JPS62201439A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproducibility by using a combination of a pyrazoazole type magenta coupler specified in structure and a specified thione type compound and improving the spectral absorption characteristics of a magenta dye image. CONSTITUTION:The silver halide color photographic sensitive material has a layer containing at least one of the magenta couplers represented by formula I [each of Za and Zb is =CR<2>- or =N-; each of R<1> and R<2> is H or a substituent, and X is H or a substituent to be released by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent], and one of the compounds represented by formula II. Said magenta coupler is added, preferably, in an amount of 5-500mol% of silver halide contained in the magenta dye forming layer, and the high-boiling solvent to be used for said coupler is added, preferably, in an amount of 0-600wt% of the coupler. The compound of formula II is added in an amount of 10<-5>-10mol%, especially, 10<-3>-1 of silver halide contained in the layer containing said compound I.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic material, and more specifically, to a silver halide color photographic light-sensitive material that has excellent color reproducibility and less unnecessary fog and stain. be. (Prior art) Silver halide color photographic light-sensitive materials generally have silver halide emulsion layers that are sensitive to each of the three primary colors of blue, green, and red, and each color develops yellow, magenta, and cyan, so-called color reduction. The reproduction of a one-color image using this method, and therefore the color image to be reproduced, greatly depends on the color sensitivity characteristics of the 6-piece and the spectral absorption characteristics of the color development. Generally, these properties are determined by restrictions such as color development properties of the compounds used. The color hue of the magenta coupler, which is not necessarily the best in theory, is particularly important for color reproduction, and various improvements have been made. Among them, pyrazoloazole magenta couplers have particularly excellent spectral absorption characteristics for one color hue. For example, to improve the coloring hue of magenta couplers, 5-
In the pyrazolone series, anilino-type magenta couplers (JP-A-49-74027, JP-A-49-11163) have better spectral absorption characteristics than ureido and acylamino types.
No. 1 etc.) were developed. Furthermore, a pyrazoloazole type magenta coupler with less unnecessary side absorption (U.S. Patent No. 3.7)
No. 25,067, etc.) have been developed. This latter coupler not only has less unnecessary absorption in the blue and red light regions compared to the color image obtained from the 5-pyrazolone type magenta coupler, and is advantageous in terms of single-color reproduction, but also has the advantage that the coupler itself can absorb light, heat, and It has the advantages of being stable against temperature, difficult to decompose, and resulting images have little yellowing over time. On the other hand, this pyrazoloazole magenta coupler has 5
- Compared to pyrazolone-type magenta couplers, those with practical coloring performance promote unnecessary fogging of silver halide grains during color development. Many of them have the disadvantage that white background areas and low-color image areas are stained with magenta color. As a method for preventing the occurrence of fogging, for example, l-phenyl-5-mercaptotetrazoles (Belgian Patent No. 6
No. 71,402, U.S. Pat. No. 3,295.976, U.S. Pat. No. 3,378,310, U.S. Pat.
Same No. 3,071゜465, Same No. 3.420,664, Same No. 2゜403.927, Special 1Sll 1983-37
No. 436. JP-A No. 58-95728, etc., benzotriazoles (
British Patent No. 919,061, British Patent No. 768.438,
U.S. Patent No. 3,157°509, U.S. Patent No. 3.082.0
German Patent No. 88, German Patent No. 617,712, etc.), benzimidazoles (US Pat. No. 3,137,578, German Patent No. 3,148.066, German Patent No. 3,511,663, British Patent No. 271. No. 475, fJJ1, 344゜5
No. 48, No. 3,148,066, No. 3゜511.
663, German Patent No. 708,424, German Patent No. 635
, 769, U.S. Patent No. 2,205.539, etc.), imidazoles (U.S. Pat. No. 3.106.467, U.S. Pat. No. 3,4
No. 20,670. A method is known in which a heterocyclic compound such as JP-A No. 1,763,990, JP-A No. 2,271-229, etc. is added to a light-sensitive material or a processing solution. (Problems to be Solved by the Invention) However, the use of these compounds alone 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 fog during storage without reducing sensitivity. Therefore, it is an object of the present invention to take advantage of the excellent features of pyrazoloazole magenta couplers and to provide a silver halide color photographic light-sensitive material with less stain and fog, which are the drawbacks thereof. More specifically, the first objective is to provide a color photographic material with better color reproducibility due to a magenta color image with good one-spectrum absorption characteristics. A second object is to provide a color photographic material which has a fast color image and has improved white background staining. The third purpose is to have a color density that is suitable for practical use.
It is an object of the present invention to provide a photosensitive material free from color contamination in white background areas and low density image areas. (R-depression for Solving the Problems) As a result of intensive research to develop a silver halide color photographic light-sensitive material that satisfies these demands, the present inventors discovered that a pyrazoloazole with a specific structure was developed. The present invention has been made based on this knowledge.The present invention has been made based on this knowledge.The present invention has been made based on this knowledge. ), and at least one of the layers contains a compound represented by the following general formula (■). I) B 1 and R2 represent a hydrogen atom or a substituent; X represents a hydrogen atom or a group that is removed by a coupling reaction with an oxidized aromatic primary amine developer; - In the case of a carbon double bond, it may be a part of an aromatic ring, and further R1, R2 or
may form a dimer or more multimer, provided that R
Or, at least one of R2 is linked to the pyrazoloazole nucleus via a secondary or tertiary carbon! General formula (■) (where R3 represents a group to be combined and R or R2 contains at least one -NH802- group) (wherein R3 is a substituted or unsubstituted alkyl group, aralkyl group, alkenyl group, aryl group or Represents a heterocyclic residue, where X is 0, S, Se! or NR' (R
' is a substituted or unsubstituted alkyl group, aralkyl group, or alkenyl group. represents an aryl group, a heterocyclic residue (which may be the same as or different from R3), Q represents an atomic group necessary to form a 5-6 negative heterocyclic ring, and is fused. The thione type antifoggant represented by the above general formula (II) will be explained in detail. The alkyl group represented by R3 and R4 is preferably IRJ
Substituents, including those having 1 to 20 atoms (for example, methyl, ethyl, (, butyl, hexyl, dodecyl, etc.) and substituted, include halogen atoms (
For example, chlorine atom), cyano group. Carboxy group, hydroxy group, acyloxino group having 2 to 6 carbon atoms, ((in other words, acetoxy group), alkoxycarbonyl group having 2 to 22 carbon atoms (e.g. ethoxycarbonyl group, butoxycarbonyl group), carbamoyl group, sulfamoyl group, sulfamoyl group group, amino group, substituted amino group, etc. Aralkyl group represented by R:l, R4 is, for example, benzyl group, phenethyl group, etc. Alkenyl group represented by R:l, R4 is, for example, allyl group, etc. The aryl group represented by R:l, R4 is a monocyclic or bicyclic, preferably monocyclic, aryl group, including substituted ones. an alkyl group (e.g., methyl group, ethyl group, nonyl group),
