British Patent No. 1.293.189, British Patent No. 1,259°398, United States Patent No. 3.589.906, British Patent No. 3.666.478, British Patent No. 3. , No. 754,924, No. 3,775,236,
No. 3,850,640, Japanese Patent Publication No. 54-48520,
56-1) No. 4944, 50-161236, 51-151) 27, 50-59025, 50
-1) No. 3221, No. 50-99525, Special Publication No. 1973
No. -43130, No. 57-6577, Patent Application No. 57-8
No. 3566, No. 57-80773, patent application No. 53-847
No. 12, No. 57-64228, Iron Easy
Product Research and Development (1)
& E CProduct Research and D
(1962゜9)
, Yukashojo 2 (12) (1963) p653, etc., but it is preferably represented by the following symbol.

Re -(A) , -x In the formula, R1 is an alkyl group having at least three fluorine atoms (including those having a fi1m group).

For example, dodecafluorohexyl group, heptadecafluorooctyl group, dodecafluorohexyloxy group, etc.), alkenyl groups (including those having substituents).

For example, heptafluorobutylene group, tetradecafluorooctyl group, tetradecafluorooctyloxy group, etc.) or aryl group (including those with substituents), such as trifumylophenyl group, pentafluorophenyl group, octafluorophenyloxy group, etc. ), A represents a divalent linking group, X represents a woody group, and m represents 0 or 1.

A is preferably an alkylene group (including those with substituents such as ethylene group, trimethylene group, oxyalkylene group, etc.), an arylene group (including those having substituents such as phenylene group, oxyphenylene group, etc.) , an alkylarylene group (including those having a substituent, such as a propylphenylene group), or an arylalkylene group (including those having a substituent, such as a phenylethylene group, a phenyloxyethylene group, etc.)
These groups also include divalent linking groups interrupted by different atoms or groups such as oxygen atoms, ester groups, amide groups, sulfonyl groups, and sulfur atoms.

X is a woody group, for example -(B-C1,R.

polyoxyalkylene group (where B is -cH* -C
Ht --cHs-CH□-CHg- or -CH,-
CH-CH-H-cHt-CH- is represented, and n represents the average degree of polymerization of the polyoxyal Hs kylene group and is an integer of 1 to 50. In addition, R1 represents a hydrogen atom, an alkyl group containing a substituent, or an aryl group including one having a substituent, such as a nonionic group represented by R2 (wherein R4 has 1 to 5 carbon atoms). represents an alkylene group such as methylene, ethylene, propylene, butylene, Re and Rs are an alkyl group including those having a substituent having 1 to 8 carbon atoms, an aryl group including one having a substituent, such as a methyl group, (represents an ethyl group, benzyl group, etc.);
represents an anion, such as a hydroxy group, a halogen group, a sulfate group, a carbonate group, a perchlorate group, an organic carboxylic acid group, an organic sulfonic acid group, an organic sulfate group, etc.); For example -So3M-03Os M
-COOM.

0-A-R.

M represents an inorganic or organic cation, preferably a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkylamine having 1 to 3 carbon atoms, or the like. A and Rt have the same meanings as above. ) and the like are wood-philic ammonium groups.

Examples of specific compounds are listed below, but are not limited to CHm Cy FtsCON CHm CH. SOs NaH
4CF*)-h CHg OOC-CH! H(CF,
h CHg OOC-CH SO3 NaCs
FtySOs NCHz COONagHs C? F tsC O O H H4CF* )-& CHm O(CHm CHx O
to. OC CHtH)CF*th CHt O(CH
i CHm Oto. QC-CH CHm Sow K
Cm FtySOs K sHq C. F17SO proverb N - C Hm OOK CsHmaCs FtySOs NWCHt CHg o)''
'fCHtfa S○. Nap: Average 4H (CFt).

COOCR Yo H8 CH Snow O3 Na l Average 7 CnFt+CH1 CHx () (CH. CH. o
) TeCH*H SOs Nap: Average 6 CHg CHg Cm FtySOs N(CHm CHg O'rs
303 NaCa Fq -(CHx CHz O)-
3Sow NaNa (C@FtySOGIN(CHx CHm O)p?z
P-ONap: Average 5 Cs FnS (h N CHt CHt OSOs
NaH (CF occupied CHt O-4CH@CH. O t
sHns: 10 C@F+vCHg CHm O-(CHt C
HtO>λ, Hnl:12CsH.

H(CF'!t'-s CHg Oi CHz CHt しょう CHJiS○, HF-32 CHs sHt Cm F+, SOx N(CHx CH寞Orb CH
x COONaH(CF*re CHt 0(Cl-poor C
H! O”rs P-ONHaONHa CI+.

Na peek ll3 CH.

