JPH01186941A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color formability by processing a silver halide color photographic sensitive material contg. specific compds. by a color developing soln. contg. an arom. primary amine color developing agent and contg. at least one kind selected from specific hydrazines and hydrazides after exposing. CONSTITUTION:The photosensitive material contg. a silver chloride emulsion in at least one layer and contg. the pyrazolone magenta coupler expressed by formula I is processed, after exposing, by the color developing soln. contg. the arom. primary amine color developing agent and at last one kind selected from the hydrazines and hydrazides expressed by formula II. In formula, R<11> denotes an anilino group, carbonamide group, sulfonamide group or ureido group; R<12> denotes a phenyl group; R<1>-R<3> denote a hydrogen atom, alkyl group, aryl group or heterocyclic group; R<4> denotes a hydrogen atom, hydroxy group, hydrazino group, etc.; X<1> denotes a divalent group; (n) denotes 0 or 1. The color formability is thereby improved.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a development processing method that causes significantly less variation in photographic properties. (Prior Art) In recent years, in the photographic processing of color photographic materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work. Common methods for shortening the time of each treatment step include increasing the temperature, increasing the amount of replenishment, increasing the concentration, etc., but there are other methods such as increasing stirring or adding various accelerators. Many proposals have been made. In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions have been developed in place of conventionally widely used silver bromide emulsions or silver chlorobromide emulsions. There are known ways to treat it. For example, International Publication No. WO 37-04534 describes a method for rapidly processing a high silver chloride color photographic material with a color developer substantially free of sulfite ions and indyl alcohol. (Problem to be Solved by the Invention) However, a high silver chloride color photographic material using a 4-equivalent 5-pyrazolone magenta coupler represented by general formula (1) as a magenta coupler was rapidly processed with the above color developer. However, it was found that the color development of the magenta layer deteriorated and the balance of the three layers was disrupted. The main cause of this is the decrease in color development due to black and white development due to the N,,N-dialkylhydroxylamine contained as a preservative in the color developer, and this effect is noticeable in the special e and magenta layers. It seems that it was Therefore, we used magenta couplers in conventional silver chlorobromide emulsions, which have higher coloring properties than the above-mentioned 4-equivalent 5-pyrazolone magenta couplers, U.S. Pat. No. 3,227,554, U.S. Pat.
No. 3, Japanese Patent Publication No. 53-34044, and Japanese Patent Publication No. 1987-61-
Although the treatment was carried out under the above conditions in place of the 5-pyrazolone magenta coupler described in No. 2, No. 122,646, the color development was rather worse. In particular, it was found that when continuous processing was performed, changes in color development and sensitivity were significant. This is probably due to some interaction between the 2-equivalent 5-pyrazolone magenta coupler and the high silver chloride emulsion. Furthermore, benzyl alcohol, which has conventionally been added for the purpose of improving coloring performance, is added to the above color developer to produce a high chloride steel color photographic material containing a magenta coupler represented by formula (1). When processed, the color development performance was certainly at a satisfactory level, but the capri increased significantly, and this tendency became even more pronounced during continuous processing. In order to suppress this capri, sulfite ion, which is a competitive compound for the developing agent, was added, but no significant reduction in capri was observed, and instead only a decrease in coloring performance occurred. Furthermore, benzyl alcohol
Because sulfite ions are harmful to pollution and on the plate, and because sulfite ions cause significant fluctuations in photographic properties during continuous processing, these two ions should not be used in color developers for processing high-silver chloride color photographic materials. It is not preferable to add it. As described above, a high-silver chloride color photographic light-sensitive material containing a magenta coupler represented by the formula (1) can be rapidly processed without deteriorating its color development, and furthermore, it has excellent photographic properties even during continuous processing. It has been desired to develop a processing technology with significantly less fluctuation. (Means for Solving the Problem) As a result of various studies, the present inventors have found that the object of the present invention can be effectively achieved by using the following means. That is, a silver halide color photographic photosensitive material having at least -11 silver halide emulsions consisting essentially of silver chloride on a support and containing at least one type of pyrazolone magenta coupler represented by the following formula (R). After exposure, the material is processed with a color developer containing an aromatic primary amine color developing agent and containing at least one selected from hydrazines and hydrazides represented by the following formula (II). This is a method for processing a silver halide color photographic light-sensitive material, characterized by the following: General formula (1) (wherein, R11 is an anilino group, a carbonamide group, a sulfonamido group), or a urey group, and R12 is a phenyl group. (represents a group) General formula (It) In the formula, R, R and R each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R4 represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group. basis,
It represents an aryl group, a heterocyclic group, an alkoxy group, an alkoxy group, a carbamoyl group or an amine group, Xl represents a divalent group, and n represents 0 or 1. However, R5-
When Q, R4 represents an alkyl group, an aryl group or a heterocyclic group. R and R may jointly form a petero ring. The details of the magenta coupler represented by formula (1) will be explained below. In the formula, R11 represents an anilino group, a carbonamide group, a sulfonamide group, or a ureido group, and R represents a phenyl group. R11 and R may be further substituted, examples of which include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, t-octyl group, todenyl group, trifluoromethyl group). groups), alkenyl groups (e.g. allyl group, octadecenyl group, etc.), aryl groups (e.g. phenyl group, p-tolyl group, naphthyl group, etc.), alkoxy groups (e.g. methoxy group, benzyloxine group, metquinethoquine group, etc.), -ruoxy group (e.g., phenoxy group, 2,4-di-tart-amylphenoxy group, 3-tart-butyl-4-hyroxyphenoquine group, etc.), acyl group (e.g., acetyl group, indiyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, toluenesulfonyl group), carboxy group, sulfo group, anano group, hydroxy group, amine group (e.g., amino group, dimethylamino group, etc.), carbonamide group (e.g., acetamide group, trifluoroacetamide group) , tetradecaneamibi group, benzamide group, etc., sulfonamide group (
For example, methanesulfonamide group, hexadecanesulfonamide group, p-)luenesulfonamide group, etc.), alkoxy group (91J, acetoxy, etc.), sulfonyl oxy7
groups (e.g., methanesulfonyloxy group, etc.), alkoxycarbonyl groups (e.g., dodecyl oxine carbonyl group, etc.)
