JPS6285247A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an excellent reproducibility of a color, the durability of a color image and an improved white ground pollution and having less tendency for reducing a sensitivity and a coloring density by incorporating at least one kind of specific mazenta couplers to a silver halide emulsion layer, and a specific compd. to said layer and/or at least one of another layers respectively. CONSTITUTION:At least one kind of the mazenta coupler shown by formula I is incorporated to the silver halide emulsion layer, and the compd. shown by formula II is incorporated to said layer and/or at least one of the another layers. In the formulas, Za and Zb are each -CH-, =C(-R2, a side chain)-, =N-, R1 is a hydrogen atom or a substd. group, R2 is a substd. group, X is a hydrogen atom or a group capable of cleaving by a coupling reaction with an oxidant of an aromatic primary amine developing agent or group capable of binding to a pyrazolone through a secondary or a third carbon atom in either the group R1 when the group R2 does not present in the same molecule or at least one of the groups R1 and R2 when the group R2 presents in the same molecule, Y is an valent group, (n) is >=2 an integer.

Description

[Detailed description of the invention]

[1! [Field of Application of Higashijou] The present invention relates to a silver halide color photographic A light-sensitive material. Excellent silver halide color photographs (related to light-sensitive materials) [Prior art] Silver halide color photographs (1 μm x:M”) are generally
It also has a silver halide emulsion layer that is sensitive to the three primary colors of green and red, and the 4S colors yellow, magenta, and cyan, using the so-called subtractive color method. Reproduce color images. Therefore, the color image to be reproduced depends on the color sensitivity of each layer and the spectral absorption characteristics of one color. Generally, these custom orders are not necessarily logical due to the tria It is not the best in the series.In particular, the coloring hue of the magenta coupler is the best in terms of color reproduction, and many improvements have been made.Among them, the lazoroazole magenta coupler is the best in color reproduction. For example, in order to improve the coloring hue of magenta couplers, 5-pyrazolone threads are used.
No. 7, Japanese Unexamined Patent Publication No. 49-111631, etc.) were developed. Furthermore, a pyrazoloazole type magenta coupler (such as US Pat. No. 3,725,067) has been developed which causes less unnecessary side absorption. This company's couplers not only have less unnecessary absorption in the blue and red light regions compared to the color painting method obtained from 5-pyrazolone type magenta couplers, and are advantageous in terms of single-color reproduction, but also have the advantage that the couplers themselves can absorb light and heat. - It has the advantage that it is stable against humidity and does not easily decompose, resulting in fewer 'fic' changes in the resulting images. On the other hand, this pyrazoloazole thread magenta coupler has the disadvantage that, compared to the 5-pyrazolone type magenta coupler, if the photosensitive material is stored for a long period of time before being photographed, it causes an inconvenient decrease in sensitivity and a decrease in sensitivity over time after photography. Was. As a method for preventing changes in photographic performance, especially the occurrence of capri, which occur during storage over time or during processing, 1, for example, 1-phenyl-5-mercaptotetrazoles (Belgium Patent No. 671,402, 1 National Patent No. 3,295) are used. , No. 976, No. 3,376.310, No. 3,615,616, No. 3,071,465
issue. same? 4fJ3.420,664, same No.2,403,9
No. 27. JP-A-50-37436% JP-A-58-95728, etc., Incyto IJ Azoles (British Patent No. 919°06
No. 1, No. 768.438, U.S.%1 No. 3.157,
509, German Patent No. 3,082,088, German Patent No. 6
17,712, etc.), benzimidazoles (U.S. Pat. No. 3,137,578, U.S. Pat. No. 3,148°066,
No. 3,511,663, British Percentage No. 271.475
No. 1,344,548, No. 3,148,06
6, German Patent No. 3,511,663, German Patent No. 708
, No. 424, No. 635,769. No. 2,205,539, etc.), imidazoles (U.S. Pat. No. 3,106,467, U.S. Pat. No. 3,420,670, etc.)
issue. A method is known in which heterocyclic compounds such as those described in Japanese Patent No. 1,763,990 and Japanese Patent No. 2,271,229 are added to a light-sensitive material or a processing solution. . [Problems to be resolved] However, using only these compounds may not be sufficient to prevent changes in sensitivity caused by pyrazoloazole couplers during storage over time or changes in sensitivity over time after photography, or Even if the prevention effect is sufficient, it has drawbacks such as causing an unnecessary decrease in sensitivity. In addition, various other compounds have been searched for, but none have been found to be effective in sufficiently preventing the increase in capri during storage without decreasing sensitivity. Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material that takes advantage of the excellent features of pyrazoloazole magenta couplers and improves their shortcomings, such as long-term storage stability and latent image storage stability. More specifically, -n1σ) The objective is to provide a color photographic A photosensitive image with a more uneven color reproducibility by producing a maze/red color image with good spectral absorption characteristics. The second objective is a color photographic material with a solid one-color image and improved white background contamination. It is about providing. A third object is to provide a color photographic material that does not substantially suffer from a decrease in sensitivity or a decrease in boiling point of one color even after long-term storage. The fourth object is to provide a color photographic material which does not substantially undergo any change in photographic properties (fa image regression) over time. Other objects of the invention will become clear from the description below. [Means for Solving the Problems] As a result of extensive research in order to develop a silver halide color photographic light-sensitive material that satisfies the above-mentioned key point 1, the present inventors have discovered a specific Denzo pyrazolo It has been found that this can be achieved by containing an azole magenta coupler and a specific hardening agent for IC1, that is, a vinyl sulfone compound.The present invention has been made based on this knowledge. Namely, the object of the present invention has a layer containing at least one of the magenta couplers represented by the general formula below, and a small amount of that layer and/or another layer (both in one layer.By containing a compound represented by the general formula below) Achieved. In the general ceremony, Za and Zb are 10H-, -C- or JJ
-, R1 is a hydrogen atom or

[Wandering through the substitutions. R2 represents a substituent; , including when it is part of an aromatic RIR
2 or X may form a multimer of two or more bodies. However, :ri) - If two R2s exist in the molecule, they may be the same or different, and 1) If R2 does not exist in the same molecule, R1, or I) If R2 exists in R1 and R
At least one of 2. Represents a group bonded to the pizzoloazole ring via a secondary or tertiary carbon atom. Furthermore, at least one of R1 and R2 is -NHSO2