C1(.

p: Average 4 Ch H+sOQC-CHi C@FuCH*CHzOOC-CHSO3Na The amounts of the anionic surfactant, nonionic surfactant, betaine surfactant, and fluorosurfactant of the present invention are determined depending on the amount used. Although it varies depending on the form, type, coating method, etc. of the silver halide photographic light-sensitive material, the amount may generally be 0.1 to 1000 μm per 1 - of the silver halide photographic light-sensitive material, particularly 0.
5 to 300 cm is preferable.

At least one selected from anionic surfactants, nonionic surfactants, betaine surfactants, and fluorine-based surfactants are added to any photographic constituent layer of the silver halide photographic light-sensitive material, but in particular It is preferable that at least one selected from anionic surfactants, nonionic surfactants, and betaine surfactants is added to the silver halide emulsion layer, and the fluorine-based surfactant is added to the non-photosensitive layer. Any of the various methods used in the photographic field can be used.

The molar ratio of the above-mentioned surfactant to the fluorosurfactant is preferably 1/10 to 10 times.

The emulsified dispersion containing the 5-pyrazolone coupler used in the present invention is generally prepared by mixing and dispersing a solution in which the compound is dissolved in a substantially water-insoluble high-boiling solvent and a hydrophilic colloid solution. prepared. Regarding this method, for example, U.S. Pat.
3.514 and 2,801.171. If necessary, a low boiling point solvent or a water-miscible organic solvent may be used, and these solvents are removed by evaporation by drying, washing with water, etc. The average particle size of the emulsified dispersion can be changed by changing the amount of surfactant used, the viscosity of the hydrophilic colloid solution, or by using a low boiling point solvent.

Further, the average particle size can be changed by changing the rotation speed of the stirring blade of the emulsifier and the emulsification time.

The average particle size of the emulsified dispersion of the present invention is 0.25 μm or less, preferably 0.01 μm or more and 0.25 μm or less,
More preferably, it is 0.05 μm or more and 0.20 μm or less. As this average particle diameter, a value measured based on a dynamic light scattering method is used. As a measuring device, there is, for example, Nanosizer manufactured by Coulter Co., UK.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, these light-sensitive emulsion layers are coated on a support in the order listed above, but they may be coated in a different order. A subtractive color method can be achieved by incorporating a silver halide emulsion sensitive in the wavelength range and a so-called color coupler that forms a complementary color relationship with the light to which the light is exposed, i.e., yellow for blue, magenta for green, and cyan for red. Color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, even if the halogen composition of the emulsion differs between grains. Although they may be equal, if an emulsion having an equal halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) A particle with a so-called layered structure in which the halogen composition differs between the [-layer or multiple layers], or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than grains with a uniform structure, and it is also preferable from the viewpoint of pressure resistance, when the silver halide grains have the above-mentioned structure. The boundaries between parts with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to compositional differences, or may be caused by active continuous structural changes. It may be something you have.

Regarding the halogen composition of these silver chlorobromide emulsions, any titanium bromide/silver chloride ratio can be used.

Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer is inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.The halogen composition of the localized layer is The silver bromide content is preferably at least 10 mol %, more preferably more than 20 mol %, and these localized layers are inside the grain, on the edges, corners or surfaces of the grain surface. One preferable example of this is one in which epitaxial growth is performed on a part of the corner of the particle.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

In addition, the particle size distribution of these particles is preferably monodisperse with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. In this case, a wide latitude can be obtained. For this purpose, it is preferable to blend the above monodispersed emulsions in the same layer or to apply them in multiple layers.

The silver halide grains contained in photographic emulsions are formed in regular shapes such as cubes, tetradecahedrons, or octahedrons.
It is possible to use those having an irregular (irre (ular) crystal shape such as spherical or plate-like), or a composite shape thereof. It may also consist of a mixture of those having the following.

In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, in addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafki
Chemle et Ph1sique Ph by des
otographique (Pau1Monte1, 1967), by G. F. Duufln P.
photographic emulsion chem
istry (Focal Press, 1966), V. L., Zelikman at al. M.
making and coating photogr
aphic E+gulsion (Focal Pre
It can be prepared using the method described in, for example, Published by S.S. Co., Ltd., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt includes the one-sided mixing method,
Any method may be used, including simultaneous mixing methods and combinations thereof. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably 101 to 104 moles relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. It is preferable to carry out this by adding an absorbing dye-spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include F, H, Warmer@Het
arocyclic compounds-Cyani
ne dies and related cospo
unds (John Wllley & 5ons
[Published by New York + London 1, 19
Examples include those described in 1964).

Examples of specific compounds include the above-mentioned Japanese Patent Application Laid-Open No. 62-21527.
Those described in the upper right column of page 22 to page 38 of the specification of Publication No. 2 are preferably used.