Alkoxy group having 1 to 20 carbon atoms (e.g. methoxy group,
ethoxy group), hydroxy group, halogen atom (for example, chlorine atom, bromine atom f-), carboxy group, sulfo group, etc. The 5- or 6-membered heterocycle formed by Q is, for example, a thiazoline ring, a thiazolidine ring, a selenazoline ring, an oxazoline ring, an oxazolidine ring, an imidacilline ring, an imidazolidine ring, l. These include a 3.4-thiadiazoline ring, a 1,3.4-oxadiazole ring, a 1,3,4-triazoline ring, a tetrazoline ring, a pyrimidine ring, and the like. Of course, these heterocycles include those in which a 5- to 7-membered carbon ring or heterocycle is fused thereto. That is, benzothiazoline nucleus, naphthothiazoline nucleus,
Dihydronaphthothiazoline nucleus, tetrahydrobenzothiazoline nucleus, benzoselenazoline nucleus, benzoxazoline nucleus, naphthoxazoline nucleus. Included are a benzimidacilline nucleus, a dihydroimidazolopyrimidine nucleus, a dihydrotriazolopyridine nucleus, a dihydrotriazolopyrimidine nucleus, and the like. These condensed ring nuclei can have one of various substituents, 6 for example, an alkyl group having 2 ax to 20 carbon atoms (e.g., methyl group), an alkoxy group having 20 carbon atoms (e.g., methoxy group), a carbon number 1 to 20 20 alkylthio groups (e.g. methylthio group), hydroxyl group, amino group (including not only unsubstituted but also substituted amino groups, for example dimethylamino group,
acylamino group such as acetylamino group), aryl group (e.g. phenyl group), alkenyl group having a2 to 20 carbon atoms (e.g. allyl group), aralkyl group (e.g. pencil group), halogen atom (e.g. basic, bromine), cyano group , carboxy group, sulfo group, carbamoyl 7! (e.g. carbamoyl group, methylcarbamoyl group), carbon number 2
-22 alkoxycarbonyl Z&i (e.g., methoxycarbonyl group), aryloxycarbonyl group (e.g., phenoxycarbonyl group), alkylcarbonyl group having 2 to 22 carbon atoms (e.g., acetyl group), and the like. The above compound is published in Japanese Patent Publication No. 48-34169, Pharmaceutical Journal 7.
No. 4, pp. 1365-1369 (I954), Tokuko Sho 4
No. 9-23368, Pilestenx (Beilste
nx)n, page 394, page IV-121, Special Publication 1977
It can be synthesized by the method described in Kasa No.-18008. Next, specific examples of the above-mentioned thione type antifoggants will be shown. α-13(X-2) [π-3) (I
-4) (T-5) C knee 6] 1"11-1 Ba-'7) (:I-B) C'K -
9) (Knee 10)EX-11)
is -12] (X-13
3 (knee 14) CX-15) (π-16] lX-17) (X-
18) [π-19) (
' 21 or a group other than an unsubstituted aralkyl group. In the compound represented by the general formula (I), a multivalent body is 1
It means a compound having two or more groups represented by the general formula (I) in its molecule, and includes bis compounds and polymer couplers. Here, the polymer coupler has the general formula (I)
It may be a homopolymer consisting only of a tj:Lf form (preferably one having a vinyl group, hereinafter referred to as a vinyl monomer) having a moiety represented by, or a homopolymer that does not cuff with the aromatic primary amine current specialized form. A copolymer may also be produced with a non-chromogenic ethylene-like ω-isomer. Generally, behind the pyrazoloazole magenta coupler represented by t (r), #? What is beautiful? The following general formulas (m), (■), (V), (l and (■)
It is expressed as (ff) (V) ('') (■) Among the couplers represented by the general formulas (III) to (■), one preferred for the purpose of the present invention is the general formula (m), (V
) and ('9T), and the most preferred one is the general formula (represented by l). In the general formulas (m) to ('9T), R11, R128 and R13 may be the same or different Hydrogen atom, halogen atom, furkyl group, 7-aryl group, heterocyclic group, cyano group, flukoxy group, aryloxy group,
peterocyclic oxy group, 7syloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, 7sylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, furkylthio group, 7lylthio group, peterocyclic thio group, flukoxyluponyl 7mino group, aryloxycarbonylamino group,
sulfonamide group, carbamoyl group, acyl group, sulfonamide group)
γmoyl group, sulfonyl group, sulfinyl 2&, alkoxycarbonyl group. represents a 7-aryloxycarponyl group, X is a hydrogen atom,
1J5A in the coupling position via a halogen atom, carboxy group or oxygen atom, nitrogen atom or sulfur atom
represents a group that binds to t, R
”, R12, R13t or In particular, a polymer derived from a vinyl monomer having a moiety represented by the general formula is preferred, and in this case, R11, R12, R1: or X represents a vinyl group or a linking group. RIl, R12 and RI3 each represent a hydrogen atom, a halogen atom (e.g. chlorine atom, 14 atoms), an alkyl group (e.g. methyl group, propyl group,
Isopropyl group, t-butyl group, trifluoromethyl group, tridecyl group, 2-[α-(3-(2-year-old ctyloxy-5-tert-octylbenzenesulfone 7mide)
phenol) latradecanamide] ethyl) A, 3-<
2.4-di-t-7milphenoxy)propyl group, allyl group, 2-dodecyloxyethyl group, 1-(2-octyloxy-5-tert-octylbenzenesulfone 7)
mido)-2-propyl group, 1-ethyl-1-(4-(2
-butoxy'y-5-tert -octylbenzenesulfonamido)phenyl)methyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group. benzyl group, etc.), aryl group (e.g., phenyl group, 4
-t-butylphenyl group, 2,4-di-t-7milphenylene group, 4-tetradecanamidophenyl group, etc.) 4hetero f5 group (e.g., 2-furyl group, 2-chenyl group,
2-pyrimidinyl group. 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g., methoxy group, ethoxy group, 2-medoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesyloxyethoxy group, etc.), aryloxy group (e.g.,
Phenoxy group, 2-methylphenoxy, 15.4-t-
butylphenoxino A'8), heterocyclic oxy (e.g., 2-penzimidazolyloxy, etc.), acyloxy (e.g., acetoxy, hexadecanoyloxy, etc.), carbamoyloxy (e.g., N- phenylcaroctamoyloxy group, N-ethylcaroctamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy, Ji, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.). Acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2゜4-di-t-
amylphenoxy)butyramide group, γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α
-(4-(4-hydroxyphenylsulfonyl)phenoxy)decane 7mido group, etc.), 7nilino group (e.g., phenylamino group, 2-chloroanilino group, 2-10ro5
-tetradecanamide anilino group, 2-chloro-5-dodecyloxycarbonylanilino group. N-7 cetyl 7nilino group, 2-chloro-5-(α-(3
-t-butyl-4-hydroxyphenoxy)dodecane 7
(mido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, 15.N, N-dibutylureido group, etc.), imide group (e.g., N-succinimide group, 3-henzylhydantoinyl 7A, 4-(2-ethylhex/ylamino)phthalimide group, etc.), sulfamoyl 7-mi7 group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-decylsulfamoylamino group, etc.), furkylthiono & ( For example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3
-(4-t-butylphenoxy)propylthio group, etc.),
7-arylthio group (e.g., phenylthio group, 2-butoxy-5-

[-cutylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4
-tetradecane 7-midophenylthio group, etc.), heterocyclic group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryl Oxycarbonyl 7-mino group (e.g., phenoxycarbonyl 7-mino group, 2,4-di-tert-
butylphenoxyl group, sulfonamide group (e.g., methanesulfonamide type, hexadecanesulfonamide group, benzenesulfonamide group, P-toluenesulfonamide group, ocitadecanesulfone group, 2-methyloxy- 5
-t-butylbenzenesulfone 7mido group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl J%, N, N
-dibutylcarbamoyl group. N-(2-dodecyloxyethyl)carbamoyl group, N
-Methyl-N-dodecylcaroctamoyl group. N-(3-(2,4-di-tert-7milfe/xy)propyl)carbamoyl group, etc.). 7syl I & (e.g. acetyl group, (2,4-dite
rt-7 milphenoxy)acetyl group, benzoyl group 4), sulfamoyl 7M (N, N-ethylsulfamoyl group, N,N-diprovirus JLt7γmoyl L N-(2-dodecyloxyethyl)sulfT moyl Jk (N-, groups, etc.), sulfinyl
, flukoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.)