It is a group having one or more - groups, and when Za is 10- and zb or -N-, sR2 is not a substituted or non-11-substituted 72 alkyl group. General formula I (CH2-CH-EiO2+X In the formula, xni represents a group, and n represents an integer of 2 or more. The present invention will be explained in detail below. It means that the molecule has two or more groups represented by the general formula [υ,
This includes bis bodies and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer (preferably one having a vinyl group, hereinafter referred to as a vinyl monomer) having a moiety represented by the general formula, or an aromatic-grade amine developer. Copolymers may be made with non-chromogenic ethylene-like I4L-mers that do not couple with the oxidation products of. Each coupler represented by the general formula symbol has the general formula Cl-
1,1, (1-2J, (1-3J, Cl-4) and Cl-5). (1-1) Cl-2) CI-3)
(1-4) General formula (1-13~[,1-
Among the couplers represented by 53, preferred ones for the purpose of the present invention are represented by the general formula %.More preferred couplers are represented by the general formula [1-2,). Substituent %R of general formulas (1-1) to (1-3)
Circles R4 and R5 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups,
Aryloxy group, heterocyclic oxy group. Acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, anruamino group. Anilino group, ureido group, imide group, sulfamoylamino group, carnomimoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonami r group, carbamoyl group, represents an acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group,
At least one of R3, R4, or R5 is a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and at least one of R3, R4, or R5 is -NH8O□ - is a group having one or more groups, and R4 in the general formula Cl-33 is I! It is not a substituted or unsubstituted aralkyl group. General formula (a substituents from 1-43 to (, 1-1). R6 represents a group bonded to the pyrazoloazole ring via a secondary, k-!, or tertiary carbon atom. General In formulas (1-1) to (1-53), X is a hydrogen atom, a halogen atom, a carboxy group, or a group that bonds to the carbon at the coupling position via an oxygen atom% nitrogen atom or a sulfur atom, and coupling^1! Represents a group that leaves. R, R4, R6, R6'?, and h'LX is 2 (the u of ub?). An association that forms a bis body is also established. In addition, the general formula 1-1
) to (, 1-53 is included in the vinyl percentage unit, R3, R4, R5 or R6 represents a mere bond or linkage -%, and the general formula (1
-13~(1-53 is bonded to the vinyl group. More specifically, R3R4 and R5 are 2 atoms at 7. Halogen atoms (e.g., chlorine atom, alkyl group (e.g., methyl group) , propyl 4, hexyl group, trifluoromethyl group, tridecyl (.3-(2,4-di-t-amylphenoxy)propyl g
, 2-vdecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfoninomonoethyl group, cyclopentyl group, benzyl group, etc.)% aryl group (e.g. phenyl group, 4-t-butylphenyl M @2*
4-V-t-amylphenyl group, 4-tetradecanamido phenyl group, etc.), heterocyclic group (e.g., 2-
furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-
(nzothiazolyl group, etc.), cyano group, alkoxy group (
For example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-Y! siloxyethoxy group, 2-methanesulfonyl ethoxy group, etc.), aryloxy group (e.g., phenolic group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2
-benzimidazolyloxy group, etc. acyloxy group (
For example, acetoxy group, hexadecanoyloxy group, etc.) % carbamoyloxy group (e.g., N-phenylcarno ζmoyloxy group, N-ethylcarbamoyloxy group 1, etc.), silyloxy group 7
group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamido group, benzamide FfF, tetradecaneamyl Ti
, α-(2,4-di-t-amylphenoxy)butyramide 9J &, γ-(3-t-butyl-4-hydroxyphenoxy)butyramide groups. α-(4-(4-Hydroxyphenylsulfonyl)phenoxy)decanami) −
5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamide)anilino M. etc.), ureido groups (e.g., phenylureido group, 1 methylureido group, N, H dibutylureido group, etc.), imide groups (e.g., N-succinimide group, 3-benzylhyda/toynyl group, 4-(2 -!+ruhexanoylamino) 7 talimito 9 groups, etc.). sulfamoylamino group (e.g., N,N-schif'lopylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group 1, etc.), furkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, 2-) Futtsuki diethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-cytoxy-5-t-octylphenyl thio group,
6-bentazosylphenylthio group, 2-carmexyphenylthio group, 4-tetradecanamidophenylthio group,
), heterocyclic thio groups (e.g., 2-benzothiazolylthio group, etc.), alkoxycarzenylamino groups (e.g., methoxycarbinylamino group, tetradecyloxycarbonylamino group, etc.), aryloxylzenylamino groups ( For example, phenoxycarbonylamino group, 2,
4-tert-butylphenoxylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2- Methyloxy-5-t
-butylbenzenesulfonamide L, etc.), carbamoyl groups (e.g., N-ethylcarbamoyl group, N,N-digtylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl &, N-methyl-N-dodecylcarbamoyl group) , N-(S-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-amylphenoxy)acetyl group, benzoyl group, ), sulfamoyl group (e.g., N-ethylsulfamoyl group,
N,N--)propylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl &, N-ethyl-
N-dotecylsulfinyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (Fll, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group,) luenesulfonyl group, etc.), sulfinyl group (
For example, octane sulfinyl group, dodecyl sulfinyl group, phenyl sulfinyl group, etc.), alkoxy ruzenyl group (e.g., methoxy ruzenyl group, dithyloxy ruzenyl group, dodecyl ruzenyl group, octadecyl ruzenyl group, etc.) , aryloxycarbonyl group (
Example; c= ha% phenyloxycarbonyl: M. 3-interdecyloxy-carbonyl: 6s, etc.). at least one of R3, R4 or R5, and R6
represents a group bonded to the pyrazoloazole salt via a secondary or tertiary carbon atom. If these groups are explained in detail, they are inzolovyl group, 1-butyl 21is t-hexyl group, and cyclohexyl group. adamannal group, 1-ethoxyisozorobyl g:j'
*1-phenoxy-1,1-dimenalmethyl toxin, α, α
-dimethyl be/zyl group, α, α-dimenalphenylethyl group, α-ethylbenzyl group, 1-ethyl-1-(4-
(2-Butoxy-5-tert-octylbenzenesulfonamido)phenylcomethyl group. 1-methyl-2-(4-(4-dobucuroxybenzenesulfonamido)phenyl]ethyl group, 1-methyl-2
-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethyl group. 1.1-dimethyl-2-(2-octyloxy-5-t
ert-octylbenzenesulfonamido)ethyl group,
1-Methyl-2-[2-octyloxy-5-(Z-octyloxy7-5-tart-octylbenzenesulfonamide)'')benzenesulfonamide]ethyl group,
1-ethyl-2-(2-dodecyloxy-5-tart
-octylbenzenesulfonamido)ethyl group, 1(2
-Hydroxyethyl)-2-(α-(:1-(2-octyloxy-5-tert-octylbenzenesulfonamide)phenoxydodecaneamide)ether group, etc. Hydrogen atoms, halogen atoms (for example, chlorine atoms, bromine atoms, iodine atoms, etc.),
carboxy/I/ group, or a group linked by an oxygen atom (e.g., acetoxy group, propanoyloxy group, i/zoyloxy group, 4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, Cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group. 4-methanesulfonamine phenoxy group, 4-methanesulfonylphenoxy group, α-su7toxy group, 3-antadecylkenoki7 group, penzyluoquine Carbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-7-netyloxy M, 2-phenoxyethoxy group b 5-7 ndyltetrazolyloxy group, 2-benzothiazolyloxy group , etc.), nitrogen 2c atoms (e.g. benzenesulfonamide) group, N-ethyltoluenesulfonamide group 0 groups, heptafluorozotanamide group% 2.