, aryloquine carbonyl group (e.g., phenoquine carbonyl group, etc.), carbamoyl group (e.g., dimethylcarbamoyl group, tetradecylcarbamoyl group, etc.), sulfamoyl group (M, t, methylsulfamoyl group, hexadecylsulfamoyl group, etc.) ), 9 imide groups (e.g., sukunimibi group, phthalimide group, 1 octadecenyl succinimide group, etc.), heterocyclic groups (2-pyridyl group, 2-furyl group, 2-thienyl group, etc.), alkylthio groups (e.g., methylthio group) etc.), arylthio groups (for example, phenylthio groups, etc.). Either R or H may become a divalent or higher polyvalent group to form a multimer such as a divalent body, or a polymeric form can be formed by linking the polymeric main chain and the coupler core. A coupler may also be formed. It is also known in the art that the coupler represented by formula (1) has the following keto-enol tautomerism. Examples of the compound represented by the general formula (1), synthesis method, etc. are disclosed in JP-A-49-111631 and JP-A-54-485.
40. 55-62454, 55-118034, 56-38043, 56-80045, 56-12
6833, 57-4044, 57-35858, 57, 94752, 58-17440, 58-50
537, 58-85432, 58-117546,
58-126530, 5B-0145944, 5
8-205151. Tokuko Sho 54-170, Sho 54-1
0491. 54-21258, 53-46452,
53-46453, 57-36577, JP 60-2953, 60-23855, 60-17085
4, U.S. Patent No. 3227554, U.S. Patent No. 3432521, U.S. Patent No. 4
310618, 4351897, etc. Examples of preferable compounds among the 5-pyrazolone 4-monomer magenta couplers represented by the formula 0 will be shown below, but the invention is not limited thereto. fL H3 H3 OF'3 CH3 (I-11) (t-13) 3C/7-60/40 (Wt) x/y-50150 (wt) (a! (I-27) Cft t C Emperor I CH3 rt 0 dishes 0 dishes 1 Two or more types of couplers of the present invention may be contained in the same layer.The same compound may be contained in two or more different layers.The couplers of the present invention are generally used for each mole of silver in an emulsion layer. Hit 2
X 10-3 mol to 5 X IO-" mol,
Preferably from 2 mol to 5 x 10
−1 mole is added. When used in combination with the above couplers, it is preferable that the total amount of the couplers that develop the same color is within the above range. In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalate alkyl esters (such as cy/tylphthalate, dioctyl phthalate), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), ), benzoic acid esters (e.g. octyl benzoate), alkylamides 9 (e.g. diethyl laurylamide 9). Fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), or boiling points of about 30
After dissolving in an organic solvent at a temperature of 150°C to 150°C, for example, lower alkyl acetate such as ethyl sulfate, butyl oxalate, ethyl zolopionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59943
It is also possible to use the polymer dispersion method described in . When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Photographic emulsions made using the present invention may contain color image-forming couplers other than those of the present invention. The coupler is preferably a non-diffusive coupler having a hydrophobic group called a ballast group in its molecule. - The compound of general formula (1) used in the present invention, that is, the hydrazine analog consisting of hydrazines and human 9 radides, will be explained in detail below. 8% R

[and R are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 20,
For example, methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, phenethyl group, etc.), substituted or unsubstituted aryl group (preferably 6 to 20 carbon atoms, for example phenyl L2. 5-dimethoxyphenyl group, 4-human90
xy7yl group, 2-carboxylic phenyl group) or a substituted or unsubstituted heterocyclic group (preferably 1 to 20 carbon atoms, preferably 5 to 6 negative rings, with oxygen, nitrogen, sulfur as the hetero atom) (eg, pyridin-4-yl group, N-acetylpiperidin-4-yl group, etc.). R4 represents a hydrogen atom, a hydroxy group, an unsubstituted human 9-radino group (e.g., hydrazines, methylhuman 9-radino group, phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably 1 to 20 carbon atoms) , for example, methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, t-butyl group, n-octyl group, etc.), substituted or unsubstituted aryl group (preferably carbon Number 6-20
For example, phenyl group, 2,5-dimethoxyphenyl group. 4-hydroxyphenyl group, 2-carboxyphenyl group, 2-carboxyphenyl group, 4-sulfophenyl group, etc.), substituted or unsubstituted heterocyclic group (preferably 1 to 20 carbon atoms, preferably 5 to 6 members) A ring containing at least one of oxygen, nitrogen, and sulfur as a hetero atom (for example, pyridin-4-yl group, imidazolyl group, etc.), a substituted or unsubstituted alkoxy group (preferably 1 to 20 carbon atoms) ．For example, methoxy group, ethoxy group,
methoxyethoxy group, benzyloxy group, cyclohexyloxy group, octyloxy group, etc.), substituted or unsubstituted aryloxy group (preferably 6 to 20 carbon atoms, such as phenoxy group, p-methoxyphenoxy group, p-carboxyphenyl group, p -sulfophenoxy group), substituted or unsubstituted carbamoyl group (preferably 1 carbon number)
~20, such as non-monosubstituted carbamoyl group, N,N-diethylcarnodimoyl group, phenylcarbonyl group, etc.)
