JPH0232342A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color formability and to decrease the processing fluctuations by incorporating a coupler the coupling position of which has a specific elimination group into the photosensitive material and dispersing the coupler therein in coexistence with a specific org. solvent. CONSTITUTION:The photosensitive material having silver halide emulsion layers on a base contains one kind of the magenta dye forming coupler the coupling position of which has the elimination group expressed by the formula I and the coupler is dispersed therein so as to coexist with the high boiling point org. solvent expressed by the formula II. In the formula I, L1, L2 denote methylene, ethylene group; l, m denotes 0 or 1; R1 denotes a hydrogen atom, alkyl group, etc.; R2 denotes a group which combines with A by carbon atom, nitrogen atom, etc.; A denotes a carbon atom, or sulfur atom; n denotes 1 when A is the carbon atom and 1 or 2 when A is the sulfur atom. B denotes a carbon atom, nitrogen atom, etc.; X denotes an atom group necessary for forming a ring; in the formula II, L3, L4 denote alkylene, cycloalkylene group, etc.; X1 denotes groups of -O-, -S-, -SO, etc.; p, q, r denote 0 or 1; R11-R13 denote a hydrogen atom, alkyl group, etc. The color formability is improved in this way and the processing fluctuations in the continuous processing are decreased.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material, and specifically relates to an improved leaving group bonded to a coupling active position via a sulfur atom. The present invention relates to a silver halide color photographic light-sensitive material containing a 5-pyrazolone type magenta dye-forming coupler having the formula in a dispersed state in coexistence with a specific high-boiling organic solvent.

(Prior Art) A 5-pyrazolone coupler is generally used as a magenta coupler to form a magenta color image in a subtractive color method. However, this 5-pyrazolone coupler causes a side reaction in the coupling reaction with the oxidation product of the developing agent, resulting in a low conversion rate to dye. When stored in cold weather, there were problems with fading or discoloration of colored iron, and even discoloration of the white background. In order to improve these problems, as couplers, for example, U.S. Pat. No. 4,351,897, U.S. Pat.
As disclosed in No. 1, a method of introducing a leaving group into the active position of a 5-pyrazolone coupler has been used, and although this has been improved, it cannot be said to be sufficient.

Recently, International Publication Patent No. WO 38104795 has been published as a coupler with several improvements including the above-mentioned problems. It is disclosed that improvements such as improved light fastness of images are achieved.

However, in order to carry out rapid processing, it is desirable to further improve color development, and in carrying out continuous processing, it is necessary that there be no processing fluctuations. The above requirements are particularly strong for processing solutions that do not contain benzyl alcohol in the color developer (
desired. Further, after image formation as a print material, storage stability of color images and no increase in staining are desired, but these are not satisfied.

No technology has been found that can fundamentally solve any of these problems, nor can they be inferred from the previously disclosed technology.

(Problem to be Solved by the Invention@) Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material that can obtain high color development in a limited development processing time. A second object of the present invention is to provide a silver halide color photographic material that exhibits little processing variation during continuous processing. A third object of the present invention is to provide a silver halide color photographic material that exhibits less fading and staining of color images during storage over time.

(Means for Solving the Problem) As a result of various studies, the present inventors were able to achieve the object by the method described below. That is, in a silver halide color photographic light-sensitive material having at least one halide steel emulsion layer on a support, a 5-pyrazolone type magenta dye-forming coupler having a leaving group represented by the general formula (1) at the coupling position is used. A silver halide color photographic photosensitive material containing at least one of This could be achieved through the use of materials.

(However, Ll and L2 represent methylene and ethylene groups.

1 and m represent O or 1. R1 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. Person 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. R1 and R2 may be combined with 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.

) General formula (ID where - and L4 represent alkylene, cycloalkylene, aralkylene, arylene and alkenylene groups,
l represents a divalent group excluding - and L4<-O--S--NHOONH- and -8O2NH-, p+q and r represent O or an integer of 1, and R1□.

R12 and R13 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group.

- Each substituent in Monka (I) will be explained in detail below.

Ll and Shame represent substituted or unsubstituted methylene or ethylene groups. Examples of substituents include halogen atoms, alkyl groups (linear and branched alkyl groups having 1 to 22 carbon atoms, etc.), alkoxy groups (methoxy, ethoxy, cycloalkyloxy, etc.), aryloxy groups (phenoxy, p-methΦ cyphenoxy, p-methylphenoxy, etc.), alkylamino group (-) methylamine, dibutylamino, etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), carbamoyl S (N, N-dimethylcarbamoyl, etc.), sulfamoyl group (N , N-diethylsulfamoyl, etc.), alkylsulfonyl groups (methylsulfonyl, ethylsulfonylnato), arylsulfonyl groups (phenylsulfonyl, tolylsulfonyl, p-
methoxyphenylsulfonyl, etc.), an acyl group (acetyl, banzoyl, etc.), a hydroxyl group, a cyano group, etc. Preferred are unsubstituted methylene and ethylene groups. l and m represent O or 1, preferably 0.

R1 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 - I am afraid of heterocyclic groups such as pyridyl groups. These are Ll,
It may further have the substituent defined in L2.

Preferably R□ 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, carbon atoms such as alkyl groups, aryl groups, heterocyclic groups (connected by carbon atoms), acyl groups, alkoxycarbonyl groups, and carbamoyl groups, etc.
Groups linked by atoms, groups linked by oxygen atoms such as alkoxy, aryloxy, alkylamino groups, anilino groups, acylamino groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, sulfonamide groups, etc. Represents a group linked via a nitrogen atom, and a group linked via a sulfur atom such as an alkylthio group or an arylthio group. Similar to R1, these may further have substituents defined in L1 and L2. Preferably R2 is an alkyl group, an aryl group, an alkylamino group and an anilino group.

The carbon atom of A represents 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-negative ring. More preferably, it 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. This ring is further described above as Ll.

R2 may have the substituent defined, and the ring containing X may be linked to another ring.

R and R2 may be bonded to each other to form a lump, preferably a 5- or 6-membered saturated or unsaturated ring. Further, these rings may further have substituents defined in Ll and R2.

When B is a carbon atom or a nitrogen atom, B and R2 may be bonded to each other to form a ring, preferably a saturated or unsaturated ring of 5 or 6A rings.

More preferably, a 5 or 6 ring saturated ring may be formed. Furthermore, on these rings there are 0. It may have the substituent defined in R2.

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

In this hole, Yl is R,! Or represents zIRb.

Ra is a substituted or unsubstituted allyl or heterocyclic group, and Rc -C- represents a secondary or tertiary group.

R1 zl represents an oxygen atom, a sulfur atom, or NRf.

Rh represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. Rc and Rct are halogen atoms, R
represents a group selected from the groups h and z2R1I.

R- represents a hydrogen atom or a group defined by Rc or Rrt.

Rf represents a hydrogen atom and a group defined by Rh.

Z represents an oxygen atom, a sulfur atom or NRA. Rli
represents a group defined by Rf. RA represents a group defined by Rf, RC may be bonded with at least one of Rd and l'b to form one or two carbocycles or heterocycles (and they may be further substituents) R1, X and B have the same meanings as the substituents, atomic groups and atoms described above.

R3 represents an anilino group, an acylamino group, a ureyl group, a cal, a dimoyl group, an alkoxy group, an allyloxycarbonyl group, an alkoxycarbonyl group, or an N-heterocyclic group, and preferably these groups contain an oil-solubilizing group. It is the basis.

R4 is a substituted or unsubstituted aryl group, preferably a substituted phenyl group, and more preferably a 2,4.6-)lichlorophenyl group.

A more preferred pyrazolone coupler of this type can be represented by the following general formula. In this pattern, R1, R3, R4, Re%Rd, Rg%X and B have the same meanings as the above-mentioned substituents.

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

R5 is in this hole! t@, unsubstituted alkyl,
Represents aryl and heterocyclic groups. R1, R3, R4
, X and B have the same meanings as the substituent atomic groups and atoms described above. Preferably R3 is a group represented by -NH-Y2, and R4 is a 2,4.6-)lichlorophenyl group. Y2 represents a substituted or unsubstituted aryl-hairylcarbonyl or arylaminocarbonyl group.

A third preferred pyrazolone coupler can be represented by the following general formula. R1, R3 in this hole
, R4 and X have the same meanings as the above substituents and atomic groups. Y3 represents a substituted or unsubstituted methylene group, ethylene group or NRf, and Rf has the same meaning as the above-mentioned substituent. A more preferred pyrazolone coupler of this type can be represented by the following general formula. R1, R3 in this hole
and R4 have the same meanings as the above substituents. R6 and R7 represent an alkyl group and an aryl group, and RB represents a substituent defined for L1 and L2 above. D represents a methylene group oxygen atom, nitrogen atom or 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 coupling-off group, and the term "coupler" refers to the whole including both the coupler part and the coupling-off group.

"Coupler moieties" are pyrazolone couplers well known and used in the photographic industry that react with oxidized color developing agents to form dyes, particularly magenta dyes. Examples of preferred pyrazolone coupler moieties include, for example, U.S. Pat.
22,915.4,336,325.4.199,36
1.4.351,897.4,385,111, JP-A-60-170854.60-194452.60-19
4451, U.S. Pat. No. 4,407,936.3.419,
391.3,311,476, British Patent 1,357,3
72, U.S. Pat. No. 2,600,788.2.908,57
3.3.062,653.3,519,429.3,1
52,896.2.311,082%2,343,70
3.2,369.489 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 by a coupling-off group represented by the general formula (I) of the present invention. The pyrazolone cabucu of the present invention can also be used in combination with other pyrazolone couplers such as those described in the above-mentioned patents.