3.4.5.6-interfluorobenzamide group. Octanesulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1-
Piperidyl group, 5,5-dimethyl=2,4-dio-3-okinazolidinyl group, 1-benzyl-ethoxy-3
-hydantoinyl group. 2N-1,1-dioxo-3 (2H-oxo-1,2
-benzointhiazolyl group% 2-oxo-1,2-dihyto90-1-pyridinyl group, imidazolyl group, pyrazolyl group% 3.5-diethyl-1,2,4-triazole-
1-yl, 5- or 6-promopenzotriazol-1-yl, 5-methyl-1,2,3,4-)lyazol-1-y/I/4, indimidazolyl, 3-
benzyl-1-hydantoinyl group, 1-benzyl-5-
Hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group%4-pivaloylaminophenylazo group, 2dihydroxy-4-propanoylphenylazo group, etc.) Sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio bridge, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group,
-octanesulfonamide V phenylthio group, 2-butoxyphenylthio group, 2-(2-hexanesulfonylethyl/I/) -5-tert-octylphenylthio group,
Benzylthio group, 2-7 anoethylthio group, 1-ethoxycarbonyltritethylthio group, 5-phenyl-2,3
, 4,5-tetrazolylthio group, 2-benzothiazolylthio group%2-dodecylthio-5-thiophenylthio group,
2-phenyl-3-)1decyl-1,2,4-triazolyl-5-thio group, etc.). R, R, R5 or X is 21. When forming a bis group as a group of IIi, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (e.g., evaporation, methylene group, ethylene group, 1-ethylethylene group). group, 1.10-
Decylene group, -ca2ca2-o-ca2ca2-. etc.) J: Substituted or unsubstituted phenylene group (e.g. 1.4-phenylene group, 1.3-phenylene group. CM, C1 -N[C0-R7-C0N! (- group (R7 is substituted or unsubstituted) represents an alkylene group or a phenylene group.R
The divalent group in which 6 becomes a 21iiti group to form a bis body is a carbon in which the above alkylene group is secondary or tertiary: AIB
It becomes a trap to bind to the pyrazoloazole salt through the L-molecule. Those represented by general formulas (1-1) to (1-5) are vinyl AAA. The linking group represented by R, R4 or R5 when present in the structure is a CIt-substituted or non-substituted alkylene group, such as a methylene group, an ethylene group,
1-methylethylene group. 1.10-decyleno group, -CH2CH20CI(2C
H2-, etc.), phenylene group (Hiro: imonme or no [straight phenylene group, e.g., 1,4-phenylene group, 11-phenylene group. CH3C3 -CO14H-, -0-%- 0CO-, aralkylene groups, etc.). R
The alkylene linking group represented by 6 represents a group in which the above alkylene group is bonded to a pyrazoloazole ring via a secondary or tertiary carbon atom. In addition, the vinyl group in the vinyl carmer has the general formula Cl-1
) to (l-53, including substituents other than those represented by l-53. Preferred i substituents include 'IK elementary atom,
It is a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms. Acrylic acid, α
- Chloroacrylic ferments, α-alacrylic acid (for example, methacrylic acid), and esters or amino acids derived from these acrylic derivatives (for example, acrylamide)4. n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propylacrylate, n-butylacrylate. t-butyl acrylate, 1 day 0-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hibiloxy methacrylate), methylene dibis acrylamide 91 Vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylate trile, aromatic vinylated 't'ir (e.g. styrene and its cast conductors, vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene) , Itako, Nba. Citracon r night, Croton late, Vinylidenk 1] Light 91 Vinyl alkyl ether (: Liehahinyl ethyl ether), Malay y + ie, m water maleic fermentation, maleic tvl ester, N-? 'Nilu 2-pyrrolidone. Examples include N-vinylpyridine, 2- and 4-vinylpyridine, and the like. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used in a set. The couplers represented by the general formulas from Cl-1) to (1-53) can be synthesized using the synthesis method K described in the following literature.
It can be synthesized by I. The compound of general formula (1-13 is % JP-A-59-16254
8, etc., the compound of the general formula Cl-23. Japanese Unexamined Patent Publication No. 59-171956, 1c% general formula Cl-3
Compound No. 3 is disclosed in Heavenly Patent No. 3,725,067, etc., compound of general formula Cl-4) is disclosed in JP-A-60-33552, etc., and compound of general formula Cl-5 is disclosed in U.S. Patent No. 3.06, etc.
It can be synthesized by the synthesis method VC1VA described in No. 1,432 and No. 3,369,897, respectively. 04H9tt) CaHt71tl C00C□8f13 '1 6H3 The vinyl sulfone type hardener represented by the general formula (n) used in the present invention is a halogen contained in the magenta coupler of the silver halide and true light-sensitive material of the present invention. It may be added to the silver oxide emulsion layer or to any other layer. Furthermore, the above-mentioned hardener may be added to two or more layers. The desirable addition amount of the hardening agent represented by the general formula (If) is about 0.01% to about 10%, more preferably about 0.1% to about 4% based on the total amount of coated gelatin. It is a genre. In the present invention, among the compounds of the general formula (II), compounds represented by the primary general formula [IIa], [IIb], or (me) are particularly preferred. (lIa) (CH2=CM-302ArYt In the formula, Yl represents an alkyl group having 1 to 12 carbon atoms. [■b] (CH2=CH-802-ecll)';ii"'→
(In the formula 2A1, R represents a hydrogen atom or an alkyl group having 3 or less carbon atoms, and each R may be the same or different), Al represents a heteroatom, and 91% is an integer of 1 to 4. (Ua), where R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (each R is the same and may be 4 different),
A2 represents a divalent group, and / represents 0 or 1. Next, the general formula [■α), CII&) used in the present invention
. and [■0] Specific examples of vinyl sulfone compounds are shown,
It is not limited to this. (II-1) CH2-aH-so2-CH2-aH
,5o2-eu=cH2(II-2) CH2=CH
-802-CH2-CH2-CH2-502-C polished dz
(TI-3) CH2=CH-802-CH2-CH
=CH2-802-(BCH2CH3 (II-4) CH2-CH-802-CH2-0-
CH2-802-CH=CH2(II-5) CH〆H-802-CH2-8-CH2-802-C
II-6) (CH2=CH-802-CH2-Q]
'JHi(rx-7) (CH2-C)1-802-
CI(-CONM-(J, -77(■-8) (CH2
=CH-Ta2-41■N-C)12π(J3 Ha (II-9) CH2=CH-s02-CH-Q)N
li-CM-CH2-Nf(Q)-082-8O2-C
)5H2 SO2-ClCH2 (■-11) (C1(2-cu-12-aH2-c
onf(-(e-cho)-Hzu0 The general formula according to the present invention (
1) The magenta coupler represented by the following can be contained in at least one hydrophilic organic colloid layer)-e which constitutes the photographic light-sensitive layer together with a high boiling point organic solvent. The preferred ratio of the magenta coupler to silver nitrate in the magenta coloring layer is 0.05 to 5 moles. As a method for introducing a coupler into a silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 are generally used. The ratio of the high boiling point solvent to the pyrazoloazole magenta coupler is desirably 1 to 6.0. If the coupler is insufficiently dissolved, use a high boiling point organic solvent.
For example, a coupler solvent such as a phosphate ester coupler solvent can be used in combination. Also, in the present invention, the boiling point of the coupler is about 30-15
0°C organic solvent 1 such as ethyl acetate, butyl acetate, %l flukylacetate, ethyl propionate,
Secondary butyl alcohol, methyl isobutyl ketone. β-ethoxyethyl acetate, methylselonlupus acetate, etc. may also be present. Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods, for example, Japanese Patent Publication No. 51-39853. The dispersion method using a monopolymer described in JP-A-51-59943 can also be used in combination. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. In the present invention, various color couplers can be used in addition to the magenta coupler described above. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthols, phenolics, pyrazolones or pyrazoloazoles, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention.