Various compounds or their precursors may be added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. be able to. These are commonly called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which develop yellow magenta and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developers are commonly used.

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

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

(Y-1) 0 0 Rt failure (Y-2) For details of the pivaloylacetanilide type yellow coupler, see US Pat. No. 4,622.287, No. 3
1) It is described in line 5 to column 8, line 39 of 1) and line 141) 50 to column 19, line 41 of the specification of 4°623.616.

For details on benzoylacetanilide type yellow couplers, see U.S. Pat.
No. 3.501, No. 4.046.575, No. 4,133
．． It is described in No. 958, No. 4,401゜752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (Y
-39), among which (Y-1),
(Y-4), (Y-6).

(Y-7), <y-ts>, (Y-21), (
Y-22), (Y-23), (Y-26),
(Y-35), (Y-36), (Y-37),
(Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623.616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be mentioned, among which (Y-2), (Y-7),
(Y-8), (Y-12).

(Y-20), (Y-21), (Y-23).

(Y-29) etc. are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical specific example (34) described in column 6 of specification No. 194
, Compound examples (16) and (19) described in column 8 of the same specification No. 3,933,501, and compound examples (9) described in columns 7 to 8 of the same specification No. 4,046,575 , 4,133
．． Compound example (1) described in columns 5 and 6 of Specification No. 958
, Compound Example 1 described in Column 5 of 401.752, and the following compounds a) to h).

Among the above-mentioned couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Other magenta couplers that can be used in combination with the pyrazolone magenta coupler used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrozolone and pyrazolotriazoles. An example is a coupler. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with a lylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include those described in US Pat. No. 2.31). No. 082, No. 2.3
No. 43.703, same No. 2. 600. No. 788, No. 2.908.573, No. 3. No. 062.653,
3.152,896 and 3.936.01
It is stated in issue 5 etc. U.S. Pat. No. 4,310.61 as a leaving group for a two-equivalent 5-pyrazolone coupler.
The nitrogen atom leaving group described in No. 9 or U.S. Pat. No. 4,
The arylthio group described in European Patent No. 351.897 is preferred, and the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, US Patent No. 2.
369.8'79, preferably pyranoO(5,1-c)(1,2,4) triazoles as described in U.S. Pat. Disclosure 24220
(June 1984) and Research Disclosure 2423G (1
Examples include pyrazolopyrazoles described in June 1984). Any of the couplers mentioned above may be polymeric couplers.

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

Among pyrazoloazole couplers, U.S. Pat.
The imidazo(1,2-b)pyrazoles described in U.S. Pat.
) Riazole is particularly preferred.

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

Specific examples of these couplers are listed below.

As cyan couplers, phenolic cyan couplers and naphthol cyan couplers are the most representative.

As a phenolic cyan coupler, US patents 2 and 3
No. 69.929, No. 4,518,687, No. 4,51
), No. 647 and 3. 772. There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position, such as those described in Canadian Patent No. 62.
Coupler of Example 2 described in No. 5.822, U.S. Pat.
, 772.002 +1), 4,56
Compounds (1-4) and N-5) described in 4゜590, compounds (1) and (2) described in JP-A-61-39045
, (3) and (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772, 162, 2. 895. No. 826, No. 4,334,01), No. 4. There are 2,5-diacylaminophenol couplers described in US Pat. , the compound αη described in 4°557.999,
Compounds (2) and (b) described in No. 4,565.777
, Compound (4) described in No. 4.124.396, No. 4
．． Compound (1-19) described in No. 613564 can be mentioned.

As a phenolic cyan coupler, U.S. Pat.
, No. 372.173, 4. 564. No. 586, No. 4,430,423, JP-A No. 61-390441, and Japanese Patent Application No. 61-100222, there are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus. are couplers (1) and (3) described in U.S. Pat. No. 4,327,173, compounds (3) and (to) described in U.S. Pat. No. 4,564.586, and U.S. Pat. No. 4,430,423. Examples include the compounds (1) and (3), and the following compounds.

H C1) (S H3 C&H13+a In addition to the above-mentioned types of cyan couplers, diphenylimidazole cyan couplers described in European Patent Application Publication EP 0,249,453A2, etc. can also be used.