! ? , : is a substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, such as an amino group, a hydroxyamino group, a methylamino group, a hexylamino group, a methoxyethylamino group, a carboxylethylamino group, a sulfoethylamino group) , N-7 enyla ξ) group, p-sulfophenylamino group). Further substituents for R1, R2, R3 and R include halogen atoms (chlorine, bromine, etc.), hydroxyl groups, carboquine groups, sulfo groups, amino groups, alkoxy groups, amide 9 groups, sulfo/amide groups, carbamoyl groups. , sulfamoyl group, alkyl group, aryl group, arylthio group, alkylthio group, arylthio group, nitro group, cyano group, sulfonyl group, sulfinyl group, etc., which may be further substituted. Xl is preferably a divalent organic residue, such as -〇〇-,, -8o2-1 and -C
-, n is O or l. However, when n=O, R4 represents a group selected from substituted or unsubstituted alkyl groups, aryl groups, and heterocyclic groups. R and R
and R and R may jointly form a heterocyclic group. When n is O, at least one of R'' and R' is preferably a substituted or unsubstituted alkyl group. In 41, R'', R2, R3 and R are hydrogen atoms, or substituted or unsubstituted alkyl groups. It is preferable that (However, R% R and R% R are never hydrogen atoms at the same time.) Especially when R, R and R3 are hydrogen atoms and R4 is a substituted or unsubstituted alkyl group, %R and When R is a hydrogen atom and R and R are substituted or unsubstituted alkyl groups, or when R and R are hydrogen atoms and R and R are substituted or unsubstituted alkyl groups (in this case R3 and R4 may jointly form a heterocycle) is preferred. In the case of nml, -CO- is preferable as Xi,
R4 is preferably a substituted or unsubstituted amino group, and R and R are preferably substituted or unsubstituted alkyl groups. More preferably, n is 0. The alkyl group represented by R1-R4 preferably has 1 to 10 carbon atoms, and more preferably has 1 to 10 carbon atoms.
~7. Further, preferable substituents for the alkyl group include a hydroxyl group, a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group. When there are two or more substituents, they may be the same or different. The compound of general formula (1) may form a bis body, a tris body, or a polymer connected by R, R% R, R. Specific examples of the compound represented by the general formula (■) are listed below, but the present invention is not limited thereto. (II-t) (II-2) CHNHNHCH3 (II-3) (II-4) (It-5) (It-6) (II-7) (II-s) HOOCCH2NHNHCH2COOH (It-9) NH2NHSo0H2iN Station H2 (u-10) NH2NHCH2CH20)1 CH (II-12) Nu2NH-(CH2)3-8o3)! (![-13) NH2NH-(CH2), -8o3H (II-14) NH2NH-(CH2) 3-Gool(II-15) (II-16) (u-17) (II-18) CHCH3 (II -19) NH2NHCH2CH2COONa (II-20) Nu2NHCH2COONa (II-21) H2NNHCH2CH2So3Na (II-22) C4H, (II) H2NNHCHCOOH (II-23) 06H13(II) H2NNHCHCOO H (II-24) C4H9(IIl 1(2NNsoCHCOOH ) 2 (u-25) H2NNsoCH2CH2SO3Na ) 2(II-2
6) H2NN%CH2CH2CH25o3Na) 2(I
I-27) 2H5 H2NNeCHCOOH) 2 (II-28) CH3 H2NNHCHCOOH (II-30) (II-31) (II-32) (CH2-N-CH2CH2CH2 Average molecular weight approximately 4,000 (II-33) x :y=60:40 Average molecular weight Approximately 20,000 (...-34) NH,NHCONH2 (II-35) NH NH2NHCNH2 (II-36) NH2N)ICONHNH2 (...-37) Nu2NH803H (II-38) NH2NH8O2NHNH2 (u- 39) OH3NHNH8O□N11NHCH8(It-40) NH2NHCONH-(CH2)3-NHCONH2H
2 (…-41) (…-42) NH2NHCOCONHNH2 (II-43) (II-44) ([[-45) (…-46) NH2COCONHNH2 (fl-47) (II-49) (II-so) ( II-51) (II-52) (II-53) (II-54) (U-SS) (...-56) (II-58) (II-59) NaO3SCH20H21cNHNH2 (...-61) HOOCCH2CM2NHCNHNH2 (II-62 ) (II-63) NH2NHCOOC2I(5 (II-64) N) (2NHCOOC)I3 (It-66) NH2NHCII2PO3H2 (II-68) (II-69) (II-70) (■-72) (It-73 ) (CH3) 3CCONHNH2 (...-74) (CH3) 3COCNHNH2 (II-75) (II-76) (■-77) (II-78) CH2GOOR (II-79) (II-so) HOCH2CH2SO□NHNH2 (■ -81) NaO3SCH2CH2CONHNH2(II-82) H2NOONHCH2CH2So□NHNH2(II-
83) (II-84) (II-85) H2NNHCH2CH2PO3H2 (...-86) H 1 + CM2NCH2CH crucible H2 Specific -J other than the above is patent application No. 61-170756
No. 61-171682 specification-1t pages 12-22, No. 61-173468 specification v
Examples of the compounds described on pages 9 to 19 can be mentioned. Many of the compounds represented by the general formula (1) are available as commercial products, and "Organic 5 syntheses J, C
o11°Vox, 2. pp 208-213;
Jour, Amer. Chim, Soa, 36.1747 (1914); Oil Chemistry. 24 e 31 (1975); Jour-Org
-Chem 6 #Main 5.44 (1960); Pharmaceutical Journal, 91.1127 (1971);
e), Co11. Mo1. is p4so;
r New Achievement Chemistry Course”, Volume 14 eL p1621-162
8 (circle '11); B411. I 2.559;B
oil,, 3.117; I, BoMohr
et a'1. . Inorg, Syn, 4.32 (1953):
F, J. Wixaon, E., C., Pickering, J.