An example of a preferred "coupler moiety" can be represented by the following general formula. In this hole, Q represents the coupling-off group of the present invention, Rg&! AIQ represents disuno, acylamino, ureido 9, carbamoyl, alkoxy, allyloxycarbonyl, alkoxycarbonyl or N-heterocyclic group, R10 is a substituted or unsubstituted allyl group, preferably 710 gene atoms, alkyl , alkoxy, alkoxycarbonyl, aralamino, sulfonamide, sulfonamide, and a cyan group. The carbon and nitrogen atoms of these substituents may be unsubstituted or substituted with groups that do not reduce the effect of the coupler. R9 is preferably an anilino group, more preferably an anilino group represented by the following general formula. In this pattern, R11 is an alkoxy group having 1 to 30 carbon atoms, an allyloxy group, or a halogen atom (preferably a chlorine atom).

Rlz and R13 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), alkyl groups (
For example, alkyl group having 1 to 30 carbon atoms) alkoxy group (for example, alkoxy-M having 1 to 30 carbon atoms), acylamino group, sulfonamide group, sulfamoyl group, sulfami) group, carbamoyl group, diacylamino group, allyloxy group aluponyl group, alkoxycarbonyl group, alfkyl disulfonyl group, allyloxysulfonyl group, alkanesulfonyl group, allenesulfonyl group, alkylthio group, arylthio group, alkoxycarbonylamine group,
Represents an alkylureibi group, an acyl group, a nitro group, and a carboxy group. For example, R12 and R13 may each be a hydrogen atom or a ballast group.

RIO is preferably an R-substituted phenyl group. 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). , an alkoxy group having 1 to 22 carbon atoms (e.g. methoxy group, ethoxy group, to9decyloxy group), an alkoxycarbonyl group having 1 to 23 carbon atoms (the list is methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group) acylamino group (e.g. Eva α-[3--
! ntadecyldinoxy]-butyramide group) and/
Or a cyano group. Rlo is more preferably a 2,4°6-dolychlorophenyl group.

R12% To explain R13 in more detail, these include hydrogen atoms, halogen atoms [e.g. chlorine atom, bromine atom, fluorine atom], straight chain or branched alkyl groups having 1 to 30 carbon atoms (e.g. methyl group, trifluoro Methyl group, ethyl group, t-butyl group, tetradecyl group) 1 to 3 carbon atoms
0 alkoxy group (e.g. me) -? cy group, ethoxy group,
2-ethylhexyloxy group, tetradecyloxy group)
Acylamino group (e.g. acetamido group, benzamide group, butyramide group, tetradecaneamibi group, α-(
2゜4-di-t-pentylphenoxy)acetamide 9
group, α-(2,4-:)-t-intylphenoxy)butyramide 9 groups) α-(4-hybyloxy-3-monobutylphenoxy)tetradecanamide 9 groups, 2-oxo-
pyrrolidin-1-yl group, 2-oxy-5-tetradecyl-virolin-1-yl group, N-methyltetradecanamide 9 group, t-butylcarbonamyl group) sulfonamibi group (e.g. methanesulfonyl group, bi-group, banzene) sulfonamibi group, p-toluenesulfonamito' group, p-todecylinzenesulfonamito'M, M-methyltetradecylsulfonamito group, hexadecanesulfonamibi group), sulfamoyl group (e.g. N-methyl Sulfamoyl group, N-hexadecylsulfamoyl 3, N, N
-dimethylsulfamoyl i, N-C3-()"7'syloxy)furovir]sulfamoyl group, N-(4-(
2,4-di-t- is methylphenoxy)phthyl]sulfamoyl group, N-methylh-N-tetradecylsulfamoyl group, N-)"decylsulfamoyl group) sulfamide group (e.g. N-methylsulfamide 9 group, N-octadecylsulfa i he 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 group) diacylamino group (e.g. N-succinimide group, N-7 talimito group, 2, S-:)oxo-1-oxazolidinyl, 3-rdecyl-2,S-)oxo-1
-imidazolyl, N-acetyl-N-1"decyloxycarbonyl group) allyloxycarbonyl group (e.g. phenoxycarbonyl group, p-)"decyloxyphenoxycarbonyl group) alkoxycarbonyl group having 2 to 30 carbon atoms (methoxycarbonyl group) group, tetradecyloxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, )"decyloxycarbonyl group) Carbon XR1-30
Alkoxysulfonyl 4 (6'll is a methoxysulfonyl group, octyloxysulfony/L4. te) labucyloxysulfonyl group, 2-ethylhexyloxysulfonyl group) allyloxysulfonyl' 5 (fll is a phenoxysulfonyl group, 2. (4-di-t-'!ethylphenoxysulfonyl group) C1-C30 alkali:/sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexa-7'canesulfonyl group) Allensulfonyl group (e.g. evabenzenesulfonyl group, 4-nonylbenzenesulfonyl i, p-)luenesulfonyl group) alkylthio group having 1 to 22 carbon atoms (e.g. ethylthio group, octylthio group,
Benzylthio group, tetradecylthio group.

2-(2,4-:)-t-pentylphenoxy]ethylthio group) -ruthio group (e.g. phenylthio group, p-
) Lilthio) Alkoxycarbonylamino group (e.g. ethoxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group)
9 alkylureidos (e.g. 9 N-methylureidos, N,N-dimethylureido", %, N-methyl-N
-to9decylureido r group, N-hexadecylureido 3
group, N, N-u octadecylureido group, N, N-dioctyl-N'-ethylureido group) acyl group (e.g. acetyl group, hanzoyl group, octadecanoyl group, p-)
``decaneamide benzoyl group, cyclohexanecarbonyl group), nitro group, cyano group, and carboxy group.

To explain in more detail about the alkoxy group and allyloxy group of R11, the alkoxy group includes a methoxy group, an ethquin group,
propoxy group, butoxy group, 2-methoxyethoxy group,
5ec-butquine group, hexyloxy group, 2-ethylhexyloxy group, 2-(2,4-X-t-bentylphenoxy)ethoxy group, 2-bidecyloxyethoxy group, and the aryloxy group is phenoxy group. , α or β-
These are naphthyloxy group and 4-tolyloxy group.

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

Acrylic acid, α
-chloroacrylic acids, α-alkylacrylic acids (e.g. methacrylic acid) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylic acid) Amir.

Methyl acrylate, ethyl acrylate, n+ propyl acrylate, n-butyl acrylate, t-butyl acrylate s 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n- butyl methacrylate and β-human 90Φ dimethacrylate), 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 esters, N-vinyl −
Examples include 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more types of the non-color-forming ethylenically unsaturated monomers used here can also be used together 6 For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide r1 methyl These include 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, specific examples of the coupling-off group represented by the general formula (I) will be shown, but the present invention is not limited thereto.

Q-1) Q-2) Q-3) Q-4) Q-11) Q-13) Q-14) Q-15) Q-6) Q-7) Q-8) Q-19) Q-20) C8H17(t) Q-21) Q-22) Q-23) Q-25) Q-31) C4H9(t) Q-32) NH8O2Ct sHx 5 (tL) Q-33) Q, -34) NH8O, C1, a33(n) Q-35) Q-26) Q-27) Q-28) Q-29) Q-30) Q-36) Q-37) Q-38) Q-39) Q-40) Q-41) Q-42) Q-43) Q-44) Q-45) (n)HlyCsOCH3 (li3 Q-53) Q-54) Q-55) Q-57) Q-48) Q-49) Q-50) Q-51) Q-52) Next, a specific example of the coupler of the present invention will be shown. It is not limited to these.

(M-1) CH3 H3 (M-3) (M-4) (M-7) (M-5) CH3 Shij CM-6) CH3 eye (M-9) CH.

(M-10) CH8 CH3 l CH3 CH3 l H3 (M-11) (M-12) (M-15) (M-16) l e H3 H3 (M-13) (M-14) (M-17) l (M-19) (M-20) (M-23) (M-24) 02B.

2H5 (M-21) (M-22) (M-25) (M-26) l 2H5 H3 (M-27) C/ (M-28) (M-31) (M-29) (M-30 ) (M-33) (M-34) l Shig (M-35) (M-36) (M-39) (M-40) l (M-37) (M-38) (M-41) (M-42) l H3 (M-43) (M-44) (M-47) (M-45) I l (M-46) H3 ○CH3 (M-51) C1 (M-52) (M-55) I (M-56) (M-53) I (M-54) (M-57) (M-58) The standard usage amount of the coupler of the present invention is 1 silver chloride.
The range is from 1 x 10 to 1 mol per mole, preferably from 3 x 10 -3 to 5 x 10 -' mol.

Further, the coupler of the present invention may be used alone, or two couplers may be used.
More than one type of these may be used in combination, and furthermore, they may be used in combination with a known coupler described below. Furthermore, it can be introduced into the sensitive material in the same manner as various known couplers described below.

The high boiling point organic solvent having an oxirane ring according to the present invention is preferably represented by 2α).