Other examples of 4HI phenolic cyan couplers include U.S. Pat. No. 4,333.999, U.S. Pat.
, 444,872, 4,427.767, 4,
No. 579,813, European Patent No. (EP) 067.689
There are ureido couplers described in U.S. Pat. No. 4,333,999, coupler +1) described in U.S. Pat. The coupler (2) described in 4,444,872, the coupler (3) described in 4,427,767, the coupler (3) described in 4,609.619
6) and (24), couplers fl+ and αυ described in 4,579,813, European Patent No. (EP) 067.689
Couplers (45) and (50) described in No. B1, JP-A No. 1983
Examples include coupler (3) described in No. 1-42658.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-carbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586).
, those having an alkylcarbamoyl group at the 2-position (for example, U.S. Pat. Those with a carbonamide or sulfonamide group in the position (for example, JP-A No. 6023
No. 7448, No. 61-145557, No. 61-153
No. 640), and those having an aryloxy leaving group, for example, US Patent No. 3. 476.563), those with substituted alkoxy leaving groups, e.g., U.S. Pat. No. 4,296.199
No.), those with a glycolic acid leaving group (e.g.
0-39217).

These couplers can be contained in the dispersed emulsion layer in the coexistence of at least one type of high boiling point organic solvent. Preferably, a high boiling point organic solvent represented by the following formula (A) to E) is used.

Formula (A) W+W, -0-P=
0 Formula (B) V/+ -Coo Wt w, -coN Expressed, W4 is W,,o
represents w, or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other; may form a fused ring).

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Also, (bissalicylaldoximado)nickel complex and (bis-N,N dialkyldithiocarbamado)
Metal complexes such as nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
Same No. 2.418,613, Same No. 2.700.453, Same No. 2.701,197, Same No. 2,728,659
No. 2. 732. No. 300, No. 2,735.
No. 765, No. 3,982.944, No. 4.430
, 425, British Patent No. 1,363,921, U.S. Patent No. 2.710.801, U.S. Pat. is U.S. Patent No. 3°432.
No. 300, No. 3.573,050, No. 3,574
．． No. 627, same No. 3. 698. No. 909, same No. 3.
No. 764,337, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,360.589, and p-alkoxyphenols are described in U.S. Patent No. 2,73.
No. 5,765, British Patent No. 2.066.975, JP-A-59-10539, JP-A-57-19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3700.4.
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,2
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3.457.079, U.S. Pat. 21) Hindered amines are disclosed in U.S. Patent No. 3,336゜1, etc.
No. 35, No. 4,268.593, British Patent No. 1.3
2. No. 889, same No. 1. 354. No. 313, No. 1,410,846, Japanese Patent Publication No. 51) 420, Japanese Patent Publication No. 58-1) 4036, No. 59-53846, No. 59
-78344, etc., and ether and ester derivatives of phenolic hydroxyl groups are disclosed in U.S. Patent No. 4,155.765,
No. 4,174,220, No. 4,254,216, No. 4,264,720, JP-A-14553-1983
No. 0, No. 55-6321, No. 58-105147,
No. 59-10539, Japanese Patent Publication No. 57-37856, U.S. Patent No. 4,279,990, Japanese Patent Publication No. 53-3263
No. 4,050,938, U.S. Pat. No. 4,241°155, British Patent No. 2,027,
731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an external ray absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferred to use the following compounds together with the above-mentioned couplers, especially with the pyrazoloazole couplers.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferable compound (F) has a second-order reaction rate constant with p-anilidine of 2 (in trioctyl phosphate at 80°C) of 1.0β/mol·sec to 1xl.
It is a compound that reacts in the range of O-'1/mol·sec.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (F) can be represented by the following symbol (Fl) or (Fn).

General formula (Fl) R1-(A), l-X General formula (F II) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (FII). represents a group that

Here, R1 and X, Y and R2, or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII),
No. 58643, No. 62-212258, No. 62-21
No. 4681, No. 62-228034 and No. 62-279
It is described in No. 843, etc.

Further, details of the above-mentioned compound (G) and its combination with compound (F) are described in Japanese Patent Application No. 18439/1983.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, aryl group-substituted hensitriazole compounds (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. Nos. 3,314,794 and 3,352°681) ), benzophenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g., U.S. Pat. No. 3,705
．． No. 805, as described in No. 3,707.375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
(as described in US Pat. No. 3,700,455) or benzoxidol compounds (such as those described in US Pat. No. 3,700,455). UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
Ultraviolet absorbing polymers and the like may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

The photosensitive material produced according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Weiss (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used. Use is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use. .

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/π of the standard deviation S of R1 to the average value (R) of R5. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S
/π can be found.

In the present invention, the coefficient of variation of the occupied area ratio (%) of fine pigment particles is 0.15 or less, particularly 0.15 or less. 12 or less is preferable. If it is 0.08 or less, the dispersibility of the particles is substantially
It can be said that it is uniform.

The color photographic light-sensitive material of the present invention includes color development, bleach-fixing,
A washing treatment (or stabilization treatment) is preferably performed, and bleaching and fixing may be performed separately rather than in one bath as described above.