, represents an aryloxycarbonyl group (e.g., phenyloxycarbonyl t, C,3-hentadecyloxy-carbonyl group, etc.), and X represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), or a carboxy group, or a group connected by a myg atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2゜4-dichlorobenzoyloxy group, ethoxoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenokidyl group, 4-methanesulfonamide phenoxygen,
4-notanesulfonylphenoxy group, α-naphthoquine crystal, 3-pentadecylphenoxy group. To/Ziroquin force Luponyloxino person, Ethoxy 2 (,
2-77 noethoxy group, hensyloxy group. 2-phenethyloxy group, 2-phenoxyethoxy group,
5-phenyltetrazolyloxy group, 2-benzothiazolyloxono&, etc.), nitrogen-linked nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide group) group, 2,3,4,5.6-bentafluoropensamito group, octane sulfonamide group, P-cyanophenylureido 1.N.N-diethylsulfTmoyl7mino group, !-piperidyl group, 5.5 -dimethyl-2,4-dioquine-3-oxazolidinyl group, !-benzylethoxy-3-hydantoynyl group, 2N-1,1-dioxo-3(2H)-oxo-1,2-benzointhi7zolyl group ,2-oxo-1
, 2-dihydro-1-pyridinyl group, imidazolyl group,
Birazolylno^, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-promopensotri7sol-1-yl, 5-methyl-1゜2.3.4-
1 rian-roo! -yl), (, penzimidanril, 3-benzyl-1-hydantoynyl 2&, t-
Benzyl-5-hexadecyloxy-3-t: dantoynyl group, 5-methyl-1-tetrazolylno! etc.), arylazo groups (e.g. 4-methoxyphenylazo group, 4-pivaloyl7minophenyl7yH, 2-naphthylazo group, 3-methyl-4-
hydroxyphenylazo group, etc.). Groups linked via a sulfur atom (e.g., phenylthiono, (
, 2-carboxyphenylthiotum, 2-methoxy-5
-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio group Base. hensylthio group, 2-cyanoethylthio x, i-ethoxycarbonyltridecylthio group, 5-phenyl-2,3
,4,5-tetrazolylthiono^. 2-Benzothiazolylthiono^, 2-dodecylthio-5
-thiophenylthiono^, 2-phenyl-3-dodecyl-1,2,4-)lyazole-5-thiono J1, etc.). In the coupler of general formula (Ill), R12 and R13 may be combined to form a 5- to 7-membered ring. R■, R12, R13trilfX! >(2fi(7)
When forming the group fX*Y-bis, IT or RIl, R12゜R13 is a substituted or unsubstituted fullkylene group (e.g., methylene group, ethylene, 1.
10-decylene group, -CI(CI(-〇-CH2CH2
-, etc.), substituted or untested phenylene & (e.g. Jf
, 1,4-phenylene group, l, 3-7 enylene-NHC
O-R14-CONH-) &(R'' represents a substituted or unsubstituted alkylene group or phenylene group, 1 for example -
NHCOCH2CH2CONH-. CH3 -s-n -s- group (R14 represents a 21st or 22nd test-free fullkylene group, e.g. -5-CH2CH2-3゜CH3 RIl, R12°R13 or The linking group that appears is a fullkylene group (a 22-substituted or 2I-free alkylene group, for example, a methylene group, ethylene > s, t, to-decylene group, -C
HCHOCH2CH2- etc.). Phenylene group (substituted or unsubstituted phenylene group, e.g. Eva, 1, 4-phenylene group, !, 3-phenylene 2&
. -NHCO-, CONH-, -0-, -0CO- and 7-ralkylene groups (for example. -0-C-. -CONH-CH2CH2NHCO-. -CHCH0-CH2CH2!-NHCO-. Vinyl groups are those of general formulas (m) (ff), (V). Other than those represented by (vI) and ([) 21 test groups may be taken for <, &f. The preferred n-group represents a hydrogen atom and a lower alkyl group (e.g., methyl group, ethyl group) having 1 to 1 prime side f- or 1 to 4 primes. Monomers containing those of formula (III), (N), (V), (■) and (■) c'P) are non-color-forming compounds that do not oxidize with the oxidation products of aromatic-grade amine developers. A copolymer may be made with a polyethylene-like monomer. Non-color forming ethylene-like FF115x compounds that do not cuff with oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), and derivatives of these acrylic acids. The esters used also contain haamides (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide; diacetone acrylamide, methacrylamide; methyl 7-acrylate, ethyl acrylate, n-propyl 7-acrylate, n-butyl 7-acrylate, t-butyl 7-acrylate, -butyl acrylate), 1so-butyl 7-acrylate, 2-ethylhexyl 7-acrylate. n-octyl acrylate, lauryl 7-acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl ester (
(eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylatetrile. Aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinylfurkyl ether (e.g. vinyl ethyl ether), maleic M, s Hydromaleic acid, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2-8
and 4-vinylpyridine. The A color-forming ethylene-like unsaturated vehicle φ body used here can also be used with two inserts. For example, n-butyl 7-acrylate and methyl 7-acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl 7-acrylate and diacetone acrylamide, etc. 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 undeveloped month may be either water-soluble or water-insoluble, but polymer coupler latex is particularly preferred. Specific examples and synthesis methods of the pyrazoloazole magenta coupler represented by the general formula (I) used in the present invention can be found in JP-A-59-162548 and JP-A-60-43659. 59-171956. 60-172982, 60-
No. 33552 and US Pat. No. 3,061,432. Next, specific examples of typical magenta couplers according to the present invention will be shown, but the present invention is not limited thereto. Knee 1゜1-2゜■-6゜Knee 8゜1-9・1-10゜l-12゜1-17゜CH3 し4! '1g111 ■-25 ) -27° knee 29°1-30°J -33°1-34° The above general formula (I) per mole of silver halide
The preferred ratio of the magenta coupler (hereinafter referred to as compound (I)) represented by is 0.05 to 5 mol,
The weight ratio of the high Buddha point solvent to the pyrazoloazole magenta coupler is preferably 0 to 6.0. The compound represented by the general formula (n) (hereinafter referred to as compound (I)
The additive layer (referred to as I) may be added to the sensitive material or this layer, or may be added divided into two or more layers, but it is preferably added to the layer containing the compound Th(I). . A desirable addition layer of compound (n) is 10-7 mol to 1 mol of silver halide in the layer containing compound (I).
