JPH0234836A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid color development by incorporating a 5-pyrazolone coupler having a specified eliminated group into a silver halide emulsion layer, coating the surface of a base paper as a substrate with a synthetic resin, and specifying a water content of the photosensitive material. CONSTITUTION:At least a kind of 5-pyrazolone couplers having an eliminated group expressed by the formula I is incorporated into a silver halide emulsion layer, and the surface of a base paper of a substrate is coated with a synthetic resin. Further, a water content of a photosensitive material is regulated to 3-10wt.%. In the formula I, each L1 and L2 is a methylene or ethylene group; each (l) and (m) is zero or 1; R1 is an H atom, alkyl group, aryl group, or a heterocyclic group; R2 is a group connecting with A through a C, O, N, or S atom; A is a C atom or S atom; (n) is 1 when A is a C atom, and 1 or 2 when A is an S atom; B is a C, O, N or S atom; X is an atomic group which forms a ring. Thus, rapid development has become possible.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material that is suitable for rapid development processing and has less stain after processing. .

(Prior Art) -M, a silver halide photographic light-sensitive material consists of a support and a photographic layer coated on the support. The photographic layer herein includes a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer.

In the case of a silver halide color photographic light-sensitive material, three types of silver halide photographic emulsion layers sensitive to blue light, green light and red light are coated on a support. These layers are
When exposed to blue light, green light, and red light, aromatic compounds are removed during development.
They contain couplers that react with the oxidation products of grade amine developing agents to form yellow, magenta, and cyan colors, respectively.

Incidentally, in recent years, there has been an increasing demand for faster color development for various purposes including improving the productivity of photographic prints.
Various measures are being taken for this purpose.

As one of these efforts, couplers with high reaction activity have been developed. As a magenta coupler, US4.
There are pyrazolone couplers having an arylthio group as a leaving group, such as those described in US Pat. No. 4,351,897, et al. The following coupler (general formula A) is a typical compound thereof.

General 2 B r However, although these magenta couplers can improve the development progress compared to the four-equivalent couplers, they have drawbacks such as a large increase in staining after processing, and further improvements have been desired. .

Various magenta couplers have been investigated with the aim of improving these drawbacks. Among them, magenta coupler (general 2B), which is an improved leaving group of the above coupler, is published in WO381.
No. 04793. However, this coupler
Although an improvement in development progress was observed, the increase in staining after processing was still unsatisfactory.

Therefore, it was necessary to find a way to use the coupler as shown in WO 38104793 in a way that takes advantage of the characteristic of progressing development and reduces staining after processing.

For the above purpose, as a result of various studies, we found that by using the coupler of General 2B above to bring the water content of the silver halide photographic light-sensitive material within a certain range, while maintaining rapid processability, We have discovered the unexpected fact that the stain after treatment can be improved, leading to the present invention.

(Problems to be Solved by the Present Invention) Therefore, an object of the present invention is to provide a system suitable for rapid color development processing;
Another object of the present invention is to provide a silver halide photographic material with less staining after processing.

(Means for Solving the Problems) The present inventors have provided a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the above object is to provide at least one silver halide emulsion layer on a support. The 5- layer further contains a leaving group represented by the general formula (1).
It contains at least one pyrazolone coupler, and the support is a paper base whose surface is coated with a synthetic resin, and furthermore, the water content of the silver halide photographic light-sensitive material is 3% by weight or more and 10% by weight or less. It has been found that this can be achieved by using a silver halide photographic light-sensitive material having certain characteristics.

(General 2 I) (However, L and Lt represent methylene and ethylene groups.

2 and m represent 0 or 1. R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R2 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, and represents 1 or 2 when A is a sulfur atom. 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+ and R2 may be bonded to each other to form a ring. When B is a carbon atom or a nitrogen atom, B and R2 may be bonded to each other to form a ring. ) (Detailed Description) Each substituent in general formula (T) will be described in detail below.

Ll and L! represents a substituted or unsubstituted methylene or ethylene group. Substituents include halogen atoms (fluorine, chlorine, bromine, etc.), alkyl groups (straight-chain and branched alkyl having 1 to 22 carbon atoms, aralkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, etc.), aryl groups (phenyl , naphthyl, etc.), heterocyclic groups (2
-furyl, 3-pyridyl, etc.), alkoxy groups (methoxy, ethoxy, cyclohexyloxy, etc.), aryloxy groups (phenoxy, p-methoxyphenoxy, p-
methylphenoxy, etc.), alkylamino groups (ethylamino, dimethylamino, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), carbamoyl groups (NN-dimethylcarbamoyl, etc.), anilino groups (phenylamino, N-ethylanilino, etc.)
, sulfamoyl group (N,N-diethylsulfamoyl, etc.), alkylsulfonyl group (methylsulfonyl, etc.), arylsulfonyl group (tolylsulfonyl, etc.),
Alkylthio groups (methylthio, octylthio, etc.), arylthio groups (phenylthio, 1-naphthylthio, etc.)
, acyl group (acetyl, benzoyl, etc.), acylamino group (acetamide, benzamide, etc.), ureido group (phenylureido, N,N-dibutylureido, etc.)
, a sulfamoylamino group (such as N,N-dipropylsulfamoylamino), an alkoxycarbonylamino group (such as methoxycarbonylamino), a sulfonamide group (such as methanesulfonamide), a hydroxyl group, a cyano group, etc. It's okay. Preferred are unsubstituted methylene and ethylene groups. E and m represent O or 1, preferably 0.

R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Specifically, hydrogen atoms, alkyl groups such as linear and branched alkyl groups having 1 to 22 carbon atoms, aryl groups such as phenyl groups and naphthyl groups, or 2-furyl, 2-thienyl, 2-pyrimidinyl, and 4 -Represents a heterocyclic group such as a pyridyl group. These beams, L
It may further have the substituents defined in 2. Preferably R8 is a hydrogen atom or an alkyl group.

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

Similar to R, these may further have a substituent defined in Ll and ①-2. Preferably R2 is an alkyl group, an aryl group, an alkylamino group and an anilino group.

A represents a carbon atom or a sulfur atom, preferably a carbon atom.

n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom.

B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, preferably a carbon atom or a nitrogen atom, and more preferably a carbon atom.

X represents an atomic group necessary to form a ring.

Preferably, it represents an atomic group composed of atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms necessary to form a saturated or unsaturated 5.6- or 7-membered ring. More preferably, this ring represents an atomic group composed of atoms selected from carbon atoms, oxygen atoms, and nitrogen atoms necessary to form an unsaturated 5- or 6-membered ring.
: It may have one substituent defined in , L, or another ring may be fused to the ring containing X.