In the case of continuous processing, it is desirable that the amount of replenishment of the developer is small from the viewpoint of resource saving and low pollution.

The preferred replenishment amount of color developer is 2 per liter of light-sensitive material.
00mA or less. More preferably 120mj! It is as follows. More preferably, it is 100 m1 or less.

However, the replenishment amount here refers to the amount of so-called color developer replenisher to be replenished, and the amount of additives and the like for correcting aging deterioration and concentration is not included in the replenishment amount. It should be noted that the additive herein refers to, for example, water for diluting the concentrate, a preservative that easily deteriorates over time, or an alkaline agent that increases p)I.

The color developing solution applied to the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, and a typical example is 3-phenylene diamine compounds.
Methyl-4amino-N,N,-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
1-luenesulfonate and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pHff1 balancing agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It generally contains an inhibitor. Also, if necessary,
Organic solvents like ethylene glycol, diethylene glycol, development accelerators like benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents like competing couplers sodium boron hydride,! - Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,l-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid,
Ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than m1. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment layer with the air.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately, or in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
II), compounds of polyvalent metals such as chromium (Vl) and w4(II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (■) or cobalt (l[[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 - Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. can. Among these, aminopolycarboxylic acid iron (I[[) complex salts and persulfates including ethylenediaminetetraacetic acid iron (I[[) complex salts] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (I[l) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A-53-32,736, No. 5357.831, No. 53
-37.418, 53-72,623, 53-
No. 95,630, No. 53-95,631, No. 53-1
No. 04,232, No. 53-124.424, No. 53-
No. 141.623, No. 53-28,426, Research Disclosure II & L No. 17.129 (197
Compounds having a mercapto group or disulfide group as described in JP-A No. 8,506/1983; thiazolidine derivatives described in JP-A-50-140-129; JP-A-45-8,506; No. 53-32,735
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
- Iodide described in No. 16235; West German Patent No. 996,4
No. 10, polyoxyethylene compounds described in Japanese Patent Publication No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42.434, No. 4
No. 9-59,644, No. 5394.927, No. 54-
No. 35,727, No. 55-26.506, No. 5B-1
Compounds described in No. 63,940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Patent No. 3,893,858 and Western Patent No. 1,290,812.
The compounds described in JP-A No. 53-95.630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, especially ammonium 1,000-sulfate salts. is the most widely used. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urna 1 of the 5ociety of M
tion Picture and Television'1
sion Engineers Volume 64-P, 2482
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, thiahendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-9. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
i at 15-45°C for 20 seconds-10 minutes, preferably 2
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8.543, 5B-14゜83
All known methods described in No. 4, No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35.628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A-56-64.339, JP-A-57-144,547, and JP-A-58-1) 5.438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. 1 Normally, the temperature is 33°C to 38°C, but it is possible to use a higher temperature to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature, and in order to save silver on photosensitive materials, it is possible to improve the image quality and the stability of the processing solution.
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

In order to fully exhibit the excellent features of the silver halide photographic light-sensitive material of the present invention, it is necessary to use a color developing solution that is substantially free of benzyl alcohol and contains 0.002 mol/1 or less of bromide ions for 2 minutes. It is preferable to process with a developing time of 30 seconds or less.

The term "substantially free of benzyl alcohol" mentioned above means 2 ml or less per color developer 1), preferably 0.5 mj! Hereinafter, it most preferably means that it is not contained at all.

Example ! A multilayer color photographic paper sample 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.

Third layer coating solution preparation Magenta coupler (ExM) 48.7 g, anti-fading agent (Cpd-3) 20.2 g and anti-fading agent (Cpd-3)
-4) 10.1g, 150cc of ethyl acetate and solvent (
Solv-1) 33.6cc and solvent (Solv-2) 3
．． Add and dissolve 4 cc, and mix this solution with surfactant (A-0
) was added to 450 cc of a 10% aqueous gelatin solution containing 3.7 g, and then dispersed using an ultrasonic homogenizer. 74.0 mol %) was mixed and dissolved in 420 g to prepare a first layer coating solution. Coating solutions for the first to seventh layers were also prepared in the same manner as the third layer coating solution.