The amount is O-1 mol, more preferably in the range of 1O-5 mol to 1O-2 mol. Coupler can also be used. Yellow couplers can be used. Typical examples of these include naphthol or phenolic compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers used in the present invention include Research Disclosure (RD) 17643 (I978). (December, 1979) and the patent cited in No. 18717 (November, 1979). The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and the coupling active position is substituted with a leaving group rather than a four-equivalent color coupler with a hydrogen atom. Two-equivalent color couplers are preferable, such as couplers in which the amount of silver to be coated can be reduced.0 Couplers in which color-forming dyes have appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor along with the coupling reaction, or DIR couplers that promote development. Typical examples of yellow couplers that can be used in the present invention that release agents include oil-protected acylacetamide couplers. A specific example is U.S. Patent No. 2,407,21
No. 0, No. 22.875,057 S and No. 3,26
The use of two-equivalent yellow couplers is preferred in the present invention, as described in U.S. Pat.
No. 408,194, No. 3,447゜928, No. 3
, No. 933, 501 and No. 4, 022, 620
%f2 Toniki t Saleta [IN 2 child detachable yellow coupler or Japanese Patent Publication No. 10739/1983, U.S. Patent No. 4,401,752, U.S. Patent No. 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5゜020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom dissociable yellow couplers described in Ibid. No. 2,261,361, Ibid. No. 2,329.587 and Ibid. No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density. Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat.
, No. 212, No. 44,146,396, No. 4゜2
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 28.233 and No. 4,296,299. Further, specific examples of phenolic couplers include U.S. Pat.
, 801° 171, 2,772,162, 2° 895.826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
Phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in No. 72,002, U.S. Pat. No. 24,126,396, 4.334. Ol No. 1, No. 24,327゜1
73, West German Patent Publication No. 23,329,729 and Japanese Patent Application No. 58-42671, etc., and U.S. Pat. No. 3,446,622, U.S. Pat. , No. 333,999,
Same No. 4,451゜559 and Same No. 4,427,76
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 7. The various couplers used in the present invention can be used in combination of one or more types in the same photosensitive layer or in two different layers in order to satisfy the characteristics required for the photosensitive material. It is also possible to introduce more than one. The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods. After dissolving in either one of the so-called auxiliary solvents alone or in a mixture of both,
Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are described in, for example, US Pat. No. 2,322,027. Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mol, and for cyan couplers 0.002 to 0.
It is 3 moles. The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide, sodium chloride, potassium glaze alone or a mixture thereof) solution with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as Silver halide grains may have different layers inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of uniform phases throughout the grain, or may contain a mixture of these. good. For example, for silver chlorobromide grains with different phases, the grains may have a core or single or multiple layers within the grain that are richer in silver bromide than the average halogen composition.
It may also be a grain having a core or single or multiple layers rich in silver chloride than the average halogen composition. Average grain size of silver halide grains (spherical or st
For particles close to , the particle diameter, for cubic particles,
Based on the projected area of each spear throw, it is preferable that the particle size is 2 or less and 0.1 or more, but particularly preferable is 0 particle size that is 1w or less and 0.15g or less. The distribution may be narrow or wide. So-called monodisperse silver halide emulsions can be used in the present invention. The degree of monodispersity is preferably 15% or less, particularly preferably 10% or less, as a coefficient of variation obtained by dividing the standard deviation derived from the grain size distribution curve of silver halide by the average grain size. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. To! One layer can be applied. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use. The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes, or may have a plate-shaped particle. Often, emulsions with a length/thickness ratio of 5 or more, especially 8 or more may be used.These various emulsions may be surface latent image type in which a latent image is mainly formed on the surface, or may be formed inside one grain. Any internal latent image type may be used. The photographic emulsion used in the present invention is by P. Gerafkides, R.
Chemistry and Physics of Photography J
photographique) (published by Paul Montell, 1967), G. F. Duffin, "Photographic Emulsion Chemistry J"
ulsion Chesistr2) (Focal Press, 1966), V. “Manufacture and Coating of Photographic Emulsions” by L. Zelikman et al.
ing and coating photog
It can be adjusted using the method described in "Raphic Emulsion" (published by Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble #[ with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. It is also possible to use a method in which good 0 grains are formed in an excess of silver ions (so-called back-mixing method). It is also possible to use a conversion method in which a halide salt is added to form a less soluble silver halide. As one of the simultaneous mixing methods, it is also possible to use a method in which the pag in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrald tuple jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. After grain formation, silver halide emulsions are usually subjected to physical ripening, deplanarization and chemical ripening before being used for coating. Known silver halide solvents (for example, ammonia, rhodankali or U.S. Pat. No. 3,271°157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.). It can be used in , physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, extrinsic method, etc. are used. The photographic emulsion used in the present invention can be spectrally sensitized with methine dyes or the like, if necessary. The photographic emulsion used in the present invention may contain one of various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, 19-esteric acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfone as color antifogging agents or color mixing inhibitors. It may also contain a 7-midophenol derivative or the like. Various anti-fading agents can be used in the light-sensitive material of the present invention. In the photosensitive material of the present invention, an ultraviolet absorber can be added to the wood-philic colloid layer. The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and increasing Ii). In addition to the above-mentioned additives, the photosensitive material of the present invention may also contain various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or their precursors, lubricants, mordants, and matting agents. , antistatic agents, plasticizers, and various other additives useful in photographic materials.Representative examples of these additives are listed in Research Disclosure.