Ro and R2 may be combined with each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring. In addition, these rings may further have a substituent as defined in [13, R2]. If 6B is a carbon atom or a nitrogen atom, B and R2 may be bonded to each other to form a ring, which is preferred. The compound may form a 5- or 6-membered saturated or unsaturated ring. More preferably, a 5- or 6-membered saturated ring may be formed. Furthermore, on these rings, there are
, R2 may have the substituent defined in R2.

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

In this maximum, Yl represents Ra, Z, or Rb.

Ra represents substituted or unsubstituted allyl or a heterotertiary group. Zl represents an oxygen atom, a sulfur atom or NRf,
Rb represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. Re and Rd represent a group selected from a halogen atom, Rh and ZtRg. Re represents a hydrogen atom or a group defined by Rc or Rd. Rf represents a hydrogen atom and a group defined by Rh. Z represents an oxygen atom, a sulfur atom, or NRh, Rg represents a group defined by Rf, Rh represents a group defined by RE, Rc is bonded to at least one of Rd and Re, and 1
may form one or two carbocycles or heterocycles, which may further have substituents, R, X and B having the same meanings as the above substituents, atomic groups and atoms. .

R3 represents an anilino group, an acylamino group, a ureido group, a carbamoyl group, an alkoxy group, an allyloxycarbonyl group, an alkoxycarbonyl group, or an N-heterocyclic group, and preferably these groups contain an oil-solubilizing group. R
4 is a substituted or unsubstituted aryl group, preferably a substituted phenyl group, and more preferably a 2.4.6-)lichlorophenyl group.

This most preferred pyrazolone coupler can be represented by the following generality. This - at maximum R
+, R1, R4, RC, Rd, R4 Re, X and B have the same meanings as the above substituents.

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

Synonymous with group and atom. Preferably R1 is NH-Y
, where R9 is a 2°4.6-dolichlorophenyl group. Y2 is substituted/unsubstituted aryl,
Represents an arylcarbonyl or arylaminocarbonyl group.

A third preferred pyrazolone coupler can be represented by the following general formula. This - at maximum RISR3
, R, and X are R at each of the above substituents
6 represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. R1, R,, R,, X and B have the same meanings as the above substituents, atoms and atomic groups. Y represents substituted or unsubstituted methylene, ethylene group, and >NRr.

Rf has the same meaning as the above substituent. This most preferred pyrazolone coupler can be represented by the following general formula. In this formula, R+, Rs and R4 have the same meanings as the above substituents. R,,R.

represents an alkyl group or an aryl group, and R represents the above L1,
Representing the substituent defined in L2, D represents a methylene group, an oxygen atom, a nitrogen atom or a sulfur atom. n represents an integer from O to 2 in the case of a methylene group, but represents 1 in other cases. P represents an integer from 0 to 4.

In the following, the term "coupler part" refers to the part excluding the campling leaving group, and the term "coupler" refers to the whole including both the coupler part and the campling leaving group.

A "coupler moiety" is a pyrazolone coupler well known and used in the photographic industry that reacts with oxidized color developing chemicals to form dyes, particularly magenta dyes. Examples of preferred pyrazolone coupler portions include, for example, U.S. Pat.
, No. 199.361, No. 4,351,897, No. 43
No. 85.111, JP-A-60-170854, 60-
No. 194452, 6 (1-194451, U.S. Pat.
, No. 407,936, No. 3.419391, No. 3.3
No. 11,476, British Patent No. 1゜357.372, U.S. Patent No. 2,600,788, No. 2,908.573, 3
, No. 062,653, No. 3,519,429, No. 3,
152.896, 2,311,082, 2,3
No. 43.703, No. 2,369.489, or 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 (T) 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 Q represents a coupling-off group according to the invention. R9 is an aniline, acylamino, ureido, or carbamoy substituent, and the carbon and nitrogen atoms thereof may be unsubstituted or substituted with a group that does not reduce the effect of the coupler. R9 is preferably an anilino group, and Preferred is an anilino group represented by the following general formula. This catalytic formula represents an 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, aralamino, sulfamide, sulfonamide, and cyano group; R1 is a C1-C30 phalkoxy group, an allyloxy group, or a halogen atom (preferably a chlorine atom).

R1□ and R1ff are hydrogen atoms and halogen atoms (
For example, chlorine atom, bromine atom, fluorine atom), alkyl group (e.g. alkyl group having 1 to 30 carbon atoms), alkoxy group (e.g. alkoxy group having 1 to 30 carbon atoms), acylamino group, sulfonamide group, sulfamoyl group, sulfamide group. group, carbamoyl group, diacylamino group, allyloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, allyloxysulfonyl group, alkanesulfonyl group, allenesulfonyl group, alkylthio group,
It represents an arylthio group, an alkoxycarbonylamino group, an alkylureido group, an acyl group, a nitro group, and a carboxy group. For example, RI! and RI3 may each be a hydrogen atom or a ballast group.

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-pentadecylphenoxy]-butyramide group), and/or a cyano group. R1° is more preferably a 2,4.6-)lichlorophenyl group.

R1! To explain sRIff in more detail, these include hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), linear and branched alkyl groups having 1 to 30 carbon atoms (e.g. methyl group, trifluoromethyl group). , ethyl group, t-butyl group, tetradecyl group), carbon number 1-
30 alkoxy groups (e.g. methoxy group, ethoxy group,
2-ethylhexyloxy group, tetradecyloxy group)
, acylamino group (e.g. acetamide group, benzamide group, butyramide group, tetradecanamide group, α~(
2,4-di-L-pentylphenoxy)acetamide group, α-(2,4-di-L-pentylphenoxy)butyramide group), α-(4-hydroquine-3-t-butylphenoxy)tetradecanamide group, 2- Oxo-pyrrolidin-1-yl group, 2-oxy-5-tetradecyl-pyrrolin-1yl group, N-methyltetradecanamide group,
L-butylcarbonamide group), sulfonamide group (e.g. methanesulfonamide group, henzenesulfonamide group, P-)luenesulfonamide group, p-dodecylhenzensulfonamide group, N-methyltetradecylsulfonamide group, hexadecane sulfonamide group), sulfamoyl group (e.g. N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N,N-dimethylsulfamoyl group, N-C3-(1"decyloxy)propyl]sulfamoyl group, N-(4-(2,4-di-pentylphenoxy)butyl)sulfamoyl group, N-dimethylN-tetradecylsulfamoyl group, N-dodecylsulfamoyl group), sulfamide group (e.g. N-methylsulfamoyl group) famid group, N-octadecylsulfamide group), carbamoyl group (e.g. N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-C4-(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. methoxysulfonyl 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), aryloxysulfonyl group (e.g. phenoxysulfonyl group, 2°4-',
-t-pentylphenoxysulfonyl group), carbon number 1-
30 alkanesulfonyl groups (e.g. methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexanedecanesulfonyl group), arenesulfonyl M (e.g. benzenesulfonyl group, 4-nonylbenzenesulfonyl group, p-toluenesulfonyl group) ,
Alkylthio groups having 1 to 22 carbon atoms (e.g. ethylthio group, octylthio group, benzylthio group, tetradecylthio group, 2-(2,4-di-L-pentylphenoxy)ethylthio group), arylthio group (e.g. phenylthio group,
p-tolylthio group), alkoxycarbonylamino group (
For example, ethoxycarbonylamino group, benzyloxycarbonylamino group, hexadenyloxycarbonylamino group), alkylureido group (for example, N-methylureido group, N,N-dimethylureido group, N-methyl-Ndodecylureido 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), nitro group , cyano group, and carboxy group.