It is described in the patents cited in Sections 1-D and 418717 (November 1979). The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A two-equivalent coupler substituted with a coupling-off group is preferable to a four-equivalent coupler in which the camping active position is a hydrogen atom, since the coated silver it can be reduced. Furthermore, there are also couplers in which coloring dyes have appropriate diffusivity, colorless couplers, and D-engineered R couplers that release a development inhibitor upon coupling reaction. Couplers that release development accelerators can also be used. Yellow couplers that can be used in the present invention include: A typical example is an oil-protected acylacetamide P coupler. Specific example Vi. U.S. Patent No. 2,407,210, U.S. Patent No. 2,875,0
No. 57 and No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
447,928, 3,933,501 and 4,022,620, or Japanese Patent Publication No. 58-10739
No. 4,401,752. No. 4,326,024, RD18053 (1979
), British Patent No. 1,425,020, West German Published Application No. 2,219,917, West German Patent No. 2,261,361
No. 2,329,587 and No. 2,433,
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 812. The .alpha.-pivaloylacetanilide coupler has excellent color fastness, especially light fastness, while the .alpha.-benzoylacetanilide 1-based coupler provides the same degree of color development. Cyan couplers that can be used in the present invention include oil protect a naphthol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat.
, No. 212, No. 4,146,396, No. 4,22
Typical examples include naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Patent Nos. 2,369.929, 2,801,171, 2,772,162,
It is described in the same No. 2,895,826. A cyan coupler that is robust against humidity and greenhouse conditions is preferred by the present invention! , L<' used. A typical example is U.S. Patent No. 3,772,002.
Phenolic cyan couplers having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus, described in U.S. Patent Nos. 2,772,162 and 3,758,30
No. 8, No. 4.126,396, No. 8! 4,334,0
No. 11, No. 4,327,173, West German Patent Publication No. 3
, 329,729 and European Patent No. 121.365
2,5-:)acylamino-substituted phenolic couplers described in US Pat. No. 3,446,622, etc.
No. 4,333,999, No. 4.451,55
No. 9 and No. 4,427,767, etc., which have a phenylureido group at the 2-position. and a phenolic coupler having an acynoamino group at the 5-position. To correct the princess absorption in the short wavelength range of the dyes generated from magenta and cyan couplers. It is preferable to use a colored coupler in combination with a color negative photosensitive material for photography. Yellow-colored magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413, etc. or U.S. Pat.
No. 9, No. 4,138,258 and British Patent No. 1,
Typical examples include the magenta-colored cyan coupler described in No. 146,368. Granularity can be improved by using a color-forming dye in combination with a coupler that has 4 degrees of diffusivity. Such couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2
Specific examples of magenta couplers are shown in , No. 125,570, and State Special Plan No. 96,570 and West German Application Publication No. 3,
No. 234,533 is yellow. For magenta, 1-< is a specific example of a cyan coupler. Dye-forming couplers and J: special couplers listed below. A polymer with two needles or more may be formed. , H+) merized dye-forming couplers are described in U.S. Pat.
Specific examples of polymerized magenta couplers described in No. 51,820 and No. 4,080,211 include:
British Patent No. 2,102,173 and U.S. Patent No. 4,
No. 367.282. The various couplers used in the present invention can be used in combinations of two or more types in the same photosensitive layer in order to satisfy the characteristics required for the photosensitive material. It can also be introduced above I-. 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. Ilv, m of gelatin manufacturing method is from Arthur Vuis, The Macromolecular Chemistry of Gelatin, (
Academic Press. (published in 1964). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver chlorobromide. Particularly preferred is silver chlorobromide containing from 20 to 100 moles of silver bromide. The average grain size of silver halide grains in photographic emulsions (the grain diameter is defined as the grain diameter for spherical or approximately spherical grains, and the ridge length for cubic grains; expressed as an average based on the projected area) is particularly important. Although not, it is preferably 2μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion layer are cubic. It may have a regular crystalline structure such as a hexagonal,
Further, it may have an irregular crystal shape such as a ring shape or a plate shape, or a composite shape of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms. It is also possible to use an emulsion in which ultratabular silver halide grains having a diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, it may be a particle in which a latent image is mainly formed on the surface, or a particle in which a latent image is formed as a crown inside one particle. The photographic emulsions used in the present invention include "The Chemistry and Physics of Photography" by P. Grass and Kitte (Paul Montel Publishing, 1967) and "Photographic Emulsion Chemistry" by G. F. Dahuin (Focal Press, 1966). "Manufacture and Coating of Photographic Emulsions" by V. L. Zelikman et al. (Focal Press, 1964) (P. Glafkidas, -CItmia at Ph
ysique Pruota-graphiqx-” (
PasL Ho5tel, (1967)
). G, F+Dsfft? l, “Photograph
i6 EmslsiosChemistry' (F
ocal Press, (1966)). V.L.Zalikman at ``Hak
tng and Coating Photography
ic Emulsiots” (11'oecLj Pr
y4 can be produced using the method described in J. D. Ess, (1964) and others. Namely. Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrolby double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening,
Cavernium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, etc. may be present together. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, please refer to H, 7 Reiser ed., "Basic Silver Halide Photographic Processing" (Akademitsche Farark, 1.
(Published in 968) (H, Frimaar. “Die Grsndla (Hndar Photo
ographhishmnProtasaamit S
ilbar-halogasidmn” (kkadam
ischa Varlagsgmsellahaft,
1968), pages 675-734, can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); , hydrazine derivatives, formamidine sulfinic acid, silane compounds); reduction sensitization method using noble metal compounds (e.g., total complex salts, complex salts of metals of group I of the periodic table such as Pt, Pd, etc.) −
Sensitization methods and the like can be used alone or in combination. The photographic emulsion used in the present invention has the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. Various compounds can be included. That is, azoles, such as (nzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds, such as oxadorinthion; azaindenes. For example, triazaindenes, tetraazaindenes (
In particular, 4-hydroxy [converted (1,3,3a,7)tetraazaindene], hantaazaindenes; anti-capri agents or stabilizers such as henzenethiosulfonate, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as agents can be added. The photographic emulsion chemical or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may include coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and photographic property improvement (e.g., development acceleration, high contrast A variety of surfactants may be included for various purposes such as sensitization, sensitization, etc. The photographic emulsion layer of the photographic X-sensitive material of the present invention contains additives for the purpose of increasing sensitivity, increasing contrast, or promoting development. For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
It may also include thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention contains five hydrophilic colloid layers including the photographic emulsion layer for the purpose of improving dimensional stability, etc.
Dispersions of water-insoluble or sparingly soluble synthetic polymers can be included. The photographic emulsions used in the present invention may be spectrally enhanced with methi/dyes and the like. The pigments used are cyanine pigments and merocyania pigments. Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are dyes that contribute to anionine dyes, merocyanine dyes, and complex merocyanine dyes. These pigments include
Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which alicyclic hydrocarbons are fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus. Sujowachi, India 3 Reni/Nuclear, Benzindolenine M,
i/)"-ru nucleus % indoxal nucleus, naphthoxazole nucleus. benzothiazole nucleus, toteazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei are carbon hK near-
), may be replaced. Merocyanine dyes and Vi complex merocyanine dyes have a nucleus with a ketomethylene structure (7, pyrazoli/-5-
5- to 6-membered heterocyclic nuclei such as on nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4-)on nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied. can. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with sensitizing dyes, dyes that do not themselves have a spectral sensitizing effect or substances that do not practically absorb visible light, 1
A substance exhibiting supersensitization may also be included in the emulsion. for example,
With nitrogen-containing heterocyclic groups! Aminostyryl compounds (e.g., U.S. Pat. Nos. 2,933,390; 3,635;
721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The present invention also lends itself to multicolor photographic materials having at least two different spectral sensitivities in the support. Multilayer natural color photographic materials are usually 1. The support has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. Different combinations may be used depending on the case. In the same or other photographic emulsion layers or non-light-sensitive layers of the photographic light-sensitive material of the present invention, in addition to the coupler represented by the general formula [x], other dye-forming couplers, ie, aromatic-grade Amine developers (e.g.