In the formula, Q represents a t-valent group, and t is an integer of 7 to 7 (
Q is preferably a heptavalent group containing no metal atom, more preferably
7- composed of u, c, o, p, s and N atoms
It is the basis of valence.

To give a specific example of Q, -Co-L1-Co-(t-2, Cocote L1 Ha formula (■)
(t=1, R11#R12 is synonymous with formula (It))
and so on.

Next, a high boiling point organic solvent having at least one oxirane ring will be explained.

L3 and L4 are alkylene group, cycloalkylene group,
It represents an aralkylene group, an arylene group, and an alkenylene group, and the alkylene group may be a straight-chain alkylene group or a branched alkylene group, such as a methylene group, an ethylene group, a propylene group, a methylene group, an intylene group, a hexylene group, a hexylene group, an octylene group, These include nonylene group, decylene group, undecyl group, bidecylene group, tridecyl group, tetradecyl group, hantadecylene group, hexadecyl group, etc., cycloalkylene group includes cyclointhyl group, cyclohexylene group, etc., and arylene group includes phenylene group, naphthylene group, etc. and the alkenylene group is a butenylene group,
These include a hantenylene group, a hexenylene group, a hexylene group, an octenyl group, a decenylene group, a dodecenylene group, and the like. These alkylene groups, cycloalkylene groups, arylene groups, and alkenylene groups may have one or more substituents, and the alkyl groups, cycloalkyl groups, and
It may have the same substituents as the aryl group and alkenyl group.

xl excludes L3 and L4 (represents a divalent group, -C-
0--CONH--NHCO--SO□NH-8 groups, etc.

p, (1 and r represent integers of 0 or 1.

R11S R12% R13 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group,
Further, R11 or R12 and L3 or L4, or R11 or R12 and R13 may be linked to each other to form a ring (for example, a 5- to 6-membered saturated or unsaturated carbon ring).

Here, specific examples of the alkyl group, cycloalkyl group and aryl group will be described.

The alkyl group may be a straight-chain alkyl group or a branched alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, R-methyl group, hexyl group, heptyl group, octyl group,
Nonyl group, decyl group, undecyl group, r-decyl group, tridecyl group, tetradecyl group, hantadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc., and the cycloalkyl group is, for example, cyclointhyl group, cyclohexyl group. Al in base et al.

The aryl group is a phenyl group, a naphthyl group, etc., and the alkenyl group is a butenyl group, a pentenyl group, a hexe=A4% hebutenyl group, an octenyl group, thecenyl group, a tridecyl group, an octadecenyl group, etc.

These alkyl groups, cycloalkyl groups, aryl groups and alkenyl groups may have one or more substituents (for example, halogen atoms (e.g. fluorine atom, chlorine atom, etc.), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, etc.), aryl group (e.g. phenyl group, tolyl group, naphthyl group, etc.), aryloxy group (e.g. phenoxy group, etc.), alkenyl group , alkoxycarbonyl group, etc., and examples of substituents for the aryl group include alkyl groups, etc. in addition to those listed as substituents for the alkyl group, cycloalkyl group, and alkenyl group. (The compound II3 may form a dimer or more multimer.

A high-boiling organic solvent having at least one oxirane ring represented by the general formula (ID) refers to an organic solvent with a boiling point of 175°C or higher at 1 atm, and these include phosphoric acid ester, 7-talic acid Esters, benzoic acid esters, fatty acid esters, amyl solvents, phenolic solvents,
It is a known high boiling point organic solvent such as an ether solvent.

In the present invention, the amount of the high boiling point organic solvent having an oxirane ring represented by -Momona (ID) may be any amount depending on the type and usage amount of the magenta coupler represented by -Momona (I). However, it is preferable that the high-boiling point organic solvent/magenta coupler ratio in terms of weight ratio is 0.05 to 20.Also, the high-boiling point organic solvent having an oxirane ring according to the present invention represented by -mona (n) is It can also be used in combination with other conventionally known high boiling point organic solvents to the extent that the purpose of the present invention can be achieved. Examples of these high boiling point organic solvents include heptal phthalate, diptyl phthalate, di-2-ethylhexyl phthalate, etc. Acid ester solvents, amyl solvents such as N,N-diethyl r-decane amide 3, fatty acid ester solvents, benzoate ester solvents, 2゜4-ditert
- Phenol solvents such as aminophenol (phosphate ester solvents such as tri-2-ethylhexyl phosphate and tricresyl phosphate), and the like.

Specific examples of the high boiling point organic solvent having an oxirane ring represented by the general formula (I[) are shown below, but the invention is not limited thereto.

P-, 1 P-12 P-13 Shie P-32 P-37 The color light-sensitive material of the present invention comprises a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. It is preferred that the silver halide emulsion layers are applied in this order or in any arbitrary arrangement thereof.

Examples of the silver halide used in the present invention include silver chloride, silver bromide, silver chloride (iodo)bromide, and silver iodobromide.
Among these, silver chloride and silver chloride(iod)bromide are preferred. Furthermore, the halogen composition of the silver decagenide grains in one emulsion layer is
It is preferable that 90 moles or more of the total silver halide constituting the 710 silver germide grains is silver chloride and consists of silver chlorobromide containing substantially no silver iodide. Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 molt or less. A particularly preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 95 moles or more of the total silver halide constituting the silver halide grains is silver chloride.

Further, the silver halide grains according to the present invention can be reacted in a simultaneous mixing method of at least 10 moles of silver bromide to form a localized phase. Furthermore, the localized phase can also be formed using the so-called converge run method, which involves converting the already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can also be formed by adding silver bromide fine particles and recrystallizing them on the surface of silver chloride particles.

Regarding these manufacturing methods, for example, the above-mentioned patent application 1986-3
It is described in the specification of No. 19741.

In the localized phase of the silver halide grains of the present invention or its substrate,
The effect of the present invention is further improved by containing a metal ion different from silver ion (for example, a metal ion from group Ⅰ of the periodic table, a transition metal ion from group Ⅰ, a lead ion, a thallium ion) or a complex ion thereof. It is preferable.

Iridium ions, rhodium ions, iron ions, etc. are mainly used for localization, and osmium, iridium, rhodium, platinum, ruthenium, palladium, etc. are mainly used as substrates.
Metal ions selected from cobalt, nickel, and iron sudo or complex ions thereof can be used in combination. Furthermore, the type and concentration of metal ions can be changed for localization and for the substrate.

In order to contain metal ions for localization of silver halide grains and/or in other grain parts (substrates), the metal ions are added to the preparation liquid before grain formation, during grain formation, or during physical ripening. do it. For example, metal ions in gelatin aqueous solution, halide aqueous solution, silver salt aqueous solution,
Alternatively, it can be added to other aqueous solutions to form silver halide grains.

Alternatively, metal ions may be introduced in advance by incorporating metal ions into fine silver halide grains, adding these to a desired silver halide emulsion, and further dissolving the fine silver halide grains. This method is particularly effective for introducing metal ions into the localized silver bromide phase on the surface of silver halide grains. The addition method can be changed as appropriate depending on where in the silver halide grains the metal ions are to be present.

In particular, the localization is preferably deposited together with at least 5 (l) of the total iridium added during the preparation of the silver halide grains.

Here, depositing the localized compound together with iridium ions refers to supplying an iridium compound simultaneously with, immediately before, or immediately after supplying silver and/or halogen to form the localized compound. say.

The silver halide grains according to the present invention have (100
) surface, (111) surface, or both surfaces, and even those containing higher-order surfaces are preferably used. It will be done.

The shape of the silver halide grains used in the present invention is cubic,
Those with regular crystal shapes such as tetradecahedrons and octahedrons, as well as six irregular crystal shapes such as spherical and plate shapes, or composites of these crystal shapes. There are things that have a shape. It is also possible to use a mixture of particles with various crystal forms, but in particular, particles with the above-mentioned regular crystal forms account for 50% or more, preferably 70% or more, and more preferably 90% or more. It is better to include at least 1.

In the silver halide emulsion used in the present invention, tabular grains having an average aspect ratio (length/thickness ratio) of 5 or more, particularly preferably 8 or more, occupy 50 or more of the total projected area of the grains. It may also be an emulsion like this.

The size of the silver halide grains related to the present invention may be within the range commonly used, but the average grain size is 0.1 μm to 1 μm.
．． The zero particle size distribution, which is preferably 5 μm, may be polydisperse or monodisperse, but monodisperse is preferable. The particle size distribution, which indicates the degree of monodispersity, is determined by the statistical coefficient of variation (standard deviation S when the projected area is approximated by a circle).
The value S/4) divided by the diameter d is preferably 20% or less,
More preferably, it is 15% or less.

Further, two or more of such tabular grain emulsions and monodispersed emulsions may be mixed. When emulsions are mixed, it is preferable that at least one of the emulsions has the above-mentioned variation coefficient, and it is more preferable that the variation coefficient of the mixed emulsion satisfies the above-mentioned range of values.

The so-called matrix portion used in the present invention, other than for localization of silver halide grains, may have different phases inside and on the surface, or may have a uniform phase.

The silver halide emulsion used in the present invention is usually one that has been physically ripened, chemically ripened, and spectrally sensitized.

Regarding the chemical sensitizers used for chemical ripening, those described in the lower right column of page 18 to the upper right column of volume 22 of the specification of JP-A-62-215272, and the spectral sensitizers are Those described in the upper right column of page 22 to page 38 of the same publication are preferably used.