17643 (December 1978) and 18716
(November 1979). Book 9.11 is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Furthermore, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may exist between two or more emulsion layers having the same photosensitivity. good. In addition to the silver halide emulsion layer, the light-sensitive material according to 1 of the present invention is preferably provided with auxiliary layers such as an a-retaining layer, an intermediate layer, a filter layer, an antihalation layer, and a second bar layer. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as a plastic film, paper, or cloth, which is commonly used in photographic light-sensitive materials, or a flexible support such as glass, ceramic, or metal. applied to the body. Among the supports used in the present invention, baryta paper and paper supports laminated with polyethylene containing a white pigment (for example, titanium oxide) in polyethylene are preferred. The present invention can be applied to various photosensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or television, color papers, color positive films, and color reversal papers. Research Disclosure 17123 (July 1978)
It can also be applied to black-and-white photosensitive materials using a mixture of three-color couplers, such as those described in The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-7 minnow N, N
-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethyl7niline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl -4-amino-N-
Examples include ethyl-N-β-methoxyethylaniline and ff1M salts thereof, hydrochlorides, p-toluenesulfonates, and the like. The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, vanzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as After color development, the photographic emulsion layer is usually bleached. The deep treatment may be performed simultaneously with the fixing treatment or separately. Examples of bleaching agents include iron (■), copal (m), chromium (■), copper OL), etc. Metal compounds, peroxidants, quinones, nitroso compounds, etc. are used. Typical bleaching agents include ferricyanide; weight 0 murate:
An example of an organic rust of cobalt (m) or cobalt (m) is ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Use of 7-minopolycarboxylic acids such as nitrilotriacetic acid, l,3-diamino-2-prohemal tetraacetate, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: peryl manganate; nitrosophenol, etc. I can do it. Of these, iron ethylenediaminetetraacetate (m)
If! and persulfates are preferred from the viewpoint of rapid processing and environmental pollution, and ethylenediaminetetraacetic acid iron(m) complexes are particularly useful both in stand-alone bleach solutions and in bath bleach-fix solutions. If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution. After bleach-fixing or fixing, washing with water is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water.For example, in order to prevent precipitation, hard water such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, etc. Softeners, bactericides and anti-pep agents to prevent the growth of various bacteria, algae, and mold, hardening agents such as magnesium salts and aluminum salts, and surfactants to prevent dry loads and unevenness. It can be added as needed. Orori, E. West “Water Quality Judgment Criteria” (enemy Qualit7
(riteria), rPhotography Science and Engineering J (
Phata, Sci, Eng,), Volume 6, 34
Compounds described on pages 4 to 359 (I965) may be added, and addition of chelating agents and anti-piping agents is particularly effective. In the washing process, it is common to wash two or more tanks in countercurrent flow to save one water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as No. 8543 may be carried out, in which various compounds are added to the stabilization bath for the purpose of stabilizing the image. 2! various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid) to Typical examples include acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone, irithiazolone, 4-thiazoline benzimidazole, etc.) as necessary. , halogenated phenols, etc.), surfactants, optical brighteners, hardeners, and the like may be used, and two or more compounds for the same or different purposes may be used in combination. In addition, ammonium chloride, ammonium nitrate, and isammonium are used as membrane pHyJ regulators after treatment. It is preferable to add various ammonium salts such as ammonium phosphate, pseudoammonium sulfate, and ammonium periosulfate. The silver halide light-sensitive material of the present invention may incorporate a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. The silver halide photosensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. Typical compounds thereof are JP-A No. 56-64339,
No. 57-144547, No. 57-211147, No. 58-50532, No. 58-50536, No. 58-
No. 50533. It is described in No. 58-50534, No. 58-50535, No. 58-115438, etc. The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C, but it is preferable to develop at a temperature of 33°C to 38°C.
226,770@ or U.S. Patent No. 3,874,49
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 9 may be performed. A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary. (Effect of Emergence 1) According to the silver halide color photographic light-sensitive material of the present invention, r
A photographic image without color staining can be obtained in the I background area or low C) 1 image area. Furthermore, the silver halide color photographic material of the present invention has a strong one-color image and is highly effective in improving white background contamination.Furthermore, the silver halide color photographic material of the present invention provides a magenta color image with good spectral absorption characteristics. A photographic image with excellent one-color reproducibility is thus obtained. EXAMPLES The present invention will be explained in detail based on specific examples below.
The present invention is not limited thereto. Example 1 A color photographic light-sensitive material was prepared by coating the following layers from the first layer to the eleventh layer on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye. (Photosensitive Layer Composition) The components and the coating weight in g/rn' are shown below, and for silver halide, the coating weight in terms of silver is shown. 1st layer (anti-halex, multilayer) Black colloidal silver ...0. lO gelatin Φ...2.00 No. 27! (Low sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (Wood 5 and Wood 4) (silver iodide 3.5 mol%, average grain size 0, 7)
#L) ...Silver 0.15 gelatin
...1.00 cyan coupler (book 3)
...0.30 anti-fading agent (book 2) ...
...0.15 coupler solvent (book 18 and book...0.0
6 Third layer (high-sensitivity red-sensitive IF) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (Books 5 and 4) (g iodide 8.0 mol%, average grain size 0, 7 #
L) ...@0.10 gelatin
...0.50 cyan coupler C tree 3)
...0.10 anti-fading agent (wood 2) ...
...0.05 coupler Yuhime (Book 18 and Book L)...0.
02 4th layer (intermediate layer) Yellow colloidal silver ・・・・・・0.02 Gelatin ・・・・・・1.00 Color mixing inhibitor (wood i4) ・・・・・・O, Oa color mixing inhibitor solvent (Thursday 13)・・・o, te polymer latex (
Zero 6)...o, i. 5th layer (low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (Ki 12) (silver iodide 2.5 mol%, average grain size 0.41 L)
・・・・・・Silver 0.20 gelatin
・・・・・・0.70 magenta coupler (Thursday 11)・
...0.40 Anti-fading agent A (wood 10) ...
0.05 Anti-fading agent B (wood 9) ...0.0
5 Anti-fading agent C (08) ...0.02 Coupler solvent (7) ...0.15 6th layer (high sensitivity green sensitive layer) Green sensitizing dye (wood 12) ) spectrally sensitized silver iodobromide emulsion (silver iodide 3.5 mol%, average grain size 0.91 L)
・・・・・・Silver 0.20 gelatin
・・・・・・0.70 magenta coupler (Thursday 11)・
...0.40 Anti-fading agent A (book 10) ...
・0.05 Anti-fading agent B (wood 9) ・・・・・・0,
05 Anti-fading agent C (08) ...0.02 Coupler solvent (wood 7) ...0.15 7th layer (
(Yellow filter single layer) Yellow colloidal silver ...0.20 Gelatin ...1.00 Color mixing prevention agent (Wood 14) ...0.06 Color mixing prevention agent solvent (Wood 13) ...0124 8th layer (low sensitivity blue feeling W
j) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (Book 16) (silver iodide 2.5 mol%, average grain size 0.51 L)
・・・・・・Silver 0.15 gelatin
ψ pot・・・0.50 yellow coupler (book 15)・
...0.20 coupler solvent (book 18) ...
0.05 9th layer (high sensitivity blue sensitivity Ia) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (Book 16) (silver iodide 2.5 mol%, average grain size 1.4#L) )
...fio, 20 gelatin
...0950 yellow coupler (book 15)
...0.20 coupler solvent (Book 18) ...