, Chem, Soc. 123* 394 (1923); L J, Leona
rd, J. H, Boyer, J, Org, Chem.
15.42 (1950); “Organic 5yn-theass, C
o11. Vol, 5. p 1055; P,
A. S, Sm1th, [Derwaitives of
hydrazine and other hylo
nitrogena having-n-bond
sJ. 1) 120-124. p 130-131; THEB
ENJAMIN/CUMMNGS COMPANY,
(1983); 5taniay R, 5andie
r Waif Karo, [organicFuna
ttonaI Group PraparattonsJ
, Vol. i. It can be synthesized according to the intramembrane synthesis method such as 5econa Altlon, p 457. The amount of the compound of general formula (II) added is as follows: color developer 11
0.019-509, preferably 0.19-30g per
, more preferably 0.5g to 109g. Next, each process will be explained. Color Development The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminecoaniline D-52-methyl-4-[N-ethyl-N-(β-human90xyethyl)′aminocoaniline D-64-amino-3-methyl-N-ethyl −N−(β
-(methanesulfonamide)ethyl-to-aniline D -7N -(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-B N,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline In addition, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, 1)-) luenesulfonate (or, depending on the purpose, two or more types may be used in combination). The amount of aromatic-grade amine developing agent used is preferably from about 0.19 to about 209, more preferably from about 0.19 to about 109, per 11 parts of developer solution. In the present invention, it is preferable that substantially no benzyl alcohol is contained. Substantially means color developer 1fi
This refers to a case in which the content is 2 rat or less, preferably 0.5 or less, and more preferably not at all. It is particularly noteworthy that by not containing benzyl alcohol, it was possible to suppress the increase in magenta capri over time in the color developing solution. Furthermore, in the present invention, it is preferable to substantially not contain sulfite ions because a high Dmax (maximum density) can be obtained and fluctuations in photographic properties during continuous processing are small. The sulfite ion concentration here refers to the concentration of 5032- and/or H3O3 substantially present in the color developer.
It shows the concentration of -, and the concentration can be determined by iodometric titration. The concentration of substantially no content is 5 x 10 mo1/
less than fi, preferably 1x t 0-3n+a1. / Polish It is below. Substantially no sulfite ions are contained, which is preferable because the coloring properties are apparently improved. In addition, as compounds for directly collecting the color developing agent, human 90 xamic acids described in Japanese Patent Application No. 61-18.6559, Japanese Patent Application No. 61-188742 and No. 61-20325 can be used.
Phenols described in No. 3, α-hydroquine ketones and α-aminoketones described in No. 61-188741, and/or various saccharides described in No. 61-180616 may be added. In addition, when used in combination with the above compounds, % Gusho 61-
No. 147823, No. 61-166674, No. 61-1
No. 65621, No. 61-164515, No. 61-17
Monoamines described in No. 0789 and No. 61-168159, No. 61-173595, No. 61-164
Diamines described in No. 515, No. 61-186560, etc. No. 61-165621, and No. 61-16978
Polyamines described in No. 9, polyamines described in No. 61-188619, nitroxy radicals described in No. 61-197760, No. 61-186561, and 61-
Alcohols described in No. 197419, No. 61-1989
Oximes described in No. 87 and tertiary amines described in No. 61-265149 may be added as necessary. Other fecal collection agents include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
It is preferable to use the aromatic polyhydroxy compound described in No. 746,544 in combination. Especially aromatic polyhuman 90oxy compounds, triethanolamine, and patent application 1986-26
Preferably, the compound described in No. 5149 is added. The color developer used in the present invention is preferably...9 to
12, more preferably 9 to 11. The color developer may contain other known development WL acid component compounds. In order to maintain the above-mentioned properties, it is preferable to use various buffering agents. Buffers include carbonate, phosphate, borate, tetraborate, human 90-benzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norloin salt, guanine[,3,4-dihydroquine phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, diphosphorus salt, proline salt, trishydroxyamine methane salt, phosphorus salt, etc. can be used. In particular, carbonates, phosphates, tetraboric acid fumes, and hydroxybenzoates are soluble, p) 19
．． They have the advantage of having excellent buffering ability in the high pH range of 0 or more, having no adverse effect on photographic performance (such as capri) when added to color developing solutions, and being inexpensive. is particularly preferred. Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, potassium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds. The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that the amount is more than 0.1 mol/part, especially 0.1 mol/part to 0.0 mol/part.
Particularly preferred is 4 mol/part. In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 227
, organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55-126241 and No. 55-6595
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-53-40900. Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ・ethylenediaminetetraacetic acid, ・N, N, N-
Trimethylene phosphone, ethylenediamine-N, N
, N', N'-tetramethylenephosphonic acid, ・transcyclohexanediaminetetraacetic acid, ・1,2-diaminopropanetetraacetic acid, ・mericol ether diaminetetraacetic acid, ・ethylenediamine orthohydroxyphenylacetic acid, ・2-phosphonobutane-1 , 2,4-) recarboxylic acid, ・l-hydroΦethylidene-1,1-diphosphonic acid, φN, N'-? (2-Hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary. The amount of these chelating agents added depends on the metal ion in the color developer. For example, it is about 0.19 to 109 per i.Any development accelerator can be added to the color developer as necessary.However, the present invention It is preferable that the color developer does not contain benzyl alcohol subtly from the viewpoint of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means 2 d or less per development Mlfi, preferably 2 d or less per development Mlfi. This means that it does not contain it at all. The foregoing compounds used in the present invention provide significant benefits in processing steps using color developers that are substantially free of benzyl alcohol. Other development accelerators include: Japanese Patent Publication No. 3/7-16088
No. 437-5987, No. 38-7826, No. 44
-12380, No. 45-9019 and U.S. Patent No. 3
, 813,247, etc.; JP-A-52-49829 and JP-A-50-15554;
p-phenylenediamine-based compounds represented by No. JP-A-50-137726, JP-B No. 44-30074,
Quaternary ammonium salts shown in JP-A-56-156826 and JP-A-52-43429, etc., U.S. Pat.