To explain in more detail the alkoxy group and allyloxy group of R1□, the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a 2-methoxyethoxy group, a 5ec-butoxy group, a hexyloxy group, and a 2-ethylhexyloxy group. group, 2-(2,4-di-L-pentylphenoxyethoxy group, 2-dodecyloxyethoxy group, oryloxy group is phenoxy group, α- or β-naphthoxy group, 4-tolyloxy group) be.

A monomer containing a pyrazolone coupler having a leaving group of formula (I) is copolymerized 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, L-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 sulfostyrene), 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. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

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 among them, polymer coupler Latinx is particularly preferred.

Next, coupling separation M(Q
), but the invention is not limited to these.

Q~1) Q-3) NHCOCt)L (t) Q-4) Q-2) Q-6) Q NHCOOCzHs CHl Q-11) CH.

2H5 Q-20) CaH+t(t) Cj! Q Q-26) NHSOzC+ 6H33(II) NHSOzC+aHz:+(II) Q-28) H3 30,) Q-31) Q-36) Q-40) Q Q-42) Q-45) Q-52) Q -53) (II)C+2Hzs (II)Ca)l++0 Q-56) Q-57) (M Next, specific examples of the coupler of the present invention will be shown, but the coupler is not limited thereto.

(M C.I.

(M-3) (M-4) H3 (M-6) (M Hz P CHl H3 NHCOC-CI+.

\ j2 H3 (M (M (M L (M P lh (M NHCOCCH3 1cH1 P C1l.

(M CH.

C) 1° (M C10゜ (M (M ! 9) P Hff CH.

(M (M (M-281 (M-29) 2H5 C1(3 P (M (M-27) (M (M l (M-32) (M-33) (M-36) (M CI! .

(M I (M (M (M-45) (M-42) C! (M lh (M CR3 CR3 ■ I i (MC11ff ■ CHi ■ P (M-48) (M-49) (M-52 ) (M C1h 吋C4L \ P (M (M (M (M-55) ffi M-56) M-58) M-57) The above coupler is produced according to the synthesis method described in the aforementioned WO38104795. be able to.

Also, the molar amount of this coupler used ranges from lo-2 moles to IO moles, preferably from 5X1O-2 moles to 5 moles, and preferably from 1X10-' moles to 3 moles per mole of il.

The silver halide photographic light-sensitive material of the present invention has an I content of 3% by weight or more.
It has a water content of 0% by weight or less. The term "moisture content" used herein refers to a value measured by the following method.

(Method for measuring moisture content) The sample to be measured was heated at 25°C and 855%RH for 12 hours.
After standing for a period of time, its weight was measured and its weight was determined as W2.Next, this jλ material was dried at 100'C for 12 hours, and its weight was again measured and designated as W2. At this time, the water content is expressed by the following formula.

Moisture content [%) -(W, -w2)/W, Xi 00 Moisture content measured by the above method is less than 3% by weight, or 1
If it is greater than 0%, the performance of the resulting silver halide photographic material will be poor. The water content is more preferably 3.5% by weight or more and 8.0% by weight or less.

Methods for controlling the moisture content include selecting drying conditions after coating the photographic layer on the support and incorporating a moisture absorbent into the photographic layer, but in the present invention, the most effective method is The method used is a method controlled by the content of the support. That is, it is preferable to use a support that is made of a paper base material coated with resin on both sides and has an appropriate moisture content.

The moisture content of the support is preferably controlled before the photographic layer is coated onto the support.

More preferably, this is carried out before coating the paper base material with the synthetic resin.

In the silver halide photographic light-sensitive material of the present invention, a paper base material whose surface is coated with a synthetic resin is used as a support. As the resin used for coating the paper base material, polyolefin resins are preferably used, such as homopolymers of α-olefins such as ethylene and propylene, or copolymers consisting of two or more α-olefins such as ethylene and propylene. or copolymers containing α-olefin as a main component and other monomers copolymerizable therewith, and mixtures thereof are preferably used. In order to obtain the support used in the present invention using the polyolefin resin described above, a so-called extrusion coating method is usually used in which the resin described in 1. is heated and melted and then cast onto a running paper base material. As a result, both sides of the paper base material are coated with the resin.

In addition, preferable methods other than the above-mentioned methods include JP-A-57-27257, JP-A-57-30830, and JP-A-60.
-249145 etc., that is, on a paper base material,
A method may be mentioned in which a coating layer that can be cured by electron beam irradiation is applied, and then the coating layer is cured by irradiating the electron beam to form the coating layer.

In the resin coating layer of the paper base material, white pigments such as titanium oxide and aluminum oxide, colored pigments, stabilizers that are usually mixed with resins, antioxidants, dispersants, slip agents, etc. are added as necessary. can be included.

The silver halide photographic light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or
It may be coated via one or more subbing layers (to improve dimensional stability, abrasion resistance, hardness, antihalation properties, and/or other properties).

The silver halide photographic emulsion layer according to the present invention is preferably hardened using at least one compound selected from the following formula (U) for the purpose of further improving the stain after processing.