Further, as the capri-preventing agent or stabilizer used during the production or storage of the silver halide emulsion used in the present invention, those described in the upper right column of pages 39 to 72 of the same publication are preferably used.

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-forming imagers are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide 9-conductors such as inzoylacetanilito 9 and bivaloylacetanili 1 are preferred.

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

(Y-1) In the formula, X represents a hydrogen atom or a coupling-off group.

R21 represents diffusion resistance with a total carbon number of 8 to 32, and R22
represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total of 8 to 32 carbon atoms.

R23 represents a hydrogen atom or a substituent. When there are two or more R23's, they may be the same or different.

For more information on pivaloylacetanilide type yellow couplers, see U.S. Pat. No. 4,622,287, No.
It is described in column 15, line 15 to column 8, line 39, and in column 14, line 50 to column 19, line 41 of the specification of 4,623,616.

For details on the benzoylacetanilide type 9 yellow coupler, see U.S. Pat. No. 3,408,194;
No. 33,501, No. 4,046,575, No. 4,13
It is described in No. 3,958, No. 4,401,752, etc.

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

(Y-4), (Y-6), (Y-7), (Y-15).

(Y-21), (Y-22), (Y-23), (Y-2
6).

(Y-35), (Y-36), (Y-37), (Y-3
8).

(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) and (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. 3.408,
Typical specific example (34) described in column 6 of specification No. 194
, Compounds (16) and (19) listed in Column 8 of Specification No. 3,933,501, Compound examples (9) listed in Columns 7 to 8 of Specification No. 4,846,575, 4.133,
Compound (1) described in columns 5 to 6 of specification No. 958, compound example 1 described in columns 51 and 11 of specification 4,401,752, and the following compounds a) to h) are listed. be able to.

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, and a typical example thereof is as described in U.S. Pat. , 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 the leaving group in U.S. Pat.
, 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As pyrazoloazole couplers, U.S. Patent No. 2,
369,879, preferably pyrazolo C5,1-c) (1,2,4)) liazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (198
Examples include the pyrazolopyrazoles described in June 2003). Any of the above-mentioned peta couplers may be a polymer coupler.

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

Here, R31 represents a diffusion-resistant group having a total carbon number of 8 to 32, and R32 represents a phenyl group or a substituted phenyl group. R33 represents a hydrogen atom or a substituent. Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring has a substituent (
fused rings) may also be useful.

X2 represents a hydrogen atom or a leaving group. For details of the substituents of R33 and the substituents of the azole ring, see, for example, U.S. Pat. No. 4,540.654, column 2, column 4.
It is described in the 1st line to the 8th column, 27th line.

Among pyrazoloazole couplers, U.S. Pat.
The imidazo[1<2-b]pyrazoles described in U.S. Pat. No. 500,630 are preferred, and the pyrazolo(x,5-b) described in U.S. Pat.

(1,2,4) triazoles are 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-61-65245, and as described in JP-A-61-65246 Pyrazoloazole couplers containing 9 sulfonamide groups in the molecule, pyrazoloazole couplers containing 9 alkoxyphenylsulfonamide groups 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
As described in No. 1,647 and No. 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; typical examples 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, No. 4,564,
Compounds (I-4) and (I-5) described in No. 590, compounds (1) and (2) described in JP-A-61-39045,
(3) and the compound described in Q Xun, No. 62-70846 (
C-2) can be mentioned.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2,895,826, No. 4.
No. 334,011, No. 4,500,653 and JP-A-5
There are 2,5-diacylaminophenol couplers described in U.S. Patent No. 9-164555, and typical examples thereof include compounds described in U.S. Pat. Compound <17+, 4.
Compound (2) and α-ri described in No. 565,777, No. 4.
Compound (4) described in No. 124,396, No. 4,613
, No. 564 (Nie 19), and the like.

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. 61-390441, and Japanese Patent Application No. 61-100222, there are compounds in which a nitrogen-containing heterocycle is fused to a 7-enol nucleus. , 327,173, compound (3) described in 4,564.586 and αe1, compound (1) and (3) described in 4,430,423. ), and the following compounds.

In addition to cyan couplers of the type, European Patent Application Publication I
Diphenylimidazole cyan couplers described in P0,249,453A2 can also be used.

Other examples of phenolic cyan couplers include U.S. Pat.
．． No. 444.872, No. 4,427,767, No. 4,
No. 579,813, European Patent (EP) 067.689B
U.S. Pat. No. 1, U.S. Pat. No. 1, U.S. Pat. ), coupler 11 described in No. 4,444.872, coupler 11 described in No. 4,427,767 (3
), the coupler (6) and Q-Xun described in No. 4,609,619, and the turnip 5-(1) described in No. 4,579,813.
or αυ, the coupler described in European Patent No. 067,689 B1 (451 or 511 JP-A-61-426)
Examples include coupler (3) described in No. 58.

Examples of naphthol-based cyan couplers 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 (e.g., U.S. Pat. No. 2,474,293, U.S. Pat. No. 4,282,312)
, those with an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 50-14523), those with nine carbonamide or sulfonamide groups at the 5-position (e.g., JP-A-60-2)
No. 37448, No. 61-145557, No. 61-15
No. 3640), and those with an aryloxy or ethyl group (
(e.g., U.S. Pat. No. 3,476,563); those with substituted alkoxy leaving groups (e.g., U.S. Pat. No. 4,296,19);
9), and those having a glycolic acid leaving group (for example, Japanese Patent Publication No. 39217/1983).

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) or 2) is used.

Formula (A1 Formula Formula (B) Wl-Coo-W2 (Q ('F5 Wl-O-W2 (wherein, Wl, W2 and W3 are each ta or an unsubstituted alkyl group, cycloalkyl group, alkenyl group ,
Represents an aryl group or a heterocyclic group, W4 is Wl, OW
l or 5-Wl, 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 ring).

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous solution of hydrophilic colloid 9 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 hyperquinone derivative, an aminephenol visiting compound, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

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, Hyde 90 quinones,
Hindered 3-phenols, mainly 6-human 90-oxychromans, 5-human 10-oxycoumarans, spirochromans, p-alkoxyphenols, bisphenols, gallic acid derivatives, methylenedioxy(benzenes), amine phenols, Typical examples include hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds.Also, (bissalicylald 9 oximado) nickel complexes and (bis-N,N- Metal complexes such as dialkyldithiocarbamide (nickel) complexes can also be used.

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

Hydroquinones are subject to U.S. Patent No. 2,360.290, U.S. Patent No. 2,418,613, and U.S. Patent 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, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-human 90 xycoumarans, or spirochromans are U.S. Patent No. 3,432゜3
No. 00, No. 3,573,050, No. 3.574.
No. 627, No. 3,698,909, No. 3,764
．． No. 337, No. 52-152225, etc., and spiroindanes are described in U.S. Patent No. 4,360.589, p.
-alkoxyphenol and 1 is U.S. Pat. No. 2,735,
No. 765, British Patent No. 2,066,975, JP-A-5
No. 9-10539, Special Publication No. 57-19765, etc.
Hindered 3-phenols are disclosed in U.S. Patent No. 3,700,4
No. 55, JP-A No. 52-72224, U.S. Patent No. 4.2
No. 28,235, Japanese Patent Publication No. 52-6623, etc., and gallic acid derivatives, methylenedioxybanzenes, and aminophenols are disclosed in U.S. Patent No. 3,457,079, respectively.
No. 4,332,886, Japanese Patent Publication No. 56-21144, etc., hindered amines are disclosed in U.S. Patent No. 3,336,
No. 135, No. 4,268,593, British Patent No. 1.
32 889, same No. 1,354.313, same No. 1,
No. 410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1973
No. 8-114036, No. 59-53846, No. 59-
78344 etc., phenolic hydroxyl wood ether,
Ester derivatives are disclosed in U.S. Patent Nos. 4,155,765, 4.174.220, 4.254,216,
No. 4,264,720, Japanese Unexamined Patent Publication No. 145530/1983
Metal complexes are described in US Pat. Patent No. 4.050,938,
4.241,155, British Patent No. 2.027,7
31 (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 that chemically bonds with the aromatic amine developing agent remaining after color development processing to form a chemically inert and substantially colorless compound (and/or an aromatic amine developer remaining after color development processing). The simultaneous or single use of compound C), which chemically combines with the oxidized form of an amine color developing agent to form a chemically inert and substantially colorless compound, can be used, for example, in the film during storage after processing. This is preferable in order to prevent staining and other side effects caused by the reaction of Kabuku with the residual color developing agent or its oxidized product to produce color pigments.

A preferable compound (g) has a second-order reaction rate constant with p-aningine of 2 (in trioctyl phosphate at 80°C) of 1.011/mob・sec ~
It is a compound that reacts in the range of I x 10-51/nno1·8θC.

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 (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. be.

A more preferable compound (g) can be represented by the following general formula (1'I) or (F'II).

General formula (FI) R1-(View-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 is 1 Or represents 0.

B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents an aromatic amine developing agent added to the compound of general formula (1'n). represents a group that promotes 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 (F'I) and (1'II),
No. 2-158643, No. 62-212258, No. 62
-214681, 62-228034 and 62-
It is described in No. 279843, etc.