, No. 494,903, No. 3.128,182, No. 4,
No. 230,796, No. 3.253,919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2,482,546,
Amine compounds described in Japanese Patent Publication No. 2,596,926 and No. 3,582,346, Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128,183
Polyalkylene oxy P1 shown in Japanese Patent Publication No. 41-11431, No. 42-23883, U.S. Patent No. 3,532,501, etc., l-phenyl-3-pyrazolidones, imidazoles, etc. as required. [Can be added. In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. As an organic anti-capri agent. For example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylincitriazole, 5-nitrobenztriazole, 5-chloro-benzo) IJ 7zole. 2-Thiazolyl-benzimidazole% Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostyrine compounds are preferred. The amount added is O~5971, preferably 0.19~4
9/Katsu. Further, various surfactants such as dialkyl sulfonic acid, alkyl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary. The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the replenishment amount is small, but preferably 20 to 600 pp per 1 m2 of photosensitive material.
0 to 300 successions. More preferably 100#d to 20
It is 0116. Next, the desilvering step in the present invention will be explained. The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. In the present invention, the effect of the present invention becomes more significant when the process time of the desilvering step is shortened. That is, it is 2 minutes or less, more preferably 15 seconds to 60 seconds. Desilvering process The bleaching solution, bleach-fixing solution, and fixing solution used in the desilvering process will be explained. Used as a bleaching agent in bleach solutions or bleach-fix solutions.
Any bleach can be used, but especially iron (
2) organic complex salts (for example, complex salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids) or citric acid, tartaric acid,
Organic acids such as malic acid; persulfates; hydrogen peroxide and the like are preferred. Among these, organic complex salts of iron(2) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or their salts useful for forming organic complexes of iron (IID) include: ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1,3-diamino Mention may be made of propanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, etc. These compounds include sodium, potassium, lithium or ammonium salts. Any of these compounds may be used. Among these compounds, iron complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in the liquor by combining the above with a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, amino, t<IJ carboxylic acid iron complexes are preferred, and the amount added is from 0.01 to 1.0 mol/day, preferably from O,OS to 0.50 mol/Q. Various compounds can be used as cleaning accelerators in bleach solutions, bleach-fix solutions and/or their prebaths. For example, U.S. Pat.
-95630 Publication, Research Disclosure No. 1
No. 7129 (July 1978 issue), compounds having a mercapto group or disulfibi bond, and
-8506, JP-A No. 52-20832, JP-A No. 53-3
Thiourea compounds described in No. 2735, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties. In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, rum, ammonium chloride) or May contain rehalogenating agents such as iodides (e.g. ammonium iodide); optionally boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate. ,citric acid,
One or more inorganic acids, organic acids, and their alkali metal or ammonium salts having a buffering capacity such as citric acid, tartaric acid, etc. Corrosion inhibitors such as ammonium nitrate and guanidine can be added. The fixing agents used in the bleach-fix solution or fixing UK according to the present invention are known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; Thioglycolic acid, 3.6-cythia 1
, 8-octanediol, etc., and water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-56-155354 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per plate is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. The range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9. Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.)% metabisulfite (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/J2, more preferably 0.04 to 0.40 mol/J2. Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added. Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary. Aqueous solution and/or stabilization In the treatment of the present invention, aqueous solution and/or stabilization treatment is generally performed after desilvering treatment such as fixing or bleach-fixing. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and other various conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method was determined by the Journal of the Society of Picture and Television Engineers.
alof the 5oiety of Motio
n Picture andtelevislon E
ngineers) Volume 64, p248-253 (19
You can request it using the method described in the May 1955 issue. Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.
In particular, 2 to 4 is preferable, and if the 1° multistage countercurrent method is used, the amount of washing water can be greatly reduced, for example, 0.5fi-1fi or less per 1 m2 of photosensitive material, and the effect of the present invention is remarkable. . The increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium content described in Japanese Patent Application No. 131632/1988 can be used in a particularly effective manner. Also, patent IF5
Chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles described in No. 57-8542, and chlorinated sodium isocyanurate described in No. 61-120145. Benzotriazole, copper ion, etc. described in Patent Application No. 105487/1987, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi, "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" by Sanitation Technology Society, Japan Antifungal Antifungal It is also possible to use the fungicides described in the Society W4 "Encyclopedia of Antibacterial and Antifungal Agents." Further, in the washing water, a surfactant as a water cutting agent and a chelating agent represented by IDTAK as a water softener can be used. The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound represented by formalin, a buffer for adjusting the membrane thickness suitable for dye stabilization, and an ammonium compound. In addition, in order to prevent the growth of bacteria in the liquid and to impart anti-fungal properties to the photographic material after processing, the above-mentioned various bactericides and anti-mold agents can be added. Furthermore, surfactants, fluorescent brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is achieved directly without passing through the water washing process, JP-A No. 57
-8543, 58-14834, 60-22034
All known methods described in No. 5 and the like can be used. In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds. In the present invention, a so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment. ... in the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 15 to 45°C, preferably 20 to 40°C. Although the time can be set arbitrarily, the effect of the present invention is more pronounced as the time is shorter, preferably from 30 seconds to 4 minutes, and more preferably from 30 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater. A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. or 11 or less per m2 of photosensitive material,
Preferably it is 500- or less. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which is reduced by a multi-stage countercurrent system, into the bleach-fix bath of the 70-year bath, and replenish the bleach-fix bath with concentrated liquid to reduce the amount of waste liquid. . The method of the invention can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but application to color paper and color reversal paper is particularly preferred. Next, details of the silver halide color photographic light-sensitive material processed in the present invention will be explained. The light-sensitive material processed according to the present invention must contain a variety of color couplers. The term "color coupler" as used herein refers to a compound that generates dye fire upon coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (December 1978).