1,2-bis(vinylsulfonyl)propane was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselena cyanine hydroxide; green-sensitive emulsion layer; anhydro-9-methoxy-5°5'-
Diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2'-dimethyl-1,3-propano)thiatribocyanine yossite.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetyl 7 minnow 1
, 3.4-) Riazole and the following were used as anti-irradiation dyes.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oxo-1-(2,5-disulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N '-(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt (layer structure) The composition of each layer is as follows: shows. The number is the coating amount (g/rIf)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support Laminated on both sides with polyethylene Support layer 1st layer (blue feel N) Silver halide hole M (Br: 90%) 0.29 gelatin
1.80 yellow coupler (
ExY) 0.60 Anti-fading agent (Cpd-1
) 0.28 Solvent (Solv-1) Solvent (3o1v 2) Surfactant (A-0) Second layer (color mixing prevention M) Gelatin color mixing prevention agent (Cpd-2) Solvent (Solv-1) Solvent (SOIV- 2) Surfactant (A-0) Third layer (green-sensitive layer) Silver halide emulsion (AgBr near 4χ) Gelatin magenta coupler (ExM) Anti-fading agent (Cpd-3) Anti-fading agent (Cpd-4) Solvent (3o1v l) Solvent (3o1v 2) Surfactant (A-0) Fourth JW (color mixing prevention layer) Gelatin 0,03 0.015 0.020 0,80 G,055 0,03 0.015 0.015 0,20 1,40 0,29 0,12 0,06 0,20 0,02 0.022 1,70 Color mixture prevention agent (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2 ) Solvent (Solv-1) Solvent (3o1v 2) Surfactant (A-0) Fifth layer (red-sensitive layer) Silver halide emulsion (Br nia 4%) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC -2) Anti-fading agent (Cpd-1) Solvent (3o1v-1) Solvent (3o1v-2) Surfactant (A-0) 61) (Ultraviolet absorption layer) Gelatin ultraviolet absorber (υv-1) Ultraviolet light Absorbent (LJV-2) Solvent (3o1v-1) 0.065 0, 45 0, 23 0, 05 0, 05 0.029 0.21 1, 80 0, 26 0.12 0, 20 0, l 6 0.09 0.035 0,70 0,26 0,07 0,30 Solvent (SOIV-2) Surfactant (A-0) Seventh IW (protective layer) Gelatin 0,09 0.010 1,07 ( ExY) Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro-5[γ-(2,4-di-tert-
amylphenoxy)butyramide]acetanilide (ExM) magenta coupler (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5[2
-(2,4-di-tert-amylphenoxy)-3-
Methylbutyramidephenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
Di-tart-amylphenoxy)butyl amide] phenol (Cpd-1) Anti-fading agent 2.5-D-tart-amylphenyl-3゜5-di-tert-butyl hydroxybenzoate (Cpd-2) Color mixing inhibitor 2.5 -G-tart-octylhydroquinone (Cpd-3) Anti-fade agent 1.4-G-tart-amyl-2.5-dioctyloxybenzene (Cpd-4) Anti-fade agent 2.21-Methylenebis(4-methyl-6-tert −
(UV-1) Ultraviolet absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) Ultraviolet absorption side 2-(2-hydroxy-3,5-di-tert-butyl Phenyl) benzotriazole (Solv 1) Solvent di(2-ethylhexyl) phthalate (3o1v 2) Solvent dibutyl phthalate Similarly, change the average particle size of the surfactant in each layer, the magenta coupler in the third layer, and the emulsified dispersion. , Samples A to A shown in Table 1 were prepared. The surfactant and magenta coupler were changed so that the number of moles coated in each layer was equal. However, when two types of surfactants were used in one layer, they were mixed at a molar ratio of 1=1.

The average particle size of the emulsified dispersion containing the magenta coupler was varied by varying the amount of ethyl acetate and the stirring frequency of the ultrasonic homogenizer during dispersion preparation.

A sensitometer (manufactured by Fuji Photo Film Co., Ltd.,
Using a FWH type (light source color temperature 3200K), gradation exposure for sensitometry was provided through three types of filters: blue, green, and red.

The exposure at this time was carried out so that the exposure time was 0°1 second and the exposure amount was 250 CMS. Thereafter, the following treatment was performed, and then the density was measured through blue, green, and red filters.

Regarding color development, the exposure amount that gives a density of 1.0 in color development for 3 minutes and 30 seconds for the area exposed with a green filter is 1 minute and 3 seconds.
The evaluation was based on the density given by color development for 0 seconds. In addition, Stine processed the sample using color development for 3 minutes and 30 seconds.
Evaluation was made based on the change in density measured through a green filter in the unexposed area before and after storage in a constant temperature room at 40% 'ctx degrees for 7 days.

The results are shown in Table 2.

Helmet in Exhibition-Hide Color development 37℃ Bleach fixing 33℃ Piece -■ 1 minute 30 seconds to 3 minutes 30 seconds 1 minute 30 seconds Water Washing 24-34℃ Dry 70-80℃ 3 minutes 1 minute The composition of each treatment liquid is as follows.

Left standing Nirikyu melon water diethylenetriaminepentaacetic acid Nitrilotriacetic acid benzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methane sulfonamidoethyl)-3-meth Chil-4-aminoaniline sulfate hydroxylamine sulfate Fluorescent whitening agent (WHITEX4B.