(-format ■) X'-3O, -L-3O2-X2 In the formula, X1 and x2 are -CH2=CH, or CH2C
It is either H or Y, and Xl and X2 may be the same or different. Y represents a group that undergoes a substitution reaction with a nucleophilic group, or a group that can be separated in HYO form by a base (eg, halogen atom, sulfonyloxy, sulfuric acid monoester, etc.).

L is a divalent linking group and may be substituted.

The amount of hardening agent added in the present invention ranges from 0.01 to 20% by weight, particularly preferably from 0.1 to 10% by weight, based on dry gelatin.

Specific examples of X' and X'' include the following.

The hardener represented by the general formula [H] will be explained in detail below.

Specific examples of Y include a halogen atom, a sulfonyloxy group, a sulfuric acid monoester group, a carboxylic acid ester group, and a trialkylammonium group. Further, as specific examples of Xl and x2, the following can be mentioned.

(X-1) -CH2=CH.

(X-2) -CII□CIl□C1(X
3) CLCLBr(X-4) −
CH1CH20SOZCH1 (X 7 )
CIIzCIIzO3OJa(X-8) −
CHzCJIzO5OJ(X-9) -co□C
JhOCOCHp(X-10) -C1l□CH
zOCOCF3(X-H) -c++□CIl□
0COCIICjl! □θ (X −12) −CIIZCH2N(C2H
5) 3 1 Among these, (X-1), (X-2)
, (χ4), (X-7), (X-12) are preferable, and (
X-1) is particularly preferred.

The divalent linkage ML is an alkylene group, an arylene group, or a group thereof, and -0--N--GO so--5o2---so.

SO□　N old It is a divalent group formed by combining.

R' represents a hydrogen atom or an alkyl or aralkyl group having 1 to 15 carbon atoms. Also, n1 zuO
When two or more sho-1-colNCO2- are included, those R1s may be bonded together to form a ring. Furthermore, L may have a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group, and an amine group.

Moreover, those substituents may be further substituted, and in the chemical structure, one or more X3-3o.

It may contain a group represented by X3 is the aforementioned Xl
and x2.

Representative examples of L include the following.

(L-1) -←Cll2-)? -(L-2)
-←CH2-)T-0+CH2+-7(L-3) RI R1 110C1l 2) "C0N-←C11z MoTNC
O+ C11z + completed (L -4) ff 10C112+-r-M-(-CI(2 丑(L-5) R4RS + C1l z +-T-CON + Ctl z ~rO+ C1l 2÷-y-NCO4 -C1lz-
)-r(L-6) -(-C)12 +Tc0o -(-C11□+70C
O+CH, -h(L-7) +CII□su-SOz
+ CHZ In the formula below, a % r is an integer from 1 to 6, and only e may be 0. Among these; 3. e, j
, , n is preferably 1 to 3, b, c, d
, f, B, h, i, l, m, q, r are preferably 1 or 2, R'-R5 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ,R
1 and R2 and R4 and R5 may be combined to form a ring. R1 to R6 are preferably a hydrogen atom, a methyl group, or an ethyl group. Further, these groups may have a substituent.

Typical examples of cases where L has a substituent and cases where R1 and R1 described above are combined include the following.

(L-9) C1hSOZCIf-CI+□ -C11□-C-C112- CIIzSOzCI! zcHzNHcLcIIzsOJ
a(L-11> In the formula, 5-W represents 1 or 2.

Among these L, (L-1), (L-2), (L-3)
, (L-8), (L-9) are preferred; (L-1), (
L-9) is particularly preferred.

Next, specific examples of hardening agents to be used without the invention will be listed, but the present invention is not limited thereto.

(H-1) CH2=C11SOtC)12SO□
Cll=CH.

(H-2) CI(=(JISO□C)lzcIh
c) lzso□CH-CH2(H-3) C1I□SO□CR=C)12 C11□=CH502C11□-CCIl, SO□Cl
l=CH2CIIzSOzC1(zcHJIIc)Iz
C1! zsOJa (H-4) C11□=CH3O□C1l□0CHzS (hctl=
cII□(H-5) C1l, = CH30□CH
zCLOCLCIlzSOzCII-CL(H-10) (H-6) CIl□=Cll5O□CIl□C0NIINHCOC
II□SO□CII=CI+□C1,C1h (H Cllz"'CH30zCHz C
Ih5O□CII=C)12CH,C11□ C0NHCIIzCth NHCO (H-8) CIl□～CH30□CIhC01llI NH
COCII2SO□Cll=CH.

C) IzGHzCIlz (H-9) CH,=Cll5O□CH.

CH, SO□C11-CL CH.

CI+.

C0C1hCII□SO□Cl1=CH2(H-11) CIl□〜Cll5O□CHz Cll
2SO□C1l□CI]2CHHz Cl
1z O20:+NaC0NIICII□CI
hNlIC0 5OJa (H-13) CI CHzCILzSO□ClIC0OI:1(2C
1hC211,0 CCIC1lSO2CH2CIl□CEC, II S (H-14) co□-C1-ISO□C)1IC
11CH! So□Cll=ClI2 The method for synthesizing the hardening agent used in the present invention is described, for example, in Japanese Patent Publication No. 47-2429.
No. 50-35807, JP-A No. 49-24435, JP-A No. 53-41221, and JP-A No. 59-18944.

In the present invention, even if the hardening agent is added to the coating solution in advance,
It may be mixed with the coating liquid immediately before coating.

The amount of hardener added in the present invention ranges from 0.01 to 20% by weight, particularly preferably from 0.1 to 10% by weight, based on the dry gelatin.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, a green-sensitive halogen north limit emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, magenta for green, and cyan for red. By containing a so-called color coupler, subtractive 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. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion in which the halogen composition is the same 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 halide root grain, and grains with a so-called uniform structure where the composition is the same in all parts of the silver halide grain, and a core inside the silver halide grain and a shell surrounding it. (Shell) Particles with a so-called layered structure in which the halogen composition differs between [-layer or multiple N], or
Particles with a structure in which portions with different halogen compositions exist in a non-layered manner inside or on the particle surface (if they are on the particle surface, the portions with different compositions are joined to the edges, corners, or surfaces of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver 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 localized silver bromide layer is provided 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 preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can then be inside the particles, on the edges, corners or faces of the particle surfaces. One preferable example is one in which epitaph kinial growth occurs in 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.
lar), irregular crystal shapes such as spherical or plate-like, or a combination of these shapes can be used. Moreover, it may be made of a mixture of crystals having various crystal forms.