It is described in Section 1-D and the patent cited in 18717 (November 1979). The yellow and cyan color couplers incorporated in the light-sensitive material are preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is preferable to a two-equivalent color coupler in which the coupling active position is a hydrogen atom, since the amount of coated silver can be reduced and the effect of the present invention is large. Diffusive couplers, non-color forming couplers, DIR couplers that inhibit development and emit etchants upon coupling reaction, or couplers that release development accelerators can also be used. A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2,875,057 and No. 3
, No. 265, 506, etc. In the present invention, it is preferable to use a yellow coupler, which is disclosed in US Pat. No. 3,408,194, US Pat.
Same No. 3,933,501 and No. 4,022,62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326,024, RD1
8053 (a nitrogen atom separation type yellow coupler described in 1979 No. 2,329,587 and 1979 No. 2,433,812) is a typical example. Couplers have excellent color fastness, especially light fastness, and α-inzoylacetanilide couplers can provide high color density. Examples of magenta couplers that can be used in combination include oil-protected intasolone-based or cyanoacetyl-based couplers, preferably 5-pyrazolone-based and male lazoloazole-based couplers such as pyrazolotriazoles. 5-2 lazolone-based couplers A coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. , No. 703,
No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896
No. 3,936,015, etc. The leaving group for the two-equivalent 5-pyrazolone coupler may be the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. preferable. Furthermore, the 5-pyrazolone coupler lacking a ballast group described in European Patent No. 73,636 provides high color density. As a pyrazoloazole coupler, U.S. Patent No. 3,
The pyrazolo described in U.S. Pat. 1
pyrazolotetrazoles described in Research Disclosure 24230 (June 1984), and may be used in combination as necessary. Imidazo(1,2-b)pyrazoles described in European Patent No. 119,741 are preferable from the viewpoint of low yellowing absorption and light fastness of coloring pigments, and pyrazolo compounds described in European Patent No. 119,860 are preferable. (1
, 5-1) (1,2,4)) Riazole is particularly preferred. Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293 and preferably U.S. Pat. No. 4,052.
, No. 212, No. 4,146,396, No. 4,22
Typical examples include the oxygen reactor demolded two-equivalent naphthol couplers described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 01,171, No. 2,772,162, No. 2,
No. 895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
Phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Patent No. 2,772,162 and No. 3,75
No. 8,308, No. 4,126,396, No. 4.3
No. 34.011, No. 4,327,173, West German patent publication! No. 3,329,729 and patent application 1986-426
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 71, etc., and U.S. Pat.
No. 2, No. 4,333,999, No. 4,451,5
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 59 and No. 4,427,767. In the present invention, if necessary, 4-equivalent yellow and cyan couplers may be used in combination, and a coupler in which the coloring dye has an appropriate diffusivity may be used in combination to improve graininess. Such dye-diffusive couplers are described in U.S. Pat. No. 4,366,237 and British Pat.
Specific examples of magenta couplers are given in European Patent No. 96,570 and West German Patent Publication No. 3, 125,570.
No. 234,533 describes specific examples of yellow, magenta or cyan couplers. The dye-forming couplers and specialty couplers described above may be polymeric fire-forming which is dimeric or higher. A typical series of polymerized dye-forming couplers is disclosed in U.S. Patent No. 3,451,82.
No. 0 and No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82. The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in combination with different couplers in the same compound. It is also possible to introduce more than one layer. Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 10.0 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Patent No. 2,322,027.
It is written in the number etc. Also. The process, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. No. 4,199,363, West German Patent R.
No. 541,230, etc. Next, the silver halide color photographic material used in the present invention will be explained in detail. The silver halide emulsion of the present invention consists essentially of silver chloride. Substantially silver chloride means that the content of silver chloride relative to the total amount of silver halide is 90 moles or more, preferably 95 moles or more, and more preferably 98 moles or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable. Further, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. This can be useful in many ways in terms of photosensitivity, such as increasing the amount of light absorption, strengthening the adsorption of spectral sensitizing dyes, or weakening desensitization caused by spectral sensitizing dyes. When the silver halide emulsion contains silver bromide or silver iodide, it may have a so-called core-shell structure. The shape of the silver halide used in the silver halide emulsion may be cubic, octahedral, tetradecahedral, rhombic dodecahedral, or spherical. Preferably it is a cube or a tetradecahedron. In addition, the grain size of silver halide is 0.15 to 1
．． 4μ current is preferred. The size distribution may be narrow (or wide), but monodisperse is preferable.In particular, the dispersion coefficient is 2.
It is preferably 0% or less, more preferably 15% or less. Cad9mium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, etc. may be allowed to coexist in the process of grain formation or physical ripening of silver halide. good. In particular, the iridium salt or its complex salt is preferably 10-9 to 10-4 mol per mol, more preferably 10-1 mol, based on silver halide.
″″8 to 10 −5 mol 1 mol is used. This is particularly useful in obtaining rapid developability and stability at high or low illuminance outside the appropriate no-light illuminance range, compared to emulsions prepared without using iridium salts or complex salts thereof. The photographic emulsion used in the present invention is described in Research Disclosure Y-(RD) vol, 170 Item
*Section 17643 (1, n, 11) (December 1978)
It can be prepared using the method described in . The emulsion used in the present invention is usually physically ripened. Use those that have been chemically ripened and spectrally sensitized. Additives used in such processes are described in Research Disclosure Vol. 176, 417643 (January 1978).