Living) 800m1 1,0g 2,0g 15mj! QmJ 2, Og 1,0g 0g 4,5g 3.0g 1.0 pH (25℃) Reduction 151 Ammonium cinnabar 100sulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (Ill) Ammonium ethylenediaminetetraacetic acid di-sodium rum water and pH (25°C) 10.25 40 QmJ 1 5 0ml 8g 5g g 1 00 0mj! 6,70 Water was added to replace 1000 ml of surfactant with F-8. All other samples are A
-0 was used.

From the results shown in Table 2, it can be seen that the present invention has excellent coloring properties and a small increase in staining. Further, this effect is greater when the sensitive material contains at least one selected from anionic surfactants, nonionic surfactants, betaine surfactants, and a fluorosurfactant.

Example 2 A multilayer color photographic paper sample A 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.

Third layer coating solution preparation Magenta coupler (ExM) 48.7 g, anti-fading agent (Cpd-3) 20.2 g and anti-fading agent (Cpd-3)
-4) 10.1g, 150cc of ethyl acetate and solvent (
Solv-1) 33.6cc and solvent (Solv-2) 3
．． Add and dissolve 4 cc, and mix this solution with surfactant (A-0
) was added to 450 cc of a 10% aqueous gelatin solution containing 3.7 g of gelatin, and then dispersed using an ultrasonic homogenizer. A first layer coating solution was prepared by mixing and dissolving 420 g of 0.7 mol %). The coating solutions for the first to seventh layers were also prepared in the same manner as the third layer coating solution.

1,2-bis(vinylsulfonyl)propane was used as the gelatin hardening agent for each layer.

The following spectral enhancing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-5'-chloro-3,3
'-Disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer i3,3'-diethyl -5 to methoxy-9
, 9'-(2,2'-dimethyl-1,3-propano)thialibocyanine iosito The following were used as stabilizers for each emulsion layer.

[3-cyano-5-hydroxy-4-(3(3-cyano-5-oxo-1-(4-sulfonatophenyl)-2-
Pyrazolin-4-ylidene)-1-pentanyl)-1-
Pyrazolyl]benzene-4-sulfonato sodium salt and the following were used as anti-irradiation dyes.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oxo-1-(2,5-disulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-vilasoylyl]benzene-2,5-disulfonate-disodium salt N,N '-(4,8-dihydroxy-9,l〇-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(amitumethane!rephonate)-tetrasodium salt (layer structure) The composition of each layer is shown below. Show, apply the numbers! The silver halide emulsion expressed as (g/d) expresses the coating amount in terms of vA.

Support No.-N (blue-sensitive layer) laminated on both sides with polyethylene Silver halide emulsion (AgBr: 0.7 mol%, cubic,
Particle size 0.9μ) 0.29 Gelatin 1.80 Yellow coupler (ExY) 0.60 Antifading agent (Cpd
-1) 0.28? Container (Solv-3
) 0. 01 Solvent (S
olv-4) 0.03 surfactant (8-0) Second layer (color mixing prevention gelatin color mixing prevention agent (Cpd-2) Solvent (3o1v 1) Solvent (3o1v-2) Surfactant (A-0 ) Third N (green sensitive layer) Silver halide emulsion (HgBr: 0.7, grain size 0.45μ) Gelatin magenta coupler (ExM) Antifading agent (Cpd-3) Antifading agent (Cpd-4) Solvent ( Solv-1) Solvent (Solv-2) Surfactant (A-0) Fourth layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) 0,020 0,80 0.055 0,03 0.015 0.015 mol%, cube, 0.20 1.40 0.29 0.12 0.06 0.20 0”, 02 0,022 1,70 0,065 Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (301v 1) Solvent (3o1v 2) Surfactant (A-0) Fifth layer (red feeling N) Halogenation 1)m (6gBr: 4 mol%, child size 0
．． 5μ) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) Solvent (Solv-1> Solvent (SOIV-2) Surfactant (A-0) Sixth 1!i (Ultraviolet absorption Jli) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) 0,45 0,23 0,05 O,OS 0.029 Cube, grain 0.21 1 .80 0.26 0.12 0.20 0.16 0.09 0,035 Solvent (Solv-2) Surfactant (A -0) Seventh layer (protective layer) Gelatin 0,09 0.010 1, 07 (ExY) Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro-5-[β-(dodecylsulfonyl)
butylamide] acetanilide (ExM) magenta coupler (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5[2
-(2,4-di-tart-amylphenoxy)-3-
Methylbutyramidophenol (ExC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
Di-tert-amylphenoxy)butylamide] phenol (Cpd-1) Anti-fading agent 2.5-Di-tert-amylphenyl-3゜5-di-tart-butylhydroxybenzoate (Cpd-2) Anti-color mixing agent tert-octylhydroquinone (Cpd-3) Anti-fade agent 1.4-di-tert-amylu-2,5-dioctyloxybenzene (Cpd-4) Anti-fade agent 2.2'-Methylenebis(4-methyl-6-tart-
Butylphenol) (Cpd-5) Ri-(p-)luenesulfonamide)-phenyl-dodecane (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV -2) Ultraviolet absorber 2-(2-hydroxy-3,5-di-tert) tylphenyl benzene triazole (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl Solvent (Solv-3) Solvent di(i-nonyl)phthalate (SOIV-4) Solvent N,N-diethylcarbonamidomethoxy-2°4-di-t-7-methylbenzene treatment Uniga l-degree color development 35°C Bleach-fixing for 20-45 seconds Stable at 30-36°C for 45 seconds
0 30~37℃ Stable for 20 seconds ■
30~37℃ Stable for 20 seconds ■ 30~
37℃ Stable for 20 seconds 0 30~37℃
Dry for 30 seconds 70-85℃
60 seconds (4 tank countercurrent system until stable ■-■.) The composition of each treatment solution is as follows.