...0.05 10th layer (ultraviolet absorption layer) Gelatin ...φΦ ...1.50 ultraviolet absorber (wood 19) ...1.00 ultraviolet absorber solvent (book 1B) ... 0.30 Color mixing prevention 11 2nd agent (wood 17) 0.08 11th layer (protective layer) Gelatin 1.00 hardening agent (book 20)・0.17 The compounds used here are as follows: Wood 1 Dioctyl phthalate 22-(2-Hydroxy-3-sec-butyl-5
-t-butylphenyl)benzotriazole 32- [α-(2,4-di-t-7milphenoxy)butanamide)-4,6-dichloro-5-ethylphenol* 4 5.5'-dichloro-3, 3'-di(3-sulfobutyl)-9-ethylthiacarbonylcyanine sodium base 5 triethylammonium-3-(2-(2-[
3-(3-sulfopropyl) naphtho(I,2-d)thiazolin-2-ylidenemethyl]-1-butenyl)-3-naphtho(I,2-d)thiazolino]propanesulfonate zero 6 polyethyl acrylate wood 7 phosphorus Acid trioctyl ester 82.4-di-hexylhydroquinone 9 di-(2-hydroxy-3-t-butyl-5-
Methylphenyl) methane to 3,3.3',3'-tetramethyl-5,6
,5',6'-tetrapropoxy-1,1'-bisspiroindane zero 11 1-(2,4,6-)dichlorophenyl)-3
-(2-chloro-5-tetradecanamido)anilino-2-pyrazolino-5-one 12 5.5'-diphenyl-9-ethyl-3,3'
-Disulfopropyloxacarbocyanine Na #1 ゛Tree 13 Phosphoric acid -〇-cresyl ester 14 2.
4-di-t-octylhydroquinone tree 15 α-pivaloyl-α-((2,4-dioxo-
1-Benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-2,4-dioxo-amylphenoxy)butane aminocoacetanilide 16) Ethylammonium 3-(2-( 3-
Benzylrhodanin-5-ylidene)-3-benzoxazolinyl]propanesulfonate 17 2.4-di-5ec-octylhydroquinone 18 Phosphate trinonyl ester 19 5-chloro-2-(2-hydroxy-3 -t-
butyl-5-t-octyl) phenylbenztriazole*20 1.4-bis(vinylsulfonylacetamido)ethane The sample prepared as above was designated as sample number 101,
This was used as a control sample for subsequent comparisons. Sample No. vf102-10911 Sample No. 101(7) The magenta coupler (zero 11) and additives in the 5.6th layer were replaced or added. After stepwise exposure for sensitometry, these samples were subjected to development measurements using the following processing steps, and the results of measurements using FAD (Fuji Photo Film Automatic Measuring Device) are shown in Table 1 below. [Processing process] First development (black and white development) 38℃ 1 minute 15 seconds Water
Washing 38℃ 1 minute 30 seconds inversion exposure
Color development for 1 second or more over 100 Lu electrons
Wash with water at 38℃ for 2 minutes and 15 seconds 38
℃ 45 seconds bleach fixing 38℃ 2 minutes 00
Wash with water for 2 seconds at 38℃ for 2 minutes and 15 seconds [
Treatment liquid composition] 1 unit 1j Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 0.6g Diethylenetriaminepentaacetic acid-11-sodium salt 4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate
35.0g hydroquinone monosulfonate potassium salt 25.0g diethylene glycol 15. Om cross 1-phenyl-4-term droxymethyl-4-methyl-3-pyrazolidone 2.
Add 0g potassium chloride 0.5g potassium iodide 5.0mg water
1 fL (pH 9,70) 11 Benzyl alcohol 15.0 m Diethylene glycol 12. OmfL3.6-Sythia 1
．． 8-octanediol 0.2g Nitrilo-N
, N,N-trimethylenephosphonic acid, pentasodium salt 0.5g Diethylenetriaminepentaacetic acid, pentasodium salt 2.0g Sodium sulfite 2.0g) Deficient potassium
25.0g hydroxylamine sulfate
3.0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 1h5, 0 g potassium bromide 0.5 g potassium iodide
Add 1.0mg water
IJl (pH 10, 40) 1st section 2-mercapto-1,3,4-triazole 1. Og ethylenediaminetetraacetic acid disodium di-salt 5.0g ethylenediaminetetraacetic acid iron acetate II [) Ammonium hydrate 80.0g sodium sulfite 15, 0g sodium 100sulfate (700gll liquid) 160. OmJL Glacial Acetic Acid 5. Add OmIL water
12 (pH 6,50) In Table 1, (Tree 21) and (Tree 22) represent the following compounds. Tree 21 C8Hfu7Cε) Tree 22 Color purity in this table means magenta filter CCC
The sum of the cyan and yellow densities (DR and DB, respectively) at a point where the magenta density (Dfl; The ratio (
DG/DR+DB). That is, it is a measure that indicates the amount of extra cyan and yellow components in magenta, and it can be said that the smaller the value, the higher the purity of the color. The increase in stain due to thermal fading is the value obtained by measuring the change in the density of yellow stain on the white background after 15 days using a B filter after placing the treated print in a constant temperature and humidity chamber AO' (knee 70%). From the results in Table 1. , sample numbers 107 and 1 according to the invention
It can be seen that Sample No. 09 not only has high color purity, but also suppresses unnecessary color staining with almost no decrease in relative sensitivity. Example 2 A color photosensitive material was prepared by applying photosensitive layers consisting of the primary FF11 layer to the third layer onto a paper support laminated on both sides with polyethylene. The polyethylene on the side coated with the first layer contains titanium diMide white pigment 1 and group N of 1111 as white pigment. (Structure of Photosensitive Layer) The numbers corresponding to each component indicate the coating value expressed in g/rn' 1st place, and the silver halide indicates the coating amount in terms of silver. 1st layer (green sensing layer) 11! Silver bromide emulsifier (silver bromide 70 mol% sensitizing dye wood 31
) ・・・・・・Silver 0.30 Magenta Coupler (Book 3
2)...0.25 Magenta coupler solvent (Tree 34)...0.30 Anti-fading agent (Book 9/Tree 10)...0.0510.10 Gelatin... ...1.00 Second layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (wood 33) ...0.50 Ultraviolet absorbing solvent (DBP) ...0.20 Gelatin
・・・・・・o, tc; Third layer (protective layer) Gelatin ・・・・・・1.50 Here, DBP represents dibutyl phthalate, and the chemical structure of The following is shown. t Umbrella 33 Also, gelatin hardening agent 2.4 is distributed equally from the first M9 to the third layer.
-Dichloro-6-hydroxy-1,3°5-triazine sodium salt was added. The trial price of this photosensitive material was $4,201. accomplished. These samples were subjected to gradation exposure for sensitometry using an enlarger (Fuji Color 7F609, manufactured by Fuji Photo Film Co., Ltd.), and then developed using the following processing steps. Temperature Time Developing solution 33°C 3.5 minutes Deep white fixation Fi:h 33°C 1.5 minutes Water Washing 28-35°C 3.0 minutes Interchange N a 2 S O32-O
g KBr 0.5
g Hydroxylamine & IL chutai! ! 3.0g4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamide) ethyl-p-phenylenediamine sulfate 5.OgN a 2
C03 (I water salt) 30 g Add water to make 1 liter (pH 1O, 1) 1 blood 1 j Ammonium thiosulfate (70%) 150.0 m Na 2 SO 315 g NH (Fe (EDTA)) 55 g EDTA
2.2Na 4. Add Og wood to 1 liter (pH 6,9) After the above treatment, blue,
A characteristic curve (D-1ogE curve) was determined using a self-recording densitometer using a green and ljt color filter. The results are shown in Table 3. The color purity in Table 3 is the DC of busenta color development when exposed to white light.