Further, details of the combination with the above-mentioned compound IG) and compound (g) 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, benzene substituted with an aryl group) IJ azole compounds (e.g. those described in U.S. Pat. No. 3,533,794), 4-thiazolido-9 compounds (e.g. U.S. Pat. No. 3,314,794)
No. 3,352,681), hanzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,352,681),
Nos. 705,805 and 3.707,375), butadiene compounds (e.g., U.S. Pat. No. 4,045,
229 or benzoxidol compounds (eg, those described in U.S. Pat. No. 3,700,455) can be used. UV-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 eradication. Such dyes include: Included are 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. For more information on how to make gelatin, see The Macromolecule Chemistry of Gelatin, 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 materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The term "reflective support" used in the present invention refers to a material that enhances the reflectivity and details of the dye image formed in the silver halide emulsion layer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, fermented zinc, 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 recommended to thoroughly knead a white pigment in the presence of a surfactant (and also to coat the surface of pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (H) per defined unit area of white pigment fine particles is determined by dividing the observed area into adjoining unit areas of 6 μm x 6 μm.

Occupied area ratio of fine particles projected on the unit area (%)
It can be determined by measuring (R1). The coefficient of variation of the occupied area ratio (%) is R for the average value of R1 < W)
It can be determined by the ratio s/R of the standard deviation day of 1. The number (n) of target unit areas is preferably 6 or more, and therefore the coefficient of variation s/R can be determined.

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

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 a stabilization treatment). Bleaching and fixing may be carried out 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 ml per photosensitive material.
00m/or less. More preferably, it is 120d or less. More preferably, it is 100d 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. Note that the additives mentioned here include, for example, water for diluting the concentrate, preservatives that tend to deteriorate over time, and alkaline agents that increase 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-t) ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-humanoxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfonamide) + T ethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphorus salts, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, human 90-xylamine, diethylhibiroxylamine, sulfite human 9-radazines, phenyl semicarnocytos, triethanolamine, catechol sulfonic acids, etc.)
') Ethylenediamine (1,4-diazabicyclo(2
, 2, 2) various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, promoters such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and pigment forming agents. couplers, competitive couplers, coupling agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphono Various chelating agents represented by carboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimidinoacetic acid, 1-human 9
0xyethylidene-1,1-Q phosphonic acid, nitrilo-
N,N,N-) dimethylenephosphonic acid. Typical examples include ethylenediamine-N, N, N/, N/-tetramethylenephosphonic acid, ethylenediamine-9 (o-human 90xyphenylacetic 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 dihydro-90xylenes such as hyde-10quinone, 1-phenyl-3
-3-pyrazolito 97 such as pyrazolysine or N-
Known black and white developing agents such as amine phenols such as methyl-p-aminophenol 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. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally 3 g or less per square meter of light-sensitive material, and the bromide ion concentration in the replenisher is reduced (possibly even 500 m2).
It can also be less than /. When reducing the amount of replenishment, it is preferable to reduce the contact area of the processing layer with the air to prevent evaporation of the solution and air oxidation. Also, use means to suppress the accumulation of bromide ions in the developer. This also allows the amount of replenishment to be reduced.

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

The bleaching process may be carried out simultaneously with the fixing process (open fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a target fixing treatment. 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. As a bleaching agent, for example, iron (2), Kobal) (I
n), chromium M.

Compounds of polyvalent metals such as copper (I[), peracids, quinones, nitro compounds, etc. are used. Representative bleaching agents include ferricyanide; dichromate; Tetraacetic acid, glycol ether diamine tetraacetic acid,
Aminopolycarboxylic acids such as or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; ditroinzenes, etc. can be used. Among these, aminopolycarboxylic acid iron complexes and persulfates, including ethylenediaminetetraacetic acid iron(2) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution.

Additionally, aminopolycarboxylic acid iron [phase] complexes are particularly useful in both bleaching solutions and brightening fixing solutions.

The pH of the bleaching solution or bleach-fixing solution used for these aminopolycarboxylic acid complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered.

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;
．． 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. 10.4232, No. 53-124.424, No. 53
-141,623, 53-28,426, Research Disclosure, (617,12940197
Compounds having a mercapto group or disulfide group as described in JP-A No. 140-129-1982; thiazolidine derivatives described in JP-A No. 8-506-1982 and JP-A No. 20-832-1983; No. 53-32,735
No. 3,706,561; German Patent No. 1,127,715;
-Iodide described in No. 16,235; West German Patent No. 996,
Polyoxyethylene compounds described in Japanese Patent Publication No. 410, 2.748,430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Others No. 53-94,927, same 5
No. 4-35.727, No. 55-26,506, No. 58
Compounds described in No.-163,940; bromide ions, etc. can be used.

Among them, compounds having 9 mercapto groups or disulfide groups are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in U.S. Pat. No. 3,893,858 and West German Patent No. 1.290,8.
No. 12 and JP-A-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 photosensitive material. These bleach accelerators are particularly effective when brightening and fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfate, thiocyanate, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfate is commonly used, and ammonium thiosulfate is 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
Urnal of the 5ociety of M
tion Picture and Te'1evis
ion Engineers Volume 64, P, 248-
253 (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. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to such problems, 1.
The method of reducing calcium ions and magnesium ions described in Japanese Patent No. 131.632/1988 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds and cyabendazole, chlorinated sodium isocyanurate, etc., and other bencito IJ azoles, etc., written by Hiroshi Horiguchi, "Chemistry of germicidal and fungicidal agents," Hygiene Technology Kanawa, "Sterilization of microorganisms," It is also possible to use the disinfectants described in ``Bactericidal and Antifungal Techniques'' and ``Encyclopedia of Antibacterial and Antifungal Agents'' by Japan Antibacterial and Antifungal Science Kinawa.

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 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 20 minutes.
5-40t:: selects a range of 30 seconds to 5 minutes. 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 Nos. 57-8,543 and 58-14.
No. 834, No. 60-220, 345! All known methods of precepts may 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 fM 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
Indo-9 aniline compound described in No. 7, No. 3,342
, No. 599, Research Disclosure 14, 85
Thick basic type compounds described in No. 0 and No. 15,159,
Aldo-9-ol compounds described in No. 13.924, metal salt complexes described in U.S. Pat. No. 3,719,492, JP-A-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 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64.339 and JP-A-57-14.4547.
No. 58-115,438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
A treatment using cobalt intensification or hydrogen peroxide intensification as described in , 674, 499 may also be carried out.

In order to fully utilize the excellent features of the silver halide photographic light-sensitive material of the present invention, it is necessary to use color development that does not substantially contain dill alcohol and contains 0.002 mol/1 or less (7) of bromide ions. It is preferable to process with a liquid for a developing time of 2 minutes and 30 seconds or less.

The term "substantially free of alcohol" as mentioned above means 92% or less per 11 parts of the color developer, preferably 0.5% or less, and most preferably no alcohol at all. .

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

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.

Preparation of coating solution for the first layer Yellow coupler (E:Y) 19.1 g, color image stabilizer (cpa -1) 4.4.9 and color image stabilizer (c
27.2 cc of ethyl acetate (Solv-3) 8.2F was added to 0.7 g of pd-7) and dissolved.
Add this solution to 1 sscc of a 10% aqueous gelatin solution containing 8 CC of sodium decylbenzenesulfonate.
It was emulsified and dispersed. On the other hand, block silver bromide emulsion (grain size 0.
85μ, a cube with a coefficient of variation of 0.07, containing 1 mol of silver bromide locally on a part of the grain surface as a proportion of the whole grain)
Two types of blue-sensitive sensitizing dyes shown below were added thereto in an amount of 2.0 x 10 moles per mole of silver, followed by sulfur sensitization. Mixing and dissolving the emulsified dispersion and this emulsion,
A first layer coating solution was prepared to have the composition shown below.

The 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, 1-oxy-3,5-:)chloro-a-)riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (2.OX10 of each of the above two types per mole of silver halide)
-4 mol) Green-sensitive emulsion layer Red-sensitive emulsion layer (14.0 x 10 mol per mol of silver halide)
and CzRs I'''' 5H11 (per mole of silver halide) 0.9
2.6 X 10 moles were added per mole.

(7.0×10 mol per mol of silver halide) Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer,
8.1-(5-methylureidophenyl)-5-mercaptotetrazole per mole of silver halide, respectively.
5X10 moles, 7.7 x 10-' moles, 2.5
X 10-' moles were added.

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

and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (y/co). The silver halogenide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti03) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion gelatin yellow coupler (EXY) Color Image stabilizer (Cpd-1) Color image stabilizer (cpa -7) Solvent (Soxv-3) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cp(1-5) Solvent (Solv-1) Solvent ( Solv-4) Third layer (green-sensitive layer) 0.30 1.86 0.82 0.19 0.03 0.35 0.99 0.16 0.08 Silver chlorobromide emulsion (grain size 0.40μ .

The entire particle is a cube with a coefficient of variation of 0.09. 1 mol of silver bromide particles as a proportion of Contained locally on a part of the surface) gelatin 0.20 1.24 Magenta coupler (EXM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) 0.29 0.09 0.06 Solvent (So], v-2) Solvent (Solv-7) Fourth layer (ultraviolet absorption layer) gelatin Ultraviolet absorber (UV-1) Color mixing prevention agent (cpa -5) Solvent (Solv-5) fifth layer Silver chlorobromide emulsion (grain size 0.36μ).