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 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 bromide emulsion used in the present invention is P, Glafkid
Chemie et Ph1sique Pho by es
tographique (published by Pau1Monte1,
(1967), G., F. Duufin, Ph.
otographic Emulsion Chemi
stry (Focal Press, 1966), V. L., Zelikman et al. M.
making and coating photo
Graphic Emulsion (Focal P
It can be prepared using the method described in (Published by Res Inc., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. A method (so-called back mixing method) in which six particles may be formed in an atmosphere containing excess silver ions can also be used. As one type of simultaneous mixing method, a method in which PAg in a liquid phase in which silver halide is produced can be kept constant, that is, a 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 over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-2 mol 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 carried out 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. In the present invention, it is preferable to add a spectral enhancing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F, H, Har+wer 1 (ete
rocyclic compounds-Cyanin
e dies and related compou
nds (John Wiley & 5ons [
New York, London], 196
4) can be mentioned. Examples of specific compounds include the above-mentioned Japanese Patent Application Laid-Open No. 62-215272.
Those described in the upper right column of page 22 to page 38 of the specification of the publication 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.

For color light-sensitive materials, a yellow primer Mazenk coupler and a cyan coupler, which develop yellow magenta and cyan colors, respectively, by coupling with an oxidized product of an aromatic amine color developer are commonly used.

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

Among them, yellow couplers have the following general formula (Y-
Those represented by 13 and (Y-2) are preferred.

(Y-1)
It is described in column 15, line 15 to column 8, line 39, and in column 14, line 50 to column 19, line 4 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
, No. 958, No. 4.401752, 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-15),
(Y-21), (Y-22), (Y-23)
, (Y~26), (Y35) (Y-36
), (Y-37), (Y-38), (Y-39), etc. are preferred.

Also, the first specification of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples of 9+1jl to 24MII (Y-1) to (Y-
33), among which (Y2), (Y-7
), (Y-8), ("y"-12) (Y-20),
(Y-21), (Y-23) (Y-29), etc. are preferred.

Other preferred examples include U.S. Patent No. 3408.1
Typical example (34) described in No. 6 of Specification No. 94,
Compound examples (16) and (19) described in column 8 of specification No. 3,933.501, compound examples (9) described in columns 7 to 8 of 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 Specification No. 4401.752 and the following compounds a) to h) can be mentioned.

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 an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. 2.3 of the same
No. 43,703, No. 2.600,788, No. 2.
No. 908,573, No. 3,062.653, No. 3
, No. 152.896 and No. 3,936,015. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
．． The arylthio group described in No. 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, US Patent No. 2.
369,879, preferably the pyrazolo(5,1-cl[1,2,4)) liazoles described in U.S. Pat. No. 3,725,067, Research. Disclosure 24220 (1
Pyrazolotetrazoles described in June 1984) and Research Disclosure 24230 (June 1984)
Examples include the virazolopyrazoles described in June 2003). Any of the couplers mentioned above may be polymeric couplers.

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

R’1 3t (M [M 1] 2] (Listed on line 27.

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

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2, 3 or 6 position of the birazolotriazole ring as described in JP-A No. 61-65245; 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. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 849.

Specific examples of these couplers are listed below.

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

As a phenolic cyan coupler, US patents 2 and 3
No. 69.929, No. 4,518.687, No. 4,51
1.647 and 3,772,002, etc.
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, and representative examples thereof include Canadian Patent No. 625.
Coupler of Example 2 as described in '822, U.S. Pat. No. 3,7
Compound (1) described in No. 72.002, compounds (1-4) and (1-5) described in No. 4.564.590, compound (1) described in JP-A-61-39045, (2),
Examples include (3), (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
772.162, 2,895.826, 4,
No. 334,011, No. 4,500゜653 and JP-A-5
There are 2,5-diacylaminophenol couplers described in US Pat. No. 9-164555, and typical examples thereof include the compound (■) described in US Pat.
Compound 07) described in No. 4゜557.999, No. 4,
Compound (2) and surface described in No. 565.777, No. 4,1
Compound (4) described in No. 24.396, No. 4.6135
Examples include the compound (1-19) described in No. 64.

As a phenolic cyan coupler, U.S. Pat.
, No. 372,173, No. 4.564,586, No. 4,
430.423, Japanese Patent Application Laid-open No. 61390441, and Japanese Patent Application No. 61-100222, in which a nitrogen-containing heterocycle is fused to a phenol nucleus. The coupler described in No. 173 (
1) and (3), the compounds (3) and 00 described in No. 4,564,586, the compounds (1) and (3) described in No. 4,430,423, and the following compounds. Can be done.

CH CzHs 0'H p C6H13++ In addition to the above types of cyan couplers, European Publication of patent applications EPO.

Diphenylimidazole cyan couplers described in 249°453A2 can also be used.

CH.

Other examples of 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, U.S. Pat. ), the coupler O described in 4.444,872, the coupler described in 4.427.767 (
3), coupler (6) described in No. 4,609.619
(24), couplers (1) and (II) described in No. 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 uncoupler include those having an N-alkyl-N-arylcarbamoyl 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. No. 2.474.293 and U.S. Pat. No. 4,282,312)
, those having an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523/1983), and those having a carbonamide or sulfonamide group at the 5-position (e.g., JP-A-60237).
No. 448, No. 61-145557, No. 61-1536
No. 40), those with aryloxo leaving groups (e.g. U.S. Pat. No. 3,476,563), and those with substituted alkoxy leaving groups (e.g. U.S. Pat. No. 4,296,199).
, those with a glycolic acid leaving group (e.g. Japanese Patent Publication No. 1983-
No. 39217).

These couplers can be contained in the dispersed emulsion layer in the coexistence of at least one type of high boiling point -+-m solvent.

Preferably, a high boiling point organic solvent represented by the following formula (A) to E) is used.

Formula (A) w.

Wt -0-P=0 2 (B) Wl Coo Wl formula
(C) 2 (D) Wl wz\ / (wherein, W, W2 and W are each a substituted or unsubstituted alkyl group, a cycloakylene group, an alkenyl group,
Represents an aryl group or a heterocyclic group, 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, and in form (E), Wl and W2 are 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 aminephenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like 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, methylenedioxyhenzenes, aminephenols, hindered amines, and silylation of the phenolic hydroxyl groups of these compounds, alkyl Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of antifading agents are described in the specifications of the following patents.