Compounds that develop color by oxidative coupling with phenylene diamine derivatives, aminophenol derivatives, etc.) may also be used. For example, as a magenta coupler, 5
-Pyrazolone coupler, pyrazolone R-tzimidazole coupler, pyrazolo(5,1-C) (1,2,4)
) lyazole coupler, pyrazolo pyrazole coupler,
There are pyrazolotetrazole couplers, open chain acylacetonitrile couplers, etc.
There are acylacetamide turnips (eg, benzoylacetanilides 0, pivaloylacetanilides), etc., and at 1° with cyan couplers, there are naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusible and have a ballast group called a ballast group in their molecules, or are polymerized. The coupler may have either 1,4-equivalent or 2-equivalent to silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called J) IR coupler). In addition to DIR couplers, there are also colorless DI couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Further, the light-sensitive material may contain a coupler or a compound that releases a development accelerator upon development. The coupler of the present invention and the above-mentioned couplers can be used in combination of two or more types in the same layer in order to satisfy the properties required for photosensitive materials.
- Of course, there is no problem in adding ≦ to the north. In the photographic light-sensitive material of the present invention, in addition to the hardening agent represented by the general formula ([1)], an inorganic or organic hardening agent is added to the hydrophilic colloid layer of each of the 11 photographic emulsion layers. good. For example, chromium salts (chromium acetate, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.). N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (2,
3-dihydroxydioxane, etc.). Active vinyl compound (1゜3.5-triacryloyl-hexahyto90-8-triazine, 1,3-vinylsulfonyl-2-7' lovanol, etc.) -gj4 halogen compound (2,4-:)chloro-6- Hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. In the photosensitive material of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber, etc. They may be mordanted, such as by cationic polymers. The light-sensitive material of the present invention is used as a one-color anti-capri agent. Hyperquinone conductor, amine phenol derivative. It may also contain gallic acid derivatives, ascorbic acid derivatives, etc. The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., U.S. Pat. No. 3,533
, 794), 4-thiazolidone compounds (
For example, U.S. Pat.
, No. 681, amended). Benzophenone compounds (e.g. those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g. those described in U.S. Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (e.g. Time 1f-
F4,045,229), or benzoxide compounds (e.g., those described in U.S. Pat. No. 3,700,
455) can be used. A UV-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or a UV-absorbing polymer may also be used. These ultraviolet absorbers may be mordanted with specific l-. The light-sensitive material of the present invention may contain a water-soluble dye as a hydrophilic colloid filter dye or for various purposes such as preventing irradiation. Such dyes include V'i, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are M
It is for use. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. A known anti-fading agent and 1. Hydroquinone derivatives, erosion fg
conductors, p-alkoxyphenols, p-oxyphenol derivatives, bisphenols, etc., Th, 6°.For photographic processing of the layer consisting of the photographic emulsion used in the present invention, for example, Research Disclosure No. 176 No. 28-
Any of the known methods and known treatment sludge as described in No. 30 can be applied. The treatment temperature is usually selected between 18°C and 50°C, but it may also be lower than 18°C or higher than 50°C. As constant*IgL, one having a commonly used composition can be used. In addition to thiosulfate and thiocyanate, M, which is known to be effective as a fixing agent, can be used as a fixing agent.
Organic sulfur compounds can be used. The fixer may contain a hardener and 17 a water-soluble aluminum salt. Color developers generally consist of an alkaline aqueous solution containing one color developing agent. Color development Gyokuraku is made using known general aromatic amine developers, such as phenylene diamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-
4-amino-N,N-diethylaniline%4-amino-
R-ethylue 1-β-hibyloxyethyl°aniline,
3-Methyl-4-amino-N-ethyl-N-β-hybroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4
-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. Other than this, l! 'Photographic Processing Chemistry' by A. Menn (Focal Press) (1966) (L.
ProamssingCh*rrsttry (F
No. 226 of ocal Prmaa) (1966)
~229 pages, U.S. Patent No. 2,193,015. Those described in JP-A No. 2,592,364, JP-A-48-64933, etc. may be used. Force 2 - The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic anti-capri agents. It can be used to treat drugs, etc. Also water softener if needed. Preservatives such as hibiroxylamine, organic solvents such as benzyl alcohol and diethylene glycol. Polyethylene glycol, quaternary ammonium salt. Visibility enhancers such as amines, 1-packet-forming couplers, competitive couplers, fogging agents such as sodium boron hydrite 9, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid systems. chelating agent, rf
! It may also contain an anti-lization agent and the like. The photographic emulsion layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include Ill.
), compounds of polyvalent metals such as cobalt (n+), chromium (■), copper (■), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide monodichromate, iron(to)
Organic complex salts of (+U) e.g. ethylenediaminetetraacetic acid, nitrilotri-D acid, 1.3=diamino-
Aminopolycarboxylic acids such as 2-pro·ξnortetraacetic acid rt, citric acid, and tartaric acid. Complex salts of organic acids such as malic acid: persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium 7-erythyanide, sodium ethylenediaminetetraacetate iron (111), and ammonium ethylenediaminetetraacetate iron (Ill) are particularly useful. Ethylenediaminetetraacetic acid iron (Ill) complexes are useful both in stand-alone bleach solutions and in -bath white fixing solutions. The color photographic emulsion layer forming a single dye image according to the present invention is coated on a flexible support such as plastic film, paper, cloth, etc. which is commonly used in photographic light-sensitive materials. What is useful as a flexible support? Cellulose acetate, cellulose acetate butyrate, polystyrene,
These include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate and polycarbonate, and papers coated or laminated with baryta layers or α-olefin polymers (eg, polyethylene and polypropylene). The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. When using these supports for reflective materials. It is preferable to add a white pigment to the support or laminate layer.1. stomach. Examples of white pigments include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, ammonium trioxide, silica white, alumina white, titanium phosphate, etc., but titanium dioxide, sulfuric acid, etc. Barium, fg, and zinc oxide Vi are particularly useful. The surface of these supports is generally subjected to an undercoating treatment to improve contact with a quaternary emulsion or the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. When these supports are used in reflective materials, a hydrophilic colloid layer containing a high degree of white pigment is further provided between the support and the emulsion layer to improve the whiteness and the sharpness of the photographic image. be able to. In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but when a synthetic resin film kneaded with a white pigment is used, it has smoothness and gloss. - In addition to the sharpness of the mukooka, a photo-X image with particularly excellent depiction of interstices and dark areas is obtained, which is particularly preferable. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as raw materials for the synthetic resin film, and barium sulfate and titanium oxide are particularly useful as white pigments. The photographic material of the present invention can currently be laminated with a plastic film on the front and back sides after processing and drying. Plastic films for lamination include polyolefin,
Polyester%, N lyacrylate, polyvinyl acetate, polystyrene. Butadiene-styrene copolymers, polycarbonates, etc. are useful, especially bD, polyethylene terephthalate, copolymers of vinyl alcohol and ethylene, J-lyethylene, etc. /'/'' (Example) The present invention will be explained in detail below based on specific examples, but the present invention is not limited thereto. (Example 1) A paper support laminated on both sides with polyethylene, A color photographic light-sensitive material was prepared by applying the following 1st to 11th layers in multiple layers.The RA7R5 side of the first layer of polyethylene contains titanium white as a white pigment and a small amount of granite as a taste dye. . (Photosensitive layer composition) Below are the ingredients! Coating Xtl shown in Z/1pt2 units
Indicates t. For silver halide, the coating amount is shown in the silver settlement. m 1 layer (antihalation layer) Black colloidal silver...0.