(Contains 1.6 mol of silver bromide localized on a part of the grain surface as a proportion of the whole grain with a coefficient of variation of 0.11) Gelatin cyan coupler (EXC) Color image stabilizer (cpa -6) Color image Stabilizer (cpa-7) Color image stabilizer (Cpd-9) Solvent (Solv-4) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (Iff-1) 0.32 0.16 1.58 0. 47 0.05 0.24 0.21 1.34 0.34 0.17 0.34 0.04 0.37 0.53 0.16 Color mixing prevention agent (cpa -5) Solvent (Solv -5) Seventh Layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin (EXY) Yellow coupler 0.02 0.08 1.33 0.17 0.03 (ExC) Cyan coupler (Cpd- 4) Color image stabilizer I R= 1:16 mixture (weight ratio) of H, C2H5, C4H, (Cpd-1) Color image stabilizer (cpa-5) Color mixture prevention agent (Cpd-3) Color image stabilization Agent H (Cpd-6) Color image stabilizer C4Hg (tl C4H9 (t+ 2:4:4 mixture (weight ratio)) (Cpcl-7) Color image stabilizer (Solv-2) Solvent -fCH2-CH piece CONHC4Hg ( tl average molecule t 60,000 (UV -1) 3-near mixture of ultraviolet absorbers (volume ratio) (Solv -3) solvent C5Hu (tl 42:4 mixture (weight ratio)) (Soxv -1) solvent C4H9 (t) (Solv-4) Solvent (Solv-5) Solvent C00C8H17 (CH2)s COOC8H1□ The silver halide color photographic light-sensitive material produced as described above is designated as sample number 01.
(green-sensitive layer) high boiling point organic solvent (hereinafter abbreviated as solvent)
Samples 02 and 03 were obtained by replacing tri-2-ethylhexyl phosphate and tricresyl phosphate in equal weights.
was created.

Subsequently, as shown in Table 1, samples were prepared by replacing the magenta coupler and solvent in the same layer with equimolar amounts of the coupler and equal weight of the solvent.

Furthermore, samples were prepared by changing the material composition of the same layer as described below.

3rd layer (4 green sensitive layers) Emulsion (same as sample 01) Gelatin magenta coupler ((1) ) Color image stabilizer (cpa -3) Color image stabilizer (*1) Color image stabilizer (*2) Solvent (Soxv -2) * 0.36g/Go1.24 0.31 0.12 0.06 0.09 0.42 Magenta coupler (1) l *1 Color image stabilizer H *2 Color image stabilizer *Solvent (Solv-2) 1:1 mixture of solvents in Sample 01 The following experiment was conducted to evaluate the photographic performance of these prepared samples.

First, a photosensitive needle (Fuji Film Co., Ltd. F
Using a WH type (light source color temperature: 3200'K), stepwise exposure for sensitometry was provided through a three-color separation filter. The exposure at this time was 0.1 seconds, and the exposure was 2500.
The exposure amount was adjusted to be that of MS.

After exposure, color development processing was performed using the following processing steps and processing solution composition.

Processing process〉 Temperature〉 Processing time〉 Color development 35℃ 45 seconds Bleach fixing
35℃ 45 seconds water washing 0 35℃
Wash with water for 30 seconds 0 35℃ Wash with water for 30 seconds 0 35℃ Dry for 30 seconds
75℃ 60 seconds Color developer water 8
00rILl Ethylenediamine-N, N, N'
μ′-tetramethylenephosphonic acid 3
．． 0 Ii Triethanolamine 8, Oy Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate N,N-bis(carboxymethyl) Human 9 radine fluorescent brightener (WH-TEX4B manufactured by Sumitomo Chemical) Add water and PR (25°C) Bleach-fix solution water thio Ammonium sulfate solution (700!il/l ammonium sulfite ethylenediaminetetraacetic acid ferric ammonium dihydrate ethylenediaminetetraacetic acid disodium chloride ammonium bromide Add ice vinegar and brewed water to pH (25°C) 1.411 5 g 5, OI 5.0!! 1.02 oooml I Q, Q 5 QQmg QQm 18.9 3g 000m 5.5 Washing liquid Tap water was treated with an ion exchange resin to reduce calcium and magnesium to 3 ppm or less (25℃) The electrical conductivity was 5 μB/CrIL).

The photographic characteristic values of the magenta color image obtained by performing the above processing are minimum density (Dmin) and maximum density (Dmax).
and sensitivity (log K value giving a reflection density of 0.5) were measured using a self-recording densitometer. The results are shown in Table 1.

Table Z (with vc) Dmin: Dmax: Sensitivity: Dmin value of sample 01? What is the difference between each sample and the standard? Indicates nine values. Plus (g) indicates an increase in Dmin.

A value showing the difference between sample 01 and each sample based on the DmaxtiY standard. Plus (± means high concentration, minus (
→ means low concentration 7.

Taking the logE value given by sample 010 reflection density 0.5'2 as the standard, calculate the difference with each sample and calculate the nine values.

Plus f-+-1 means high sensation t, minus (→ means low sensation 7.

From the results in Table 1, it is clear that, using high silver chloride emulsions and short color development times, the couplers of the present invention in combination with the solvents of the present invention provide high Dmax and high sensitivity without increase in Y1Dmin.

On the other hand, with comparative couplers, although an increase in Dmax and an increase in sensitivity are certainly observed when the solvent of the present invention is used, the effects cannot be said to be sufficient. It is also clear that, compared to another comparative coupler (Sample 37), the sample using the combination of the coupler of the present invention and the solvent of the present invention exhibits superior photographic performance.

Example 2 Samples 01 to 35 prepared in Example 1 were exposed in the same manner as described in Example 1, and using a Beno R-processor, the following processing steps were carried out to expose samples 01 to 35 that were twice the tank capacity for color development. Continuous processing (running test) was performed until replenishment.

Processing process Color development bleach fixing rinse ■ Rinse ■ Rinse ■ Drying temperature Time Replenishment Tank capacity 35°C 30-35°C 30-35°C 30-35°C 30-35°C 70-80°C 45 seconds 45 seconds 20 seconds 20 seconds 20 Seconds 60 seconds 61d 215 Wtt 50d Photosensitive material 1m (4 tank countercurrent system was used for rinsing ■-■) The composition of each processing solution is as follows.

Color developer tank liquid water
800 at ethylenediamine-N,N,N,N-1,5,9 tetramethylenephosphonic acid replenisher 800 gotriethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl- 4-aminoaniline sulfate a, oI! 1.4 I 5 I s, og 12.0.9 5 F 7.09 N, N-bis(carboxymethyl)hydrogen 5.5 g Dorazine fluorescent brightener (WH Techex 4B, Sumitomo Chemical 'A) 1. 01 Add water and pHc 25℃) 000d 10.05 7, Of! 2.Ol 000m7 10.45 Bleach-fix solution (tank solution and replenisher are the same) water
100 ammonium gothiosulfate (70%) 100 iu sodium sulfite 179 iron ethylenediaminetetraacetate (
III) 55N ammonium ethylenediaminetetraacetic acid disodium Add 5fI water to pH (25℃) 000m 6.0 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium each 34 or less) Continuous processing Before starting and after finishing, the sensitometric samples were processed as described in Example 1 and the photographic performance of the magenta images obtained was evaluated. The results are shown in Figure 2.

Table 2 Table 2 (Continued) The numerical values in the table indicate the differences in the respective characteristic values before and after the continuous processing started. The larger the value, the greater the processing variation.

From Table 2, it is clear that by using the coupler of the present invention in combination with the solvent of the present invention, stable processing with small processing fluctuations can be achieved in continuous processing.

Finally, it was observed that the sample using the coupler of the present invention in combination with the solvent of the present invention gave high D w&x and high sensitivity, similar to the results obtained in Example 1.

From these results, the silver halide color photographic material using a high silver chloride emulsion and a short color development time in combination with the coupler of the present invention and the solvent of the present invention shows no increase in Dmin, and has high Dmax and high sensitivity. It is clear that it is possible to perform stable processing with little processing fluctuation in continuous processing.

Example 1 The same g element Z as described in Example 1 was applied to the sample exploded in Example 1, and the same color development process was performed to obtain a developed color image. These color images were evaluated for color image fastness and staining in white areas under the conditions shown below.

(1) 100℃, 7 days (2) 80℃, 70%RH, 2 weeks Results are shown in Table 3
Shown below. Regarding color image fastness, the displayed values are based on the density (Do) 1.0 before the start of the test. The percentage of the ratio of o to the concentration (D) at the end of the test, D/Do x 100
The stain is expressed as the difference (ΔDB) between the density of blue light in the white background area before the start of the test and the density after the end of the test. Therefore, the higher the color image fastness value, the more solid it is, and the smaller the color image fastness value, the less contamination on the white background area, and the better the image quality.

Before starting the color image fastness test, the samples were treated with a 5-cell red blood salt aqueous solution for 3 minutes (and then washed with water for 5 minutes) to ensure that no leuco dye remained (especially samples 01 to 01).
09) and then conducted this experiment.

(Continued) As a result of this experiment, the color image of the sample using the coupler of the present invention in combination with the solvent of the present invention was more robust than that of the comparative coupler under both high temperature and high temperature/high humidity conditions, and It is clear that the image shows excellent image stability with little increase in stain.