Hydroquinones are U.S. Patent No. 2,360,290,
No. 2,418,613, No. 2,700.453, No. 2.701.197, No. 2,728,659
No. 2,732,300, No. 2.735.76
No. 5, No. 3,982.944, No. 4.430.4
25, British Patent No. 1,363.921, U.S. Patent No. 2,710.801, United States Patent No. 2,816,0.28, etc., 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, etc. Type is U.S. patent cylinder 3°432.3
No. 00, No. 3,573,050, No. 3,514,
No. 627, No. 3,698.909, No. 3.764
．． No. 337, JP-A No. 52152225, etc., and spiroindanes are described in U.S. Patent No. 4.360,589, p-
Alkoxyphenols are US Patent No. 2.735.76
No. 5, British Patent No. 2.066.975, Japanese Patent Application Publication No. 1983-
No. 10539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are described in U.S. Patent No. 3700.455,
JP-A No. 52-72224, U.S. patent cylinder 4.5E28,
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. No. 3,457,079 and U.S. Pat.
332.886, Special Publication No. 56-21144, etc.
Hindered amines are disclosed in U.S. Patent No. 3.336135,
No. 4,268,593, British patent cylinder 1.32. 8
No. 89, No. 1.354.313, No. 1,410,
No. 846, Japanese Patent Publication No. 511420, Japanese Patent Publication No. 58-114
No. 036, No. 59-53846, No. 59-78344
Ether and ester derivatives of phenolic hydroxyl groups are described in U.S. Patent Nos. 4,155,765 and 4,17.
4.220, 4,254.216, 4.2
No. 64,720, JP-A-54-145530, JP-A No. 55
-6321, 5B-105147, 59-10
No. 539, Japanese Patent Publication No. 57-37856, U.S. Patent No. 4.
279,990, Japanese Patent Publication No. 53-3263, etc.; metal complexes are described in U.S. Pat.
41°155, British patent tube 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 preferred compound (F) has a second-order reaction rate constant with p-anilidine of 2 (in 80'c trioctyl phosphate) and 1. Oj2/mol ・sec~I
It is a compound that reacts in the range of X 10-'f/mol-sec.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 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 format (Fl) or (FII).

General formula (FI) R1-(A)ll-X General formula (FII) 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 (Fn). 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 (Fn), see Japanese Patent Application Nos. 62-158342 and 62-15.
No. 8643, No. 62-212258, No. 62-214
No. 681, No. 62-228034 and No. 62-2798
It is described in No. 43, 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, benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, as described in U.S. Pat. ), benzophenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g., U.S. Pat. No. 3,705
．． No. 805, those described in No. 3,707,375),
Butadiene compounds (such as those described in U.S. Pat. No. 4,045,229) or benzoxidole compounds (such as those described in U.S. Pat. No. 3,700,455)
can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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 ab dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are used.

Gelatin is useful as a binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, 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 (published by Academic Press, 1964).

As the support used in the present invention, a paper substrate coated with a synthetic resin such as polyethylene containing a dispersed light-reflecting substance such as titanium oxide or zinc oxide is preferably used.

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 projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R,) of fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/R of the standard deviation S of R3 to the average value (R) of R8. The target unit [Ii7 product number (II) is preferably 6 or more]. Therefore, the coefficient of variation s, /R can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

The color photographic light-sensitive material of the present invention includes color development, bleach-fixing,
It is preferable to perform a water washing treatment (or stabilization treatment).'a Whitening and fixing may be performed separately instead of 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 200 d or less per 41 holes of photosensitive material. More preferably, it is 120d or less. More preferably, it is 100 ml or less. However, the replenishment amount here refers to the amount of so-called color developer replenisher that is replenished, and the amount of additives, etc. to replenish aging deterioration and a shrinkage is not included in the replenishment amount. .

Note 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 the pH.

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-4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-)
Examples include luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, various compounds such as hydroquinlamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo "22.2] octane), etc. Preservatives, organic carriers such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol alcohol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, 1 -phenyl-3
- Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. , diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,
1-Hydroxyethylidene-1,1 diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N, NN', N'-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid) and their salts are representative examples.

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 dihydroxyhenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-virapritone, or aminophenols such as N-methyl-ρ-aminophenol. It can be used alone or 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 to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
m/! You can also do the following: 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. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (II), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (1), 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 (In) complexes such as ethylenediaminetetraacetic acid iron (I [[) complex salts] and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(1) complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron ([11) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. can.

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

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 No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95.630, 53-95,631, 53-
No. 104.232, No. 53-124.4.24, No. 5
Compounds having a mercapto group or disulfide group as described in No. 3-141623, No. 53-28.426, Research Disclosure No. 17,129 (July 1978); Thiazolidine derivatives described: Japanese Patent Publication No. 45-8.506, Japanese Patent Publication No. 52-20.832, Japanese Patent Publication No. 53-32,735,
Thiourea derivatives described in U.S. Patent No. 3706.561; West German Patent No. 1.127,715, JP-A-58-16
Iodide described in No. ゜235; West German Patent No. 996,410
polyoxyethylene compounds described in Japanese Patent Publication No. 2.748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836;
59.644, 5394.927, 54-35
, No. 727, No. 55-26, 506, No. 58-163
, No. 940; bromide ion, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, U.S. Pat.
The compounds described in JP-A No. 53-95.630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photographic use.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfates being the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalof the 5ociety of
Motion Picture andTe
levision Engineers Volume 64, P.
248253 (May 1955 issue) by the method described in
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in 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, Hygiene Technology Kinkan [Sterilization of Microorganisms] It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japanese Society of Antibacterial and Antifungal Agents.

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 be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40'C. A range is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8,543, 5E114
All known methods described in No. 834, No. 60-220,345 can be used.

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 1.4, 85
Schiff base type compounds described in No. 0 and No. 15.159,
Aldol compounds described in No. 13□924, metal salt complexes described in U.S. Pat. No. 3,719,492, JP-A No. 53
Examples include urethane compounds described in No.-135.628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 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-58115.438.

The various treatment liquids in the present invention are used at 10'C to 50C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, and conversely, lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may 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 containing substantially no benzyl alcohol and containing 0.0 (12 mol/1 or less) bromide ion. It is preferable to process with a developing time of 30 minutes or less.

The term "substantially free of benzyl alcohol" mentioned above means 2 ml or less per 12 color developing solution, preferably 0. 5mff1 or less, most preferably not at all.

/ / Example = 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

150 cc of ethyl acetate was added to 60.0 g of yellow coupler (ExY) and 28.0 g of antifading agent (Cpd-1) to prepare the coating solution for the first layer.
and solvent (So 1v-1) 3.0cc and solvent (So
l v-2) was added and dissolved, and this solution was added to 450 cc of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then dispersed with an ultrasonic homogenizer. A first-class coating liquid was prepared by mixing and dissolving 420 g of 90.0 mol %).