10 gelatin...0
．． 2 Second layer (low sensitivity variable red sensitivity layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and *4) (silver iodide 3.5 mol/y; J grain size ( 0,
7μ) ... Silver 0.15 Gelatin ... 1.0 Cyan coupler (*3) ... 0.3
0 Anti-fading agent (*2) ...0
．． 15 turnip 7-mu (*I8 and *1) --
-0,06 Third layer (highly sensitive red-sensitive layer) Silver iodobromide emulsion (silver iodide 8.0 molar ratio, average grain P size 0.7μ
・・・Silver 0.10 Gelatin ・・・0.50
Cyan coupler (*3) ...0.1
0 Anti-fading agent (*2) ...0.
05 coupler solvent (*18 and *1)...0
02 No. 414 (middle layer) Yellow: lOil-'M-
・0.02 gelatin
...1,00 Color mixing prevention agent (*14)
...0.08 color mixing inhibitor solvent (lcl3)
...0.16 volumer latex (
*6) ...040 No. 5) vi (low sensitivity q green sensitivity, I-) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (*12) (silver iodide 2.5 mole, average particle size 0.4μ)
...silver 0.20 gelatin, ...0.70 magenta coupler (*11') ...0.4
0 Anti-fading agent A (*10)...
・0.05 anti-fading agent B (*9)
...0.05 anti-fading agent C (*S)
...0.02 coupler solvent (*7)
...0,15 6th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 3.5 molti, average grain size 0.9 μm) )
...Silver 0.20 gelatin
...0.70 magenta coupler (*11") ...0.40
fJA color inhibitor A (*10)...
0.05 Anti-fading agent B (*9)
...0.05 anti-fading agent C (*8)
...0.02 coupler solvent (*7)
...0115 7th layer (yellow filter single layer) Yellow colloid) "Silver --0,20 Gelatin ...1.0
0 Anti-fading agent (*14)...
0.06 anti-fade solvent (*13) ・
... o, 24 No. 8 M ([sensitivity 1 corpse kidney sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2.5 molar ratio, average grain size 0.5μ)
...Silver 0.15 gelatin
...0.50 yellow coupler (*15) ...0.20
Coupler solvent (*18)...0
．． 05 No. 91- (high sensitivity wg layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 265 molφ, average grain size 1.4μ)
...Silver 0.20 Gelatin ...0.50 Yellow coupler (*15) ...0.2
0 coupler solvent (*is)...
・0.05 10th layer (ultraviolet absorption J-) Gelatin ・・・1.5
0 UV absorber (*19) ・・・i
,. Ultraviolet absorber solvent (*18)...0
．． 30 color mixing prevention agent (*17) ・
...O, OS 11th layer (protective layer) Gelatin ...1.0
Hardener (*20) ...0.
17 The compound used here is of the first order: *
1 Dioctyl phthalate* 2 2-(2-hydroxy-3-see-butyl-5-t-butylphenyl)benzotriazole* 3 2-Cα-(2,4-di-t-amylphenoxy)butaneamibi)-4, 6-dichloro-5-ethylphenol* 4 5.5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbonylcyanine Nα
Salt* 5 Triethylammonium-3-(2-(2-(
3-(3-sulfopropyl)su7)(1,2-d)thiazolin-2-ylidenemethyl-1-zuthenyl)-3-
Naphtho(1,2-d)thiazolino]propanesulfonate* 6 Polyethyl acrylate* 7 Trioctyl phosphate* 8 2.4-S-g-hexylhydroquinone*
9 Di(2-hydroxy-3-t-butyl-5-methylphenyl)methane*10 3,3.3', 3'-tetramethyl-5,6,
5',6'-tetrapropoxy-1,1'-bisspiroindane *11 1-(2,4,6-trico o ) x nyl)
-3-(2-chloro-5-tetosidecanamibi)anilino-2-pyrazolino-5-one*12 5.5'-diphenyl-9-ethyl-3,3'
-Disulfopropyloxacarbocyanine Na salt *13! J-n Pik-o-cresyl ester *14
2.4-di-t-octylhypyroquinone *15 α-
Piparoyl-α-((2,4-dioxo-1-benzyl-5-ethoxyhytantoino-3-yl)-2-chloro-5-(α-2,4-dioxo-t-amylphenoxy)butamino]acetanilide *Engineering 6 Triethylammonium 3-C2-C3-benzylrhodanine-5-(
! J Ten)-3-A? [Zoxazolinyl] propane sulfonate*172,4-di-3e(-octylhyde 10quinone*181J-acid trinonyl ester*195-chloro-2-(2-hydroxy-3-C-butyl-5-tert-octyl ) Phenylbenztriazole*20 2,4 dihuman 90-6-hypiroxy 1.3.
5. Samples prepared in the same way north of the triazine Na salt were sample numbers 101 and 1.
2. This was used as a control sample for subsequent comparisons. Magenta coupler (*11) in the 5th and 6th layers of sample number 101
) and the hardening agent (*20) of the 11th layer were changed as shown in Table 1, and samples were designated as sample numbers 102 to 111. Table 1 also shows the results of these samples, which were subjected to stepwise exposure for sensitometry and then developed according to the processing steps listed below. [Processing process] First development (black and white development) 38°C 1' 15
"Water wash 38℃ 1'30" Reverse exposure North of 100 Luz 1"
Color development 38℃ 2'1
5" Washing with water 38℃ 45" Fixing in a 38℃ tyJ
o o I? Washing with water 38℃ 2'15'' [Processing solution combination release] 1st developer solution Nitrilo N, N, N-)rimethylenephosphonic acid, pentasodium field 0.69 Diethylenetriaminepentaacetic acid, pentasodium salt 4401
Potassium sulfite 30.0.
9 Potassium thiocyanate 1.2
g Potassium carbonate 35. O
fl Hyde 90 Quinone Monosulfonate
25.0, F potassium salt diethylene glycol 15.