When evaluated in conjunction with the photographic performance of Example 1, Comparative Sample 37 has better photographic performance than Comparative Samples 01 to 09, but is significantly inferior in color image fastness and stain of image storage. On the contrary, Comparative Samples 01 to 09 are somewhat good in terms of staining, but inferior in photographic performance.Although the comparative samples both have advantages and disadvantages in performance, the combination of the coupler of the present invention and the solvent of the present invention significantly improved both performances. , it is clear that it shows excellent performance.

Subsequently, a test was conducted under the following conditions in order to evaluate the fastness of the color image to light and stain.

Test conditions: xenon fading tester, 100,000 lux, 1
The 0-day evaluation was carried out in accordance with the method for evaluating color image fastness described above. The results are shown in Table 4.

Table (Continued) From the results in Table 4, it is clear that the sample using the coupler of the present invention in combination with the solvent of the present invention has a remarkable improvement effect in both light fastness and stain compared to the comparative coupler.

Example 4 A multilayer photographic paper having the following layer structure was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

1st layer coating solution preparation Yellow coupler (EixY) 60.01 and antifading agent (Cpd-1) 2 & 0.9 to ethyl acetate 15
0 ee and solvent (Solv-3) 1. OCC and solvent (Solv-4) 3. OCC was added and dissolved, and this solution was mixed with 10% OCC containing sodium dodecylbenzenesulfonate.
After adding it to an aqueous solution of tisgelatin 450 ee, it was dispersed with an ultrasonic homogenizer, and the resulting dispersion was converted into a silver chlorobromide emulsion (silver bromide 0.7 mol %') containing a blue-sensitive sensitizing dye 4209 A first layer coating solution was prepared by mixing and dissolving the above ingredients. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer,
1. Ita for 2-bis(vinylsulfonyl)ethane.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer: anhydro-5-5'-dichloro-3°3'-disulfoethylthiacyanine hydroxide Green-sensitive emulsion layer: anhydro-9-ethyl-5,5'-
Diphenyl-3,3'-9 sulfomethyloxacarbocyanine hydroxide red-sensitive emulsion layer: 3,3'-diethyl-5-methoxy-9
゜9'-(2,2'-dimethyl-1,3-proA))
Thiacarbocyanine yosemite and the following were used as stabilizers for each emulsion layer.

In addition, the following was used as an irradiation-preventing dye.

[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-)sulfonate disodium salt N , N'-(4,8-dihydroxy-9,10-:)oxo-3,7-cisulfonatoanthracene-1,5-diyl)bis(aminemethanesulfonate)-tetrasodium salt [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 (layer structure) Below are the details of each layer. Indicates the composition. The number is the coating amount (,9/m2)
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) The above-mentioned silver chlorobromide emulsion (AF Br: 0.70.
29 molti cube, particle size 0.9μ) Gelatin 1.80 Yellow coupler (EXY) Anti-fading agent (Cpcl-1) Solvent (Solv-3) Solvent (Solv-4) Second layer (color mixing prevention layer) Gelatin color mixing prevention Agent (Cpd-2) Solvent (Solv-1) Solvent (Solv-2) Third layer (green-sensitive layer) 0.80 0,055 0,015 0.60 0.28 0,01 0, O3 Chlorobromide Silver emulsion (AEBr: 0.7 molt cubic, particle size 0.4511') Gelatin magenta coupler (ExM) Antifading agent (Cpd-3) Antifading agent (Cpd-4) Solvent (Solv-1) Solvent (Solv - 2) Fourth layer (color mixing prevention layer) Gelatin 1.70 0.305 1. 40 0.67 0.23 0.20 Color mixture prevention agent (Cpd-2) Ultraviolet absorber (UV-x) Ultraviolet absorber (Uy-z) Solvent (Solv-1) Solvent (Solv-2) Fifth layer ( Red sensitive layer) 0.065 0.45 0.23 0.05 Silver chlorobromide emulsion (AgBr: 4 molti cube, grain size 0.5μ) 0.21 Gelatin cyan coupler (ExC-1) Cyan coupler (EExC- 2) Anti-fading agent (cpa-t) Solvent (Solv-1) Solvent (Solv-2) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (Uv-1) Ultraviolet absorber (UV-2) Solvent (solv -1) Solvent (Solv-2) 1.80 0, 12 0.20 0.09 0.70 0.26 0.07 0.30 0.09 Seventh layer (retaining layer) Gelatin 1.07 (ExC -2) Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
tert-amylphenoxy)butyramide] phenol (Cpd-1) antifading agent 2.5-tart-amyl phenyl-3,5-tsrt-7' hydroxybenzoate (Cpd
-2) Color mixing inhibitor 2.5-di-tert-octylhydroquinone (Cp
d-3) Anti-fading agent 1.4-Di-tert-amyl-2.5-dioctyloxybenzene (EXY) Yellow coupler α-pivalyl α-(3-benzyl-1-hydantoinic)-2#RORO5[β -(dotecylsulfonyl)butyramide]acetanilide (EXM) magenta coupler 1- (2,4,6-dolichlorophenyl) -3(2
-chloro-5(3-octenylsuccinimide)anilino-5-pyrazolone (ExC-1) cyan coupler 2-interfluorobenzamide-4-chloro-5(2
-(2,4-:)-tert-amylphenoxy)-3
- Methylbutyramide phenol fifth layer (red-sensitive layer) Silver chlorobromide emulsion (A,!i' Br: 4 molti cube, grain size 0.5 μ) Gelatin cyan coupler (E: cC-1) Cyan coupler (EXC -2) Anti-fading agent (Cpd-1) Solvent (Solv-1) Solvent (Solv-2) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-S) Ultraviolet absorber (UV-2) Solvent ( Solv -1) 0.21 1.80 0.26 0.20 0.09 0.70 0.07 0.30 Solvent (Solv -2) 0.09 Seventh layer (
Protective layer) Gelatin 1.07 (EXY
) Yellow coupler α-piparyl α-(3-benzyl-1-hydantoini IL)-2-chloro-5[β-(dodecylsulfonyl)
butyramide] acetanilide (ExM) magenta coupler 1-(2,4,6-trichlorophenyl)-3(2-
Chloro-5(3-octenylsuccinimide)anilino-5-pyrazolone (EICC-1) Cyan coupler 2-pentafluorobenzamide-4-chloro-5(2
-(2,4-ditθrt-amylphenoxy)-3-
Methylbutyramidephenol (ExC-2) cyan coupler 2,4-dichloro73-methyl-6-[α-(2,4-
di-tert-amylphenoxy)butylamidocyphenol (cpa-1) antifade agent 2,5-di-tert-amylphenyl-3,5-di-tert--1 thylhydroxybenzoate (cpa-1)
2) Color mixing inhibitor 2.5-di-tart-octylnohydroquinone (C
pd-3) Antifading agent 1.4-di-tert-amyl-2.5-dioctyloxybenzene (Cpa-4) Antifading agent 2.2'-methylenebis(4-methyl-6-tert-
butylphenol) (Cpd-5) p-(p-)cyansulfonamide)-phenyludeone (Solv-3) solvent di(1-nonyl)phthalate (Solv-4) solvent N N-diethylcarbonamide-methoxy-2 ,4
-di-t-amylbenzene 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy-3,5-di-tert-butylphenyl ) Benzotriazole (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl phthalate The sample obtained as described above is referred to as 41. Next, the magenta coupler in Sample 71 was replaced with the coupler shown in Table 4 in an equimolar weight, the coating silver amount was reduced to 0.23.9/m2, and the solvent was also replaced with the solvent shown in Table 4 in an equal molar weight. exploded.

These samples were subjected to the exposure described in Sample K and Example 1, and processed in the following steps. The results are shown in Table 5.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

(UV-x) Ultraviolet absorber treatment process Temperature Time color development 35℃ 45 seconds bleach fixing
30~36℃ Stable for 45 seconds ■ 30~37℃
Stable for 20 seconds■ 30~37℃ Stable for 20 seconds■ 30~37℃ Stable for 20 seconds■ 30~
Dry at 37℃ for 30 seconds 70-85℃
60 seconds (4 tank countercurrent blade type from stable ■ to ■) The composition of each treatment solution is as follows.

Color developer water ethylene diamine tetraacetic acid triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate N,N-diethylhydroxylamine 4.2g 800 1 2, O,! i+ 8,Ol 1.4g 5.0g 5.6-hydroxybenzey-1,2,4-trisulfonic acid fluorescent brightener (4,4'-diaminostyl water added to pH (25℃) Bleach-fix solution water Ammonium thiosulfate (70%) Sodium sulfite Iron ethylenediaminetetraacetate (I Chloro-2-methyl-4-y0.3y 0g 100071g 00d 100!!11 8g 55!j 3g 1000, tl 5.5 0.1y 0,7,!i+ 0.02g Phthiazolin-3-one 2-methyl - Add 4-inch silica steel sulfate water and pH (25°C) No 3-one 0.01.9 0.001 000d 4.0 From the above table, the coupler of the present invention has a higher Dmax and higher sensitivity than the comparative coupler. Furthermore, it is clear that the combined use with the solvent of the present invention provides higher Dmax and sensitivity without increasing Dmin, demonstrating excellent performance.

Subsequently, the above sample was evaluated for color image fastness under the same conditions as shown in Example 3.

The results are shown in 6.