(February) and Vol. 187, Mu 18716 (November 1979), and the relevant sections are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below. Additive type RD17643 RD187
161, chemical sensitizers page 23 64
Page 8 right column 2 Sensitivity enhancer
Same as above 3 Spectral sensitizer pp. 237-24
Page 648 right column ~ 4 Supersensitizer
Page 649 Right Column 5 Brighteners Page 24 6 Antifoggants and Stabilizers Pages 24-25 Page 649 Right Column 7 Coupler Page 25 8 Organic Solvents Page 25 9 Light Absorbers,
649 Right column - Filter dyes pages 25-26 650 Left column 10 Ultraviolet absorbers l] Stain inhibitors Page 25 Right column 65
Page 0 Left to Right Column 12 Pigment-faced Ishi-Kiyaku 25
Page 13 Hardener Page 26 Page 651 Cotton 1 Fuku Binder Page 26 Same as above 15 Plasticizer% Lubricant Page 27 650 Right column 16
Coating aid, surfactant, pages 26-27 Same as above 17
Static top coat agent 27Jr
The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. be done. For details on the support and coating method, please refer to Research Disclosure R-176.
17643 Section XV (P. 27) Section X4 (P. 28) (December 1978 issue). In the present invention, a single reflective support is preferably used. A "reflective support" is a material that increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support. The light-sensitive materials used in the present invention include color paper, color reversal R-par, direct positive color paper, and various other color light-sensitive materials. (Example) Example-l Table A was placed on a paper support laminated on both sides with polyethylene.
Create multilayer color photographic paper with the layer structure shown in Figure 9. The coating solution was prepared as follows. 19. Yellow coupler (a) for preparation of coating liquid for layer-19. 27.2 ml of ethyl acetate and the solvent [(7.9-) were added to 4.49 and dissolved, and this solution was mixed with a 10% aqueous gelatin solution containing 10 sodium tidodecylbenzenesulfonate Brrtt. 185rR1. On the other hand, the blue-sensitive sensitizing dye shown below was added to a solid silver bromide emulsion (1 mole of silver bromide, containing 4 to 70 g of Ag) at a concentration of 5.0 x 10" per mole of silver chlorobromide. 90g of the blue-sensitive emulsion was prepared by adding molar to it.The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to the composition shown in Table A/4 to prepare the first layer coating solution. Coating solutions for layers 2m to 7 were also prepared in the same manner as the coating solution for layer 1. As a gelatin hardener for each layer, 1-oxy-3,5-
Dichloro-8-triazine sodium salt was used. The following spectral sensitizers were used in each emulsion. Blue-sensitive emulsion layer (halogen (t [1 mol) 5.OX 10-' mol m
+) Green-sensitive emulsion layer 5O3HN(C2H5)3 (4.OX l O-' mol m per 81 mol of halogenide)
A) So3IN (02H5)3 (Hao /F' per mole of silver ionide?, OX 10-
Red-sensitive emulsion layer The following dyes were used as irradiation prevention dyes in each emulsion layer. The structural formulas of the compounds used in this example, such as the coupler in the green-sensitive emulsion layer and the red-sensitive emulsion layer, are as follows. (a) Yellow coupler D (C) Solvent ldl Color mixing inhibitor H (6) Magenta coupler See Table 1 (f) Color image stabilizer (g) 2:1 mixture of solvents (weight ratio) (!1) Ultraviolet absorption 1:5:3 mixture of agents (molar ratio) (1) Color mixing inhibitor lj) Solvent (tso 08H1,0h-P-0 (k) l:1 mixture of cyan coupler C (molar ratio) (1) Color Image stabilizer C, H8(t) 1:3:3 mixture (molar ratio) (m) Solvent The following experiment was conducted to investigate the photographic properties of coated samples with these modified magenta couplers. First, the coated sample was exposed to a sensitometric scale through a green filter using a photosensitive needle (Fuji Photo Film Co., Ltd. back F'WH model, color temperature of the light source 3200'Kl).
4 exposures were given. The exposure at this time was carried out for an exposure time of 1710 seconds so that a brightness of 250 M5 was obtained. Next, in the processing steps shown below, processing is performed by changing the composition of the color developer as shown in Table 1.
), and the gradation ('I! from the point representing 0.5 degrees, f
/, density change up to the density point on the high exposure side of 0.3 in OgE)
was measured using a Fuji self-recording densitometer. Furthermore, each color developer rL5fi was heated to an aperture ratio of 1×10 at 35°C.
-2(S/V
&t (cm3), S is the area of the opening (cWL2))
) for 6 weeks, and the color photographic paper was treated in the same manner. Processing using the color developer (aged solution) that has been left for the past 8 weeks.