Left standing two village demon blood water 800
ml Ethylenediaminetetraacetic acid 2.0g Triethanolamine 8.0g Sodium chloride 1.4gRH')ym
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 5.0g thyl-4-aminoaniline sulfate N,N-dihydroxydylamine 4.2g 5.6-dihydroxybenzene 1.2.4 -Trisulfonic acid 0.3g Fluorescent brightener (4,4'-diaminostilhene) Add water to pH (25℃) HoshiwataU Guazu ammonium thiosulfate (70%) Sodium sulfite iron (III) ethylenediaminetetraacetate Ammonium ethylenediaminetetraacetic acid di-sodiumtrirum 2.0 1 000ml 10.10 400ml 00ml 1L 8g 5g g Add ice water to pH (25°C) Chidingkai formalin (37%) Formalin-sulfite adduct 5-chloro-2-methyl-4 1000ml 5.5 0.1g 0.7g Isothiazolin-3-one 0.0282-Methyl-4-isothiazolino-3-one O.01g0.005 Add water to 1000ml pH (2
5°C) 4.0 Samples A to A shown in Table 3 were prepared by changing the surfactant in each layer, the magenta coupler in the third layer, and the average particle size of the emulsified dispersion. The surfactant and magenta coupler were changed in each layer so that the number of moles applied was equal. However, when using two types of surfactants in one layer,
They were mixed at a molar ratio of 1:1 and used.

The above sample was subjected to the following treatments and evaluated in the same manner as in Example 1. In other words, color development is evaluated by the exposure amount that gives a density of 1.0 with 45 seconds of color development, and the density given with 20 seconds of color development. Evaluation was made based on the increase in stain in the green-sensitive emulsion layer before and after storage for 7 days in a thermostatic chamber with a humidity of 40%.

The results are shown in Table 4.

From the results shown in Table 4, it can be seen that the present invention has excellent coloring properties and a small increase in staining. Further, this effect is greater when the sensitive material contains at least one selected from anionic surfactants, nonionic surfactants and betaine surfactants, as well as a fluorine surfactant.

(Effects of the Invention) According to the present invention, even if rapid processing is performed, color development is high;
Color photographs with less stain after processing can be obtained. This effect is greater when at least one selected from anionic surfactants, nonionic surfactants and betaine surfactants and a fluorosurfactant are used together in the sensitive material.

Claims (2)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide photographic light-sensitive material has a detachment represented by the following general formula (I) at the coupling position. 1. A silver halide color photographic material containing a 5-pyrazolone coupler having a 5-pyrazolone group, wherein the average particle diameter of an emulsified dispersion containing the coupler is 0.25 μm or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼General formula (I) (However, L_1 and L_2 represent methylene and ethylene groups. l and m represent 0 or 1. R_1 is a hydrogen atom,
Represents an alkyl group, aryl group or heterocyclic group. R
_2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. A represents a carbon atom or a sulfur atom. n represents 1 when A is a carbon atom,
When A is a sulfur atom, it represents 1 or 2. B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. X represents an atomic group necessary to form a ring. R_1 and R_
2 may be bonded to each other to form a ring. When B is a carbon atom or a nitrogen atom, B and R_2 may be bonded to each other to form a ring. ) (2) The halogen according to claim (1), wherein the silver halide photosensitive material contains at least one selected from anionic surfactants, nonionic surfactants, betaine surfactants, and a fluorine-based surfactant. Silver chemical photographic material.