0mj1-phenyl-4-hydroxymethyl-2,0,
94-Methyl-3-pyrazolidone potassium bromide 0.5
1 Potassium iodide 5.
0 ■ Add water 1
1 (pH 9,70) Color developer benzyl alcohol 15. O
mJ diethylene glycol 1
2.0yt13.6-cythia1.8-octane
0.2 F diol nitrilo-N, IJ, N-trimethylene
0.5,? Phosphonic acid, pentasodium salt diethylenetriaminepentaacetic acid 2.0
, V pentasodium salt sodium sulfite 2,
0g potassium carbonate 2
5.09 Human 90xylamine sulfate
3.0.9N-Ethyl-N-(β-methanesphonamibiethyl)-3-methyl-4-amine aniline sulfate 50g Potassium conjugate 0.5.9 Potassium iodide 1.0■ Add water 11 (pHx
o, 40) Bleach-fix solution 2-mercapto-1,3,4-triazole 1.0
gEthylenediaminetetraacetic acid, disodium, trihydrate
5.0g ethylenediaminetetraacetic acid/F#(111)/ammonium hydrate salt 80.
0.9 normal sodium sulfate 15
．． 0F sodium thiosulfate (700&/l liquid) 160.
Yama d ice vinegar 1'ze 5
．． Add 0-g water and 11(
pH6,50) Color purity in this table refers to magenta filter ccx
The cyan and yellow densities (DR, DB, respectively) at the point where the magenta density (DG) measured with the Macbeth densitometer Stetus AA filter is 1.0 when stepwise exposure is performed using two images (made by Fuji Film). It represents the ratio to the sum (DG/DR+DB). That is, it is a scale that indicates the value of extra cyan and yellow components in magenta color, and it can be said that the smaller the value, the higher the purity of the color. Storage conditions for measuring changes over time are 35°C, 55% RH.
This is the value obtained in . As shown in Table 1, sample number 108 according to the present invention
It can be seen from the above that 111 has a high monochromatic linearity and little unnecessary change over time. (Example 2) A color photosensitive material was prepared by coating the following photosensitive layers consisting of the first layer to the third layer on a paper support laminated on both sides with polyethylene. The polyethylene on the side coated with the first layer contains titanium dioxide as a white pigment and a trace amount of #blue as a white pigment. Contains in (Structure of Photosensitive Layer) The numbers corresponding to each component indicate the coating needle expressed in units of g/n2, and for silver halide, the coating amount is indicated in terms of silver. 1j Eel (green feeling, 1ij) Silver chlorobromide emulsifier (bromide 70 mole sensitized color v powder 37)
・・Silver 0.30 Magenta coupler (*32) ・・0.25
Same as above solvent (*36)...0.30 Anti-fading agent (*33/*34)...0.0510.10 Gelatin...1.00 Second layer (UV absorbing intermediate layer) UV absorber (*35) Same as above solvent (DBP)...0.20
Gelatin...0.15 Third layer (protective layer) Gelatin...1.5 Here, pnp represents dizitylphthalate, and the chemical structures of *31 to *36 are shown below. *31 *32 l *33 *34 *35 *36 Also, add the hardening agent (*20) used in the example process equally from the first layer to the third layer. This light-sensitive material was used to create sample 201 (and samples 202 to 2100) in exactly the same manner except for the changes shown in Table 1. The development process was carried out using the following processing steps.Processing process Temperature Time Developer solution 33℃ 3.5 minutes Bleach-fix solution
33℃ 1.5 minutes water washing 28-35℃ 3
．． 0 minute developer nitrilotriacetic acid/3Nα 2.
OI benzyl alcohol 1
5ml diethylene glycol 1
0. lN(!2803
2.0:! KB r
O,5g human 10xylamine am salt3.
0 F4-amino-3-methyl-N-ethyl-N-[β
-(methanesulfonamido)ethyl]-p-phinylene diamine sulfate 5.011Nα2CO3 (monohydrate)
Add 30g water to make 1 liter (, uio, i) Bleach-fix solution Ammonium thiosulfate (70wt%) 15
0dNcL2SO315jl' NH4(F a (EDTA) ]551h:D'L
'A2 ・2Na 4,
9 Add water to make 1 liter (pH 6, 9) After the above-mentioned treatment, the characteristic direction W (D -10gK curve) was determined using a self-recording thermometer using blue, green, and yellow filters. The results are shown in Table 2. As shown in Table 2, sample 205 according to the present invention. It can be seen that it is the most preferable not only in terms of color purity but also in terms of storage stability. (Example 3) Next, a sample 301 was prepared by applying the first to twelfth layers on the triacetate film base in the following order. 1st layer; antihalation layer UV absorber 5-chloro-2-(2-hydroxy-3,
5-di-t-butylphenyl)-2B-benzotriazole15. F, 2-(2-human 10x-5-t-butylphenyl)-2H-/citriazole 30,9.2
-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)-2H-benzotriazole 35y1 and to1decyl 5-(N,N-diethylamino)-
2--” zenesulfonyl-2,4-pentagenoate 1001:, tricresyl phosphate 200rIL
t, ethyl acetate 200d, )' sodium decylbenzenesulfonate 201! , an emulsion obtained by stirring a 10% gelatin aqueous solution at true speed (hereinafter referred to as emulsion (α)). Mix 10 Tigelatin, black colloidal silver, water, and a coating aid and coat to a dry film thickness of 2μ. Second layer: gelatin middle layer 2.5-di-t-octylhydroquinone. An emulsion (hereinafter referred to as emulsion (1,)) obtained by dissolving 1 ounce of dibutyl phthalate and 100 ml of ethyl acetate and stirring at high speed with 1 ml of 10 tizelatin in water (hereinafter referred to as emulsion (1,)) was prepared by adding 10% 9 to 2.
Gelatin 1.5 kl? The mixture was mixed and applied to a dry film thickness of 1 μm. 31st machine; low sensitivity red-sensitive emulsion layer cyan coupler 2-(heptafluoromethylamide)-5-(2'-(2", 4"-di-C-aminophenoxy)butyramide-phenol 100!y 't. An emulsion obtained by dissolving 100cc of tricresyl phosphate and 100cc of ethyl acetate and stirring at high speed with 100% aqueous solution of tizelatin (hereinafter referred to as emulsion (e))
500, @ to red-sensitive silver iodobromide emulsion 1 to 9 (silver 701
．． It contains 60 g of gelatin and is mixed with 4 mol % of gelatin. The coating was applied to a dry film thickness of 1 μm. (Silver f O, 51
/'m2') 4th layer: Highly sensitive red-sensitive emulsion layer The emulsion (c) was mixed with red-sensitive silver iodobromide emulsion 1 ml (Silver 701
, gelatin (60.9%, iodine content: 2.5 mol), and coated to a dry film thickness of 2.5 μm. (Silver amount 0.817 pieces 2) No. 57! ;Mix 1 kg of middle layer emulsion (6) with 1 g of %10 Tigelatin. The coating was applied to a dry film thickness of 1 μm. 6th r? a; 1-, which is a magenta coupler instead of a cyan coupler in the low-sensitivity green-sensitivity emulsion layer;
(2,4,6-)lichlorophenyl)-3-(3-(2
, 4-di-t-aminophenoxyacetamido)benzamide)-5-pyrazolone was used in the same manner as emulsion 31- (hereinafter referred to as emulsion (d)). ) was coated on 1 kg of edge-sensitive silver iodobromide emulsion (containing 701 silver, 60!! gelatin, and iodine 9 content of 3 mol) to give a mixed t/% dry m1% thickness of 2.0 μm. . (Silver amount: 07 g/inertia 2) 7th layer: Highly sensitive green-sensitive emulsion layer Emulsion (d) 1000 N was added to green-sensitive silver iodobromide emulsion 1 to 9 (containing silver 7011, gelatin 6ON, and iodine-containing garnish. (2.5 mol %) and coated to a dry film thickness of 2.0 μm. (Silver fit 0.7 g/m2
) 8th layer: 1 kg of gelatin intermediate 111# emulsion (6) was mixed and coated on 1' kg of 10 gelatin to give a dry film thickness of 015 μm. Ninth layer: Yellow filter One layer: An emulsion containing 9 silver of yellow colloid was coated to give a dry film thickness of 41 μm. 10th layer: low-sensitivity blue-sensitivity emulsion layer with yellow coupler instead of cyan coupler
(pivaloyl)-α-(1-benzyl-5-ethoxy-
3-hydantoinyl)-2-chloro-5-to-1decyloxycarbonylacetanilide
An emulsion obtained in the same manner as the ring emulsion (hereinafter referred to as emulsion (#)')) 100 (1) was mixed with 1 kg of f-sensitive silver iodobromide emulsion (@70.V, containing 60 & gelatin, The iodine-containing material was mixed with 2.5 molti) and coated to give a dry film thickness of 1.5 μm. (Amount of silver 0.6j9/washing 2) Layer 11: Highly sensitive blue-sensitive emulsion layer Emulsion (a ) 1000.9, blue-sensitive silver iodobromide emulsion 1
kIl/(contains silver 7011 gelatin 6ON, iodine 9
The silver content was 2.5 mol%) and was mixed (7) and applied to a dry film thickness of 3μ. (Amount of silver 1.1 g/m2) No. 127
The second protective layer emulsion *<α) was mixed with 10% gelatin, water, and a coating aid, and coated to a dry film thickness of 2 μm. 13th layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0.06μ,
A 10% gelatin aqueous solution containing 1 mol polyiodobromide emulsion) was prepared with a silver coating amount o, I Ji' / fA2*dry probe film thickness 0.