=1. From the values of DB and DR at O, the formula (DB +D
R/DC). The meaning is the same as in Example 1. Also, ΔD■1n(DG
) indicates the increase in D■in when the sample was left at 50° C.-80% for 7 days under high temperature and high humidity. As can be seen from Table 3, while the pyrazoloazole couplers have much better color purity than the 5-pyrazolone couplers, they have an undesirable high Dmin. On the other hand, by combining a specific pyrazoloazole coupler included in the scope of the present invention and an additive, it is possible to lower Dmin and obtain desirable photographic properties without decreasing sensitivity. Example 3 Undercoat on a cellulose triacetate film support subjected to
A multilayer color photosensitive material consisting of each layer having the following composition was prepared and designated as Sample 301. 1st layer: Antihalation layer Black colloid J 0.25g/rn' Ultraviolet absorber U-10.24g/m' High boiling point' 2nd PF+: intermediate layer compound H-10,05g/rn' gelatin layer containing high point organic solvent 0-2 0-05cc/m' (dry film thickness 1end) 3rd layer: 1st red Sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 f: IIM" 0.5 g/nf (Iodine content: 4 mol%, average grain size: 0.3 μ) Coupler C-10, 25 g/m' Gelatin layer containing high boiling point organic solvent 0-2 0, 12 cc/rn' (dry film thickness l) 4th layer: 2nd red-sensitive emulsion layer I?I-sensitive dye S-1 and S-2 spectrally sensitized silver iodobromide emulsion ffi-.0.8 g/d (Iodine content M2.5 mol%, average grain size 0.55 final) Coupler C-10,70 g/rn Gelatin layer containing 'high melting point organic solvent 0-20, 33cc/rn' (dry film thickness 2.5l) 5th layer: Intermediate layer compound H-10,1g/rn' High melting point, high melting point Gelatin layer containing organic solvent 00.1 cc/m' (dry film thickness 1 g) 6th layer: First green-sensitive emulsion layer #? Silver iodobromide spectrally sensitized with sensitive dyes S-3 and S-4 Emulsion silver ω...0.7 g/ba (Iodine content M-3 mol%, average grain size 0.3%) Coupler C-20, 35 g/high boiling point 41 solvent 0-20, 26 cc/rn' Gelatin layer containing (dry film thickness 1 final) 7th layer: 2nd &j emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 1.o, 7 g/m (2.5 mol% of iodine joints, average particle size 0.81 L) Power!5- C-20,25 g/rn' Gelatin layer containing high boiling point organic solvent 0-2 0.0 cLce/rn' (
Dry film thickness 2-5 #L) 8th layer: Intermediate layer compound 0+ H-10,05 g/m'n boiling point organic solution 1110-20, 1 g/rn' gelatin layer (dry film thickness 1 end) 9th layer: Reconnaissance filter → Reconnaissance colloidal silver 0.1 g/go compound
H-20.05g/rn' High boiling point organic solvent 0-2 0
．． Gelatin layer containing 04cc/ba (dry evJV! final) 1st Q layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 jljM=0.6 g/rn' ( Iodine content M2.5 mol%, average particle size 0.full) Coupler C-30.5 g/rn' Gelatin layer containing high boiling point organic solvent 0-2 0.1 cc/rn' (dry film thickness 1.51 L) 11th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 1M...1.1 g/rn' (Iodine content 2.5 mol%, average grain size 1.2) Coupler C-31,2glrrl Gelatin layer containing high boiling point organic solvent 0-20, 23cc/rn' (dry film thickness 3 ends)! RI2W: ff1l protection W UV absorber U-10, 11g/rrf UV absorber U
-20,29g/rrf high Buddha point organic solvent 0-1 0,
Gelatin layer containing 28cc/gold (dry film thickness 2#L) 13th layer: Fine grain silver iodobromide emulsion covered with the surface of the second protective layer Silver 1t--0.1g/rrr' (Iodine content 1 mol% , average particle size 0.061L) Gelatin layer containing polymethyl methacrylate particles (average particle [1.5 pots) (dry film thickness 0.8 final) In addition to the above composition, each layer contained gelatin hardening agent H-3. , and surfactants H-4 and H-5 were added. The compounds used to prepare the samples are shown below. -I U-2 r) 14 II (JlI CH2 Award CH30□CH2C0NHCH2CH2=CI
(So□C1(2CONI(CI+2-I +1-5 Na03S CHCOOCH2CH(C2H5)C4H
BCH2COOCH2CH(C2H5)C4HgTest sample 1 prepared as above was designated as sample number 301, and this was used as a comparative sample thereafter. Next, as shown in Table 4, coupler C-2 and coated silver in the PJ17 layer were changed so that sample 30 had almost the same gradation.
2,303 were produced. These Test Samples 4 were subjected to white wedge exposure and developed according to the following steps. Table 4 shows the results measured with a Fuji concentration meter FAD type. Process: Temperature first development 6 minutes 38℃ water washing
2 minutes 11 reversals 2
Minutes // Color development 6 minutes
/l adjustment 2 minutes l/bleaching 6 minutes
! / Fixation 4 minutes /
Wash with water for 4 minutes
constant 1 minute normal wet dry
The composition of the drying treatment liquid used is as follows. Water 70
0mNitrilo-N,N,N-) rimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monosulfone) 30g Sodium carbonate (-hydrate)
30g 1-phenyl-4methyl-4-hydroxymethyl-3pyrazolidone 2g potassium bromide 2.5g potassium thiocyanate
1.2g potassium iodide (0.1% soluble m)
ZmJL Add water looo
m-bun tile cover water 70
0m nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 3g Tin chloride (di-salt) Igp-7
Minophenol O, 1g Sodium hydroxide 8g Hydroacetic acid
Know everything about 15m water exchange 100
0m Bun Moxibustion Sj Water 7
00rnlNitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Sodium tertiary phosphate (
I2 water source) 36g potassium bromide
1g potassium iodide (0.1% solution) 90m
Sodium hydroxide 3g Citrazine r-&1,5 gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-7minoaniline/sulfur P&salt 11g3.6-cythiaoctane-1.8-diol 1g add water
1000m alternating JL liquid water 70
0m Ilk Sodium Karate 12g
Sodium ethylenediaminetetraacetate (double salt) 8g Thioglycerin 0.4m Bunhyochu resistant
Add 3mm ice water
1000m intersection is breathtaking 80
0g Sodium ethylenediaminetetraacetate (2 11 ml) Add 2g Iron (m) ethylenediaminetetraacetate Ammonium (double salt) 120g Potassium bromide 100g Water
loooom Mitsada Goyaki 80
0m sentence thio&! Sodium L 80.0g
Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000m friendship water 8
00m Also formalin (37%) 5.0m
Also, add Fuji Drywell (Fuji Film Co., Ltd. S8! Superactive Agent) 5.0mM wood, and the magenta color purity (DR+DB)/DG i1 definition at 1000m intersection 4 is ¥Example 1 and Young It's different. Macbeth Color Checker Color Rendissi, 7-Chart (The M
acbeth Color
Rendition Chart)? Made by Kubes
The magenta color all' obtained by shading 1 m was calculated using the values of DR, Dll, and 0G measured using the Macbeth density j1. Also, in the case of reversal processing, the fog in the seventh layer that occurs in the first developing bath is as follows. When all processes are processed, it appears in the image as a decrease in DC DBax (color development - reduction), so D is used as a measure of fog.