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, those shown in Table 1 were used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'methyl-3,3'-disulfopropylselenacyanine hydroxide; green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2'-dimethyl-1,3-propano)thiacarbocyanine yossite.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 34-) 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-4ylidene)-1-propenyl)-1- [Virazolyl] Hensen-2,5-disulfonate-disodium salt N, N'-(4,8-dihydroxy-9,10dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate) -Detrasodium salt (layer structure) The composition of each layer is shown below. Numbers are applied ff (g/po)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support Laminated on both sides with polyethylene Support Layer (blue sensitivity N) Silver halide emulsion (Br: 90%) 0.29 gelatin
1.80 yellow coupler (
ExY) 0.60 Anti-fading agent (Cpd-1
) 0.281 volume (Solv-1)
0. 037 capacity (S
olv-2) 0. 01
5 Second N (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Solvent (Solv-1) Medium (Solv-2) Third N (green feeling N) Silver halide emulsion (Br near 4%) Gelatin magenta coupler (Table 1) Anti-fading agent (Cpd-3) Anti-fading agent (Cpd-4) 2 containers (Solv-1) ? Container (Solv-2) Fourth layer (mixing prevention N) Gelatin mixing inhibitor (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv 1) 7 medium (Solv -1) 0,80 0.055 0,03 0.015 (Table 1) 1.40 (Table 1) 0.23 0,20 1,70 0,065 0,45 0,23 Fifth layer ( Red Sensation N) Silver halide emulsion (4% Br) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) 7 volumes (Solv-1) 7 volumes (Solv -2) Sixth layer (ultraviolet absorption layer) Gelatin Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) Seventh N (protective layer) Gelatin 1,07 (Ex Y) Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro-5[γ-(2゜4-ditert
-amylphenoquine) butyramide] acetanilide (ExC-1) cyan coupler 2-pentafluorohenzamide-11-chloro-5 (
2-(2,4-tert-amylphenoxy)-
3-Methylbutyramidophenol (ExC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α(2,4-di-tert-amylphenoxy)butyramide]phenol (Cpd-1) Antifading agent 2 .5-di-tert-amylphenyl-3,5-';
-tert-butylhydroxyhendoate (Cpd-
2) Anti-fading agent 2.5-tert-octylhydroquinone (C
pd-3) Anti-fading agent ■, 4-Jerk-amy-2,5-dioctyloxybenzene (Cpd-3) Anti-fading agent 22'-methylenebis(4-methyl-6-ert-butylphenol) (UV-1 ) UV absorber 2-(2-hydroxy-35-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole ( Solv-1)? Each section Di(2-ethylhexyl) phthalate (Solv-2) Each section Dibutyl phthalate In the above layer structure, the magenta coupler and Age of the third layer were changed, and the water content and hardening agent of the sensitive material were changed. 1 to 14 were produced.

Table (A) The above photosensitive materials were exposed through an optical wedge and then processed in the following steps.

Processing process iLL single-solid color development
37'C 2 minutes 30 seconds, 3 minutes 30 seconds bleach fixing 33
'C1 minute 30 seconds washing 24-34'C3 minutes drying 70-80°c 1
The composition of each treatment solution is as follows. The processing solution having this composition was used after running the photosensitive material.

Hair growth JH Toli water 8
00 magnetic diethylene triamine pentaacetic acid 1.0 g nitrilotriacetic acid 2.0 g 1-hydroxyethylidene-1 1-diphosphonic acid (60χ solution) 1.0 vol benzyl alcohol 15 layer diethylene glycol 10 d sodium sulfite
2.0g potassium bromide
1.0g Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-aminoaniline sulfate Hydroxylamine sulfate 1 salt Optical brightener (WHITEX4, pH by adding water (25χ) Hair Spring water sprinkling Ammonium thiosulfate (70χ) Sodium sulfite Iron ethylenediaminetetraacetate (lI[) Add ammonium ethylenediaminetetraacetic acid disodium water to pH (25χ) 0g 4,5g 3,0g 1000ml 10.25 400ml 50d 8g 5g 1000 Sei 6 and 70 For each sample after processing, the development progress and
The degree of staining after treatment was investigated.

Regarding development progress, when the exposure amount that gives a density of 1°5 after 3 minutes and 30 seconds of development is D, the color density that develops after 2 minutes and 30 seconds of development is D/1.5xlOO, which was used as a measure of development progress. . The closer this value is to 100, the faster the development progresses, and it can be said that it is suitable for rapid processing.

In addition, the magenta density of the fogged area immediately after processing of the sample developed for 3 minutes and 30 seconds is taken as DO, and this sample is
When the magenta density after storage for 7 days in % is D',
D'-Do was taken as a measure of stain after treatment. It can be said that the smaller this value is (ideally 0), the less staining occurs after processing.

The results are shown in Table 2.

Table 2 As can be seen from the results in Table 2, with the configuration of the present invention,
It can be seen that a sensitive material with fast development progress and less staining after processing can be obtained. Furthermore, it can be seen that the performance is improved by using a vinyl sulfone hardener as the hardener.

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

150 cc of ethyl acetate was added to 60.0 g of yellow coupler (ExY) and 28.0 g of antifading agent (Cpd-1) to prepare the coating solution for the first layer.
and Sol e, (S o l v-3) 1. 0cc
Calo each section (So 1v-4) 3.0cc? After adding this solution (8) to 10% aqueous gelatin solution H4 containing sodium dodecylhenzenesulfonate, it was dispersed with an ultrasonic homogenizer, and the resulting dispersion was added to a solution containing the following blue-sensitive sensitizing dye. A first layer coating solution was prepared by mixing and dissolving the mixture in 420 g of a silver chlorobromide emulsion (silver bromide 0.7 mol %). Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, those shown in Table 3 were used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-chloro3.3'
-disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-55'diphenyl-3,3'-disulfoethyloxacarbonanine 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.

-Mercaptotetrazole and the following were used as anti-irradiation dyes.