Takashi 6 (Continued) The evaluation method was carried out in accordance with the method used to evaluate the fortitude described above. The results are shown in Table 7.

Table 7 From the results in the above table, the color image of the sample using the coupler of the present invention in combination with the solvent of the present invention is more robust than that of the comparative coupler under both high temperature and high temperature/high humidity conditions, and the color image is stable. It is clear that this shows excellent image stability with significantly less increase in .

Subsequently, a test was conducted in the same manner as in Example 3 to evaluate light fastness.

Table 7 (Continued) From the results in Table 7, it can be seen that the combination of the coupler of the present invention and the solvent of the present invention improved both the light fastness of the color image and the stain of the white background compared to the comparative coupler, similar to the previous results at high temperature and high temperature and high humidity. compared,
It is clear that there is a marked improvement. This result is consistent with the result obtained in Example 3 above.

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

Preparation of coating solution for the first layer Yellow coupler (ExY) 19.11 and color image stabilizer (cpa-1) 4.4 g and (Cpd-7) 1.
Ethyl acetate 27.2Ce and solvent (Solv
-3) and (5oxv -cs) were added and dissolved, and this solution was mixed with 185 c of a 10% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate Bee.
It was emulsified and dispersed in c. On the other hand, a silver bromide emulsion (silver bromide 80.
0 molti, cubic, average grain size 0.85μ, coefficient of variation 0.08, silver bromide 80.0 molti, cubic,
The blue-sensitive sensitizing dye shown below was added to the sulfur-sensitized product (mixed at a ratio of 1:3 (Ag molar ratio) with particles having an average particle size of 0.62μ and a coefficient of variation of 0.07 per mole of silver). )5,
0XIO moles were prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared v4 in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-
Oxy-3,5-dichloro-8-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (per mole of silver halide) 7.0 x 10 mol) Red-sensitive emulsion layer (CH2)4(CH2)4303H-N(C2H5)3
(5.0 x 10 mol per 1 mol of silver halide) Green-sensitive emulsion layer (0.9 x 10 mol per mol of halogen (tJ!)) For the red-sensitive emulsion layer, add the following compounds to 1 mol of silver halide. 2.6 x 10 moles were added.

(4.0 x 10 moles per mole of silver halide) and also 1-(5-methylureidophenyl)-57mercaptotetrazole for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively. 4. per mole.
0X10 mole, 3.0X10 mole, 1.0X1
0 mole and 2-methyl-5-1-octylhydroquinone, respectively, at 8×10 per mole of silver halide.
Mol, 2X10. Added 2X10-2.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added at 1.2XIO mol per mol of silver halide, respectively.
1. 1×10 mol was added.

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

and (layer structure) The composition of each layer is shown below. The numbers are the amount of coating (,!i'/
m). Silver halide emulsions represent silver conversion X coverage.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (T10□) and a bluish dye (ulmarine)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr:8O-r = Nil)
0.26 gelatin 1.
83 Yellow coupler (EXY) 0
．． 83 color image stabilizer (Cp, 1-1)
0.19 color image stabilizer (Cp(1-7)
0.08 Solvent (Solv-3) Solvent (Solv-6) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-6) Solvent (Solv-1) Solvent (Solv-4) Third layer (green feeling layer) 0.99 0.08 Silver chlorobromide emulsion (AgBr 90 mole, cubic, average grain size 0.47μ, coefficient of variation 0.12 and Ag
Br90 molti, cubic, average particle size 0.36μ,
Gelatin color image stabilizer (Cpd-3) (Cpd -8) Color image stabilizer (Cpd-4) (Cpd -9 ) Magenta coupler (EXM) Solvent (Solv-2) 0.18 0.18 Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-x) Color mixing inhibitor (Cp(1-5) Solvent (Solv-5) ) Fifth layer (red sensitive layer) 1.58 0.47 0.05 0.24 0.16 Silver chlorobromide (A, 5IBr70 molti, cube, average grain size 0.49μ, coefficient of variation 0.08) and A.J.B.
r 70 molti, cubic, average particle size 0.34μ,
Gelatin cyan coupler (EXC) Color image Stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Solvent (Solv-6) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (tJv-1) Color mixing inhibitor (Cpa-5) Solvent (Solv -5) 0.53 0.16 0.02 0.23 1.34 0.30 0.17 0.40 0.20 Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (denaturation degree 17 H) Fluid nozzle rough-in (Cpd-1) Color image stabilizer 1.33 0.17 0.03 (Cpd-5) Color mixing inhibitor (Cpd-6) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) 2:4:4 mixture of color image stabilizers (weight ratio) (CpcL-7) Color image stabilizer average molecular weight so, oo.

(Cpd-8) Color image stabilizer (cpa-c+) Color image stabilizer (UV-1) 4:2:4 mixture (weight ratio) of ultraviolet absorber (Sol, v -6) Dissolved C8H□, CHCH ( 0H2)7COOC8H□7゛0
' (ExY) Yellow coupler (IXM) Magenta coupler (Solv-1) Solvent (Solv-2) 2:1 mixture (volume ratio) of solvent (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent ('f2xc) Cyan coupler Sample 81 is the silver halide color photographic light-sensitive material prepared as described above.

Next, the magenta coupler of the third layer (green-sensitive layer) was added to Example I.
Sample 82 was prepared by substituting the coupler ExM described in K in an equimolar amount and keeping the other conditions the same.

Subsequently, the solvent was replaced with the solvent of the present invention in equal weight, and the magenta coupler was replaced with the coupler of the present invention in equimolar amounts to prepare samples as shown in Table 8VC.

These samples were exposed to light under the exposure conditions described in Example 11C, and the following color development process was performed.

Fujicolor uses a color processing machine FPRP115,
Continuous processing (running test) was performed until twice the capacity of the color development tank was replenished in the following processing steps.

Color development, bleaching, fixing, washing ■ Washing ■ Washing ■ Drying 37°C 33°C 24-34°C 24-34°C 24-34°C 70-80°C 3 minutes 30 seconds 1 minute 30 seconds 1 minute 1 minute 1 minute 00d 51L1 Not yet The composition of each processing solution per 1 m of photosensitive material (3 tanks were cascaded from washing ■ to ■) was as follows.

Color developer tank replenisher water diethylenetriaminepentaacetic acid 800 rILt 1.0. F 800 Go 1, OF Nitrilotriacetic acid benzyl alcohol diethylene glycol strain value "acid sodium potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate hydroxylamine sulfate Salt fluorescent whitening agent (WH Kogyo TEX4B, Sumitomo Chemical Co., Ltd.) Add water to pH (25°C) Ammonium water thiosulfate (70%) Sodium sulfite 5d 0d 2, o, p 1.21 30!! 5, Og 3. 0g 1.011 000mJ 10.20 00m 50WL1 3g oIi 3d 0d 3.09 25, F 9, O, F 4.51! 2.0g 000d 10, 80 00d 00d 26r!I!! Iron (III) ethylenediaminetetraacetate Ammonium ethylenediaminetetraacetic acid di110!! 0g Add water and pH (25°C) 1000 ground, 70 000d 6.30 Measure the density of the magenta color image of the color image obtained before and after the start of the running of the above process, Example 2 of its photographic performance
The same evaluation method was used. The results are shown in Table 8.

From the results in Table 8, it can be seen that even when a silver chlorobromide emulsion is used and a color developer containing benzyl alcohol is used, the photographic performance of the photosensitive material using the coupler of the present invention and the solvent of the present invention does not change due to continuous processing. It can be seen that it is small and can perform stable processing.

In terms of photographic performance, it was observed that the constituent light-sensitive materials of the present invention had higher sensitivity and higher Dmax than Comparative Samples 82 to 88. It was confirmed that this result had the same tendency as the result obtained in Example 1 for the high silver chloride emulsion system.

Furthermore, when comparing the processing stability in continuous processing between the high silver chloride emulsion system of Example 2 and the silver chloride bromide emulsion system of this example, it is found that the high silver chloride emulsion system of Example 2 processing is less variable and more stable, and the configuration of the present invention is believed to be particularly useful in high silver chloride emulsion systems.

I will write a procedural amendment) 1.Display of the incident 1986 Patent Application No. 11'2-76/No. 2, Title of Invention Silver halide color photographic material 3. Person who makes corrections Relationship to the case: Patent applicant 5. Correction measures: Specification Patent applicant: Fuji Photo Film Co., Ltd.\2 Display of incidents name of invention person who makes corrections Relationship with the incident Showa J Special Application No. 1127 Kota Silver halide color photographic material

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, a 5-pyrazolone having a leaving group represented by the general formula (I) at the coupling position. containing at least one type of magenta dye-forming coupler, and the coupler is allowed to coexist with at least one high-boiling point organic solvent having at least one oxirane ring constituent moiety represented by general formula (II). A silver halide color photographic light-sensitive material characterized in that silver halide is dispersed therein. ▲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. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, L_3 and L_4 represent alkylene, cycloalkylene, aralkylene, arylene, and alkenylene groups, and X_1 is -O-, -S-, ▲Mathical formula, There are chemical formulas, tables, etc.▼, -SO-, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONH-, -NHCONH-
represents a divalent group selected from and -SO_2NH-, p
, q and r represent integers of 0 or 1, R_1_1,
R_1_2 and R_1_3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group. Also R
_1_1 and R_1_2 may form a ring.