wzag (DC) was used. Further, the degree of increase in first development fog when the coated film was left for 3 days (3d) at 45° C. and 80% RH was expressed as the value of ΔD++Iax (DC). In addition, moist heat (
ΔD period i
It is shown as the value of n (DB). As can be seen from Table 4, the undeveloped [J+ sample has a negative effect on sensitivity and T51 development fog without impairing the one-color purity or the characteristic of having little stain due to wet heat treatment! It can be seen that it is possible to improve the storage stability of raw film over time. Example 4 Paper support laminated on both sides with polyethylene] 2-1
Next, photosensitive layers consisting of the first layer to the seventh layer were coated to prepare a silver halide color photographic material. The polyethylene on the side coated with the first layer contains titanium dioxide and a fine ultramarine blue. (Structure of Photosensitive Layer) The numbers corresponding to each component are expressed in units of g/rn' and indicate the amount of coating, and for silver halide, the number indicates the calculated coating weight of silver. 1st layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (silver bromide 80 mol%) Silver 11 0.30 Yellow coupler (015) - Fight 0.70 Solvent (T N P) ・...0.15 gelatin
・Curn φ・1.20 2nd layer (middle layer) Gelatin φ・・−0.90 Gt−
Octylhydroquinone-・Q・0.05 times 1; Solvent (DBP)・・Φ・o, t. 3rd layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (bromide ff170 mol%)...φ silver 0.4
5 Magenta coupler (Book 11) --- 0.35 Same as above solvent (TOP) ... ψ 0.44 Antifading agent (Book 97 Wood 10) ... 0.05/Q, IQ Gelatin ・-ψ- 1,00 4th layer (
UV absorption intermediate H) UV absorber (end 41/wood 427 pieces 2) - 0.06
10.2510.25 Same as above solvent (TNP) ---0.20 G and mono-octylhydroquinone ---0,05 Same as above solvent (D B P) ...-0,10 Gelatin Fist... Prefecture 1. 50th 5th F+(
Red-sensitive emulsion layer) Silver chlorobromide emulsion (silver bromide 50 mol%) - Silver 0.20 Cyan coupler (Ki 437 Zero 44) φ... 0.2010.20 Same solvent as above (TNP/DBP) - -0,1010,20 Gelatin ・Fist・Fist 0.90 6th layer (
UV absorbing intermediate JF? ) Ultraviolet absorber (Book 41 / Tree 427 Tree 2) @,, 0.06
10.2510.25 Same as above Solvent (D B P) ... 0.20 Gelatin ・Φ ・1,50 7th layer (protective layer) Gelatin ・・Φ ・1.50 Here,
DBP is dibutyl phthalate. TOP is tri(n-octyl) phosphate, TNP
represents tri(n-nonyl)phosphate. (Book 41) (Book 42) (Book 43) (r (Book 44) The following dyes were used as spectral sensitizers in each emulsion layer. Blue-sensitive emulsion layer; (Addition of 2 ,) Green-sensitive emulsion layer; (Addition of 2.5 x 10-' mol per 1 mol of halide tM,) Red-sensitive emulsion layer; (Addition of 2.5 x 10-' mol per 1 mol of halide jl,) Prevention of irradiation in each emulsion layer The following dyes were used as dyes: Green-sensitive emulsion layer: Red-sensitive emulsion layer: This silver halide color photographic light-sensitive material was designated as Sample 401. Next, the same process was carried out except for the changes shown in Table 5. Samples 402-405 were prepared.
) After applying mA light for sensitometry, development processing was carried out according to the following processing steps. The results are shown in Table 5. Processing process Temperature Time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ 1 minute 30 seconds Water a 24-34
℃ 3 minutes dry 80℃
The components of each 1 minute treatment solution are as follows. Color developer water 8
00m diethylene triamine pentavinegar 1%j 3.
0g benzyl alcohol 15m diethylene glycol Ion sodium sulfite 2.0g potassium bromide
0.5g potassium carbonate 3
0.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-7minoaniline sulfate 5.0g hydroxylamine fEI'l salt 4.0g optical brightener (4,
4'-distilpene type) Add 1.0g water and heat at 1000mip1000℃')
10.10 Bleach-fix solution water 4
00m Ammonium crossthiosulfate (70% solution) 150m Sodium crosssulphite 18g Iron ethylenediaminetetraacetate (m) Ammonium 55g Ethylenediaminetetraacetic acid/2Na 5g Add water
1000m pH (25℃)
6.70 The definition of magenta color purity in Table 5 is the same as in Example 1. Further, ΔDmin (DB) showed that the yellow stain in the white background area of the print after the development process ff increased at 60° C.-70%-6 weeks F for the prints produced by moist heat. As can be seen from Table 5, the sample according to the present invention can obtain favorable photographic properties (brightness of color, less fogging over time, less moxibustion blur in prints) without causing a relative decrease in sensitivity. I understand.

Claims (1)

[Scope of Claims] A silver halide color characterized by containing at least one pyrazoloazole coupler represented by the following general formula (I) and at least one compound represented by the following general formula (II) Photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Za and Zb are ▲There are mathematical formulas, chemical formulas, tables, etc.) or =N-, and R^1 and R^2 are hydrogen It represents an atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. When Za=Zb is a carbon-carbon double bond, It may be a part of an aromatic ring, and R^1, R^2 or X may form a dimer or more multimer, provided that at least one of R^1 or R^2 One represents a group bonded to the pyrazoloazole nucleus via a secondary or tertiary carbon, and R^1 or R^2 contains at least one -NHSO_2- group.) General formula (II) ▲Mathematical formula, chemical formula , tables, etc. ▼ (In the formula, R^3 is a substituted or unsubstituted alkyl group,
represents an aralkyl group, alkenyl group, aryl group or heterocyclic residue, and X is O, S, Se or NR^4(R
^4 represents a substituted or unsubstituted alkyl group, aralkyl group, alkenyl group, aryl group, or heterocyclic residue;
may be the same as or different from R^3). Q represents an atomic group necessary to form a 5- to 6-membered heterocycle, and may be fused. )