The treatment using was used as a fresh liquid test. The photographic properties obtained through the fresh liquid test and the aged liquid test were evaluated as
Shown in the table. The processing steps are as follows. Processing process Temperature Time Color development 35℃ 45 seconds Bleach fixing 35℃ 45 seconds stable ■
Stable at 35℃ for 20 seconds■
Stable at 35℃ for 20 seconds■ 35
℃ Stable for 20 seconds ■ 35℃
Dry for 30 seconds at 80℃
60 seconds (stable ■ → ■ 4-tank countercurrent force type) The composition of each treatment solution is as follows. color developer water
800d ethylenediaminetetraacetic acid
2.09 Additive A (compounds of the present invention, etc.)
See Table 1 Benzyl alcohol
(See Table 1) IJum
See Table 1 Sodium chloride
1.49 diethylene glycol
1QaJ potassium carbonate 2
59N-Ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate 5.09 Triethanolamine 8.095.6
-Syhydroxybenzene-1.2.4-) Lysulfonic acid 0.3g
Fluorescent brightener (add 4,4'-diaminos water 1000a/
pi ((25℃) 10.1
0 bleach-fix water 40
0114 Ammonium thiosulfate (70%)
1001117 Sodium sulfite
189 Iron ethylenediaminetetraacetate (m) Ammonium 559 Disodium ethylenediaminetetraacetate Add 3g water 100011up
H (25°C) 5.5 Stabilizer 5-chloro-2-methyl-4-isothiazolin-3-one 0.0292-
Add 0.01 of methyl-4-isothiazolino-3-one to 0.0059 of copper sulfate and add 1QQQaA! …
(25°C) 4.0 *1: Comparative magenta coupler (M-I) Cl Comparative magenta coupler (M-mouth) Cl However, when using M-I and M-B, the amount of silver in the green-sensitive layer is 0. 16
9/m2. Table 1 shows that when a color developer other than the present invention is used, the D can and gradation are lower, the color development is inferior, and J)=
and large gradation changes (/161~4 and 7f65~
18 comparisons). According to the present invention, the fluctuations in the above photographic properties are reduced, and the effect is more pronounced in the absence of sulfite and benzyl alcohol.
,49. and Comparison of Mu 19-28). Example 2 Color photographic papers A to F were prepared in the same manner as in Example 1 except for changing the magenta coupler in the color photographic paper prepared in Example 1 as follows. Sample A: Magenta coupler M-i (see Example 1)/
/B: // M-mouth (〃)“ C:
“Knee 24” D: “Knee 26 // E, // l-27〃 F:
〃 Knee 30 For each of samples A-F after imagewise exposure of each upper period sample,
The composition of the color current gR solution was changed and running was performed in the following steps. The processing steps are as follows. The amount of treatment per day was 15 m each, and the treatment was carried out for 30 days. Color development 35℃ 45 seconds 14 Qat1
7 fi bleach fixing 35℃ 45 seconds 215
+11117fi water washing ■ 35℃ 20 seconds
-10 wash ■ 35℃ 20 seconds
10fi water washing ■ 35℃ 20 seconds
2001M! 10-part drying 80°C 60 seconds *per 1 m" of photosensitive material (4 tanks countercurrent flow method from water washing to ■) The composition of each processing solution is as follows. Water 800
at 800d ethylenediaminetetraacetic acid
2.09 2.095.6-Sihydroxybenzene-1.2.4-trisulfone i! ! 20.39
0.39 triethanolamine
8.09 8.09 Sodium chloride
1.49 - potassium carbonate
259 259N-ethyl-N-(
β-Methanesulfonamidoethyl)-3-methyl-4-
Aminoaniline sulfate 5.09
7.09 Compound B of the present invention 2nd
Refer to the table Fluorescent brightener (add 4,4'-diamino water to 1000 at
1000ralp)l (25℃)
10.05 10.45 Bleach-fix solution (tank solution and replenisher solution are the same) water
400d ammonium thiosulfate (
70%) 1001d Sodium sulfite 17g Ethylenediaminetetraacetic acid (iron) Ammonium 559 Disodium ethylenediaminetetraacetate 5g
Add water 1000
d...(25℃) Water washing (tank fluid and replenishment fluid are the same) Ion exchange water (calcium, magnesium each 3pp1
(Below) Continuous processing (running test) is performed until the color developer tank capacity - [(1711) is refilled three times as much. It was conducted under each condition. Each color photographic paper was then exposed to light through an optical wedge and processed at the start and end of the running process. Then, we set Δ5O15*ΔDw and Δgradation as shown below. Δ86,5: Change in logarithm value (So, s) of the exposure needle that gives a magenta density of 0.5 before and after running. ΔD-Increase in D- at the end of the run relative to f)m at the start. Δgradation 2 The increase in magenta density in the gradation area at the end of running compared to the magenta density in the gradation area at the start of running. In addition, comparison! For zenta couplers (M-i) and (M-mouth), see Example 1. The photographic characteristics of the above magenta at the start and end of the running last are shown in Table 2. From Table 2, in the comparative example, color developer additive (
When N,N-diethylhydroxylamine is used as compound B), there are large changes in ΔS0, 5#ΔDsw, and Δgradation, and even when the compound described in the present invention is used as compound B, there are When a magenta coupler is used, the change in ΔSo, s is particularly large.However, it can be seen that if the configuration of the present invention is followed, good results can be obtained (the range surrounded by 'FW). Example 3 When the same procedure as in Example 1 was carried out using Magenta Coplany 25 instead of Magenta Coplany 27 used for Fu 7 in Example 1, favorable results were obtained. Patent Attorney (8107) Kiyotaka Sasaki Procedural Amendment April 1, 1986

Claims (1)

[Claims] (1) A silver halide color containing at least one layer of a silver halide emulsion consisting essentially of silver chloride on a support, and containing at least one type of pyrazolone magenta coupler represented by the following general formula (I). After exposure, the photographic light-sensitive material is processed with a color developer containing an aromatic primary amine color developing agent and at least one selected from hydrazines and hydrazides represented by the following general formula (II). A method for processing a silver halide color photographic material, characterized in that: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1^1 is an anilino group, a carbonamide group,
Represents a sulfonamide group or ureido group, R^2
represents a phenyl group. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1, R^2 and R^3 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^4 represents a hydrogen atom, hydroxy group, hydrazino group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group, X^1 represents a divalent group, and n is 0 Or represents 1. However, when n=0, R^4 represents an alkyl group, an aryl group, or a heterocyclic group. R^3 and R^4 may jointly form a heterocycle.