[3-Carboxy-5-hydroxy-4-(3(3-carboxy-5-oxo-1-(2,5disurnenatophenyl)-2-bilapurin-4ylidene)-1-propenyl)-1-pyrazolyl ]Benzene-2,5-disulfonate-disodium salt N,N'-(4,8-dihydroxy-9,10dioxo-3,7-cissulfonatoanthracene 1,5-diyl)bis(aminomethanesulfonate)- Detranatrium salt [3-cyano-5-hydroxy-4-(3(3-cyano-5-oxo-1-(4-sulfonatophenyl)-2-
Pyrazoline-4-indene)l-pentanyl)-1-pyrazolylbenzene 4-sulfonato sodium salt (N composition) The composition of each layer is shown below. Numbers are coated ft (g/i)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Paper support laminated on both sides with polyethylene Support First layer (blue sensitive layer) Silver halide emulsion (AgBr: 0.7 mol cube,
Particle size 0.9μ) 0.29 gelatin
1.80 yellow coupler (ExY
) 0.60 Anti-fading agent (Cpd-1)
0.28 solvent (Solv-3)
0.01 solvent (Solv-4)
0.03 Second layer (color mixing prevention N) Gelatin 0.80 Color mixing prevention agent (Cpd-2) 0.055 Solvent (Solv
-1) 0.03 solvent (Solv-2
) 0.015 Third layer (green-sensitive layer) Silver halide emulsion (AgBr:O.

Cube, particle size 0.45μ) Gelatin magenta coupler color mixing prevention agent (Cpd-3) Color fading prevention agent (Cpd-4) Solvent (Solv-1) Each section (Solv-2) Fourth layer (color mixing prevention layer) Gelatin color mixing prevention agent Inhibitor (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) 7 medium (Solv-1) ) 8 medium (Solv-2) 5th layer (red sensitive layer) Halogenated 111JI (AgBr: 4 mol% cubic, particle size 0.5 μ) Gelatin cyan coupler (ExC-1) 7 mol Table 3 1.40 Table 3 0.23 0.1] 0.20 0.02 1, 70 0 .065 0, 45 0, 23 0, 05 0, 05 0, 21 1, 80 0, 26 Cyan coupler (ExC-2) Anti-fading agent (Cpd-1) Solvent (Solv-1) Each section (Solv-2) ) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) Seventh layer (protective layer) Gelatin 1, 07 ( Ex Y) Yellow coupler α-Vivalyl α-(3-benzyl-1-hydantoinyl)-2-chloro-5[β-(dodecylsulfonyl)butyramide]acetanilide (ExC-1) Cyan coupler 2-pentafluorobenzamide-4 -chloro-5(2
-(2,4-di-tert-amylphenoxy)-3-
Methylbutyramide pheno-JishiExC-2) cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
G-tert-amylphenoxy)butyramide]phenol (Cpd-1) antifading agent 25-G-jert-amyl phenyl-3,5-G-te
r t-butyl hydroxybenzoate (Cpd-2)
Color mixing inhibitor 25-tert-octylhydroquinone (Cpd
-3) Antifading agent 1.4-di-tert-amylu-2,5-dioctyloxybenzene (Cpd-4) Antifading agent 22'-methylenebis(4-methyl-6-tert-
butylphenol) (Cpd-5) p-(p-)luenesulfonamide)-phenyl-dobuone (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV- 2) Ultraviolet absorber 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole (Solv-1)? 8 solvent di(2-ethylhexyl) phthalate (Solv-2) solvent dibutyl phthalate (Solv-3) solvent di(i-nonyl) phthalate (Solv 4) solvent N,N-diethylcarbonamidomethoxy-2,4- Samples 15 to 28 were prepared in which the layer structure of di-t-amylbenzene was used, but the magenta coupler and Ag content of the third layer were changed, and the moisture content and hardening agent of the window material were changed.

(A), (B), (C)H-2, and H' in Table 3 have the same meanings as in Example 1, respectively.

After exposing the above light-sensitive material through an optical wedge, the following It was processed using the following steps.

Processing process: 1-stage color development
35'C 30 seconds, 45 seconds bleach fixing 30-36'
Stable at C for 45 seconds ■ Stable at 30-37°C for 20 seconds ■ Stable at 30-37°C for 20 seconds ■ Stable at 30-37°C for 20 seconds ■ Dry at 70-85°C for 60 seconds (stable ■→■
A four-tank countercurrent force type system was adopted. ) The composition of each treatment liquid is as follows. The processing solution having this composition was used after running the photosensitive material.

Light Wataru ■1 Hill Water Ethylenediamine Tetraacetic Acid Triethanolamine Sodium Chloride Potassium Carbonate N-Ethyl-N 00d 2,0g 8,0g 1,4g 5g (β-methanesulfonamidoethyl)-3 Methyl-4-aminoaniline Sulfuric acid Salt NN-diethylhydroxylamine 5.6-cyhydroxybenzene-1.2.4-) lysulfonic acid optical brightener (4,4'-diazinostilbene Add water to pH (25°C) 1 foot■ Ammonium thiosulfate (70χ) Sodium sulfite Iron ethylenediaminetetraacetate (I ) Formalin (37χ) Formalin-sulfite adduct 5-chloro-2-methyl-4 isothiapurin-3-one 2-methyl-4-isothiazolino-3-one Add water to pH (25°C) 000d 5. 5 0, 1 g 0, 7g 0.02g 0.01g iooo* 4.0 The same evaluation as in Example 1 was performed for each sample after treatment, and the results are summarized in Table 4.

As can be seen from the results in Table 4, it can be seen that with the structure of the present invention, a photosensitive material with rapid development progress and less staining after processing can be obtained. Furthermore, it can be seen that the performance is improved by using a vinyl sulfone hardener as the hardener.

No. table A sensitive material with less subsequent staining can be obtained.

This effect teeth, When a vinyl sulfone hardener is used as a hardener, Improve even more.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula (I).
contains at least one 5-pyrazolone coupler having a leaving group represented by: the support is a paper base whose surface is coated with a synthetic resin, and the water content of the silver halide photographic light-sensitive material is is 3% by weight or more and 10% by weight
A silver halide color photographic material characterized by the following: General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (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, and represents 1 or 2 when A is a sulfur atom. 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 combined with each other to form a ring. If B is a carbon atom or a nitrogen atom, B and R_
2 may be bonded to each other to form a ring. ) (2) A silver halide photographic light-sensitive material, characterized in that the light-sensitive material is hardened using at least one compound selected from the following general formula (II): The silver halide photographic material described in . (General formula II) X^1-SO_2-L-SO_2-X^2 In the formula, X^1 and X^2 are -CH_2=CH_2 or,
-CH_2CH_2Y, X^1 and X
^2 may be the same or different. Y represents a group that undergoes a substitution reaction with a nucleophilic group, or a group that can be removed in the form of HY by a base. L is a divalent linking group and may be substituted.