It was applied to a thickness of 8μ. A surfactant is added to each layer. Sample 302 is obtained by adding the additive (*22) to the 6th layer and 7th layer of sample 301. Sample 303 was obtained by changing the coupler and hardener as shown in Table 2. (422, l-22) is a 2-part coupler, so use a coupler coated Jjik, 60 inches each of gold, reduce the amount of silver halide coating to 70 inches, and adjust it so that it has about the same level as C1, 174 inches. there was. For these samples 301-303, a white wedge exposure (red+green+blue light) was given. These exposed samples were subjected to the following development process, 8! I did it. Processing process Step Time Temperature first development 6f+ 38℃ water washing
2 minutes inversion 25+ “Color development & image 65 points” Adjustment 2 minutes bleaching 6 juices
1/Fixing 4 minutes "Washing 4 minutes" Stable 15+ The following composition of the normal temperature drying treatment liquid is used. No. - developer water
700d Nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 2I
Sodium sulfite 20
g High hydroquinone monosulfonate 30
．． 9 Sodium carbonate (-water salt)
3091-phenyl-4methyl-4-hydroxymethyl-3pyrazolidone 2I Potassium bromide 2.5
Potassium thiocyanate 1
62I potassium iodide (0.1% ordinary liquid)
Add 2ml water
1000d inverted liquid water
700 Gonitrilo N,N,N-trimethylene
3g phosphonic acid pentasodium salt stannous chloride (2 water) 1g p-aminephenol 0.
1/Sodium hydroxide
8g glacial acetic acid 1
Add 5 liters of water and 100
0d color developer water
700 Gonitrilo N,N,N-trimethylene
3g Phosphonic acid pentasodium salt Sodium sulfite 7
g Sodium phosphate (12 hydrate) 3
69 potassium bromide
1g potassium iodide (0.1 g)
90ml sodium hydroxide
3y citradinic acid
1.51N-ethyl-N-(β-methanesulfone IIN amidoethyl)-3-methyl-4
-Aminoaniline f&ful Hanawa 3.6-cythiaoctane-1.8-diol
Add 1y water 1000
ml adjusted liquid water
700 - Sodium sulfite
12 & Sodium ethylenediaminetetraacetate (dihydrate) 8I Thioglycerin 0.4
rrtl glacial acetic acid
Add 3ml water
100011 bleach solution water
80ON ethylenediaminetetraacetic acid sodium salt (dihydrate) 2g Ethylenediaminetetraacetic acid ammonium (dihydrate) 1
2ON potassium bromide
Add 100N water 1
000 liters of fixer water 8
0 mountain d sodium thiosulfate
8009 Sodium sulfite
5.0 N sodium bisulfite
Add 560g water
1000d stable liquid water
800d formalin (37wt%)
5.0rnl Fuji Drywell (interfacial activator manufactured by Fuji Film Co., Ltd.) 5.0
! ! i/add water 10
A similar experiment was carried out after storing it at 35°C and 60% for 2 months. The same measurements as in Example 1 were carried out, and the results of color purity and sensitivity reduction are shown in Table 2. It can be seen from Table 2 that sample 204 according to the invention exhibits particularly good color purity and shelf life. [Effects of the Invention] As described above, according to the present invention, a pyrazoloazole-based magenta coupler capable of forming a magenta color image of an excellent hue with a sharp end of absorption on the long wavelength side is used, and the preservability is improved. A silver halide color photographic material with improved color purity can be obtained.

Claims (4)

[Claims] (1) A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer provided on a support,
The silver halide emulsion layer contains at least a part of a magenta coupler represented by the following general formula [I], and the layer and/or at least one other layer contains a compound represented by the following general formula [II]. A silver halide color photographic material characterized by containing. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_a and Z_b are -CH-, =C- or =
represents N-, R_1 represents a hydrogen atom or a substituent, R_2 represents a substituent, X represents a hydrogen atom or a group that can be separated by a coupling reaction with an aromatic primary amine developer acid, and Z_a = When Z_b is a carbon-carbon double bond, including the case where it is part of an aromatic group, R
_1, R_2 or X may form a dimer or more multimer. However, if two R_2 exist in the same molecule, they may be the same or different, and i) if R_2 does not exist in the same molecule, R_1, or ii) R_2 in the same molecule. At least one of R_1 and R_2 represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and furthermore, at least one of R_1 and R_2 is -NHS
It is a group having one or more O_2- groups, and if Z_a is ▲There is a mathematical formula, chemical formula, table, etc.▼, and Z_b is =N-, R_2 is a substituted or unsubstituted aralkyl group. do not have. General formula [II] (CH_2=CH-SO_2)-_nY In the formula, Y represents an n-valent group, and n represents an integer of 2 or more. (2) The compound represented by the general formula [II] has the following general formula [
IIa] is the compound represented by Claim No. (1)
) Silver halide color photographic light-sensitive material. General formula [IIa] (CH_2=CH-SO_2)-_2Y_1 In the formula, Y_
1 represents an alkyl group having 1 to 12 carbon atoms. (3) The compound represented by the general formula [II] is the following general formula [
IIb] is the compound represented by Claim No. (1)
) Silver halide color photographic light-sensitive material. General formula [IIb] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or an alkyl group having 3 or less carbon atoms (Rs may be the same or different), and A_
1 represents a heteroatom, and m represents an integer of 1 to 4. (4) The compound represented by the general formula [II] has the following general formula [
IIc], which is a compound represented by
) Silver halide color photographic light-sensitive material. General formula [IIc] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (each R may be the same or different), A
_2 represents a divalent group, and n' represents 0 or 1.