JPS60162256A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To increase color developing density by processing a silver halide color photosensitive material contg. one or more of the 4-mercapto-5-pyrazolone magenta coupler expressed by the specific formula with a developing soln. contg. benzyl alcohol. CONSTITUTION:A silver halide color photosensitive material contg. one or more of the 4-mercapto-5-pyrazolone magenta coupler expressed by the formula I (W denotes an aryl group, X denotes an alkyl group, aryl group or heterocyclic group, Y denotes an acylamino group, ureido group or anilide group, respectively) is processed with a color developing soln. contg. 2-8ml/l benzyl alcohol. The above-described silver halide color photosensitive material is applicable to all of color photographic materials such as a color negative film, color paper, color positive film, etc. followed by a color developing process.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application in CM Industry) The present invention relates to a method for processing silver halide color light-sensitive materials, and more particularly to a method for processing silver halide color light-sensitive materials with improved color developer and excellent color development.

(Prior Art) Various measures have been taken to speed up color development. Among them, color developing agents have low hydrophilicity, so their penetration into the sensitive material is slow.
To speed up this process, various penetrants have been investigated, especially:
The method of accelerating color development by adding benzyl alcohol to the color developer has a great effect on promoting color development.
At present, it is widely used for processing color photographic materials, especially color bases.

However, when benzyl alcohol is used in an amount of lθml/II to trwt/II or more, which is the amount commonly used for color paper processing, due to its low water solubility, diethylene glycol, triethylene glycol, In addition, alkanolamines are required, but benzyl alcohol, glycols, alkanolamines, etc. have low pollution load values such as BOD and CO.
Since D is high, it is desirable to reduce the amount of benzyl alcohol used for the purpose of reducing the pollution load.
If the amount used is less than ttt/11, the solvent is no longer necessary, and the pollution load can be significantly reduced.

Furthermore, when benzyl alcohol is brought into the bleach bath, which is a bath after the color development bath, or the bleach-fixing bath, it causes the formation of leuco dye of cyankazolar, which reduces the color density of the cyan dye, and furthermore, If it is carried into the post-bath rinsing water, the storage stability of the color image will be deteriorated. Therefore, for this reason as well, it is preferable that the benzyl alcohol concentration in the color A image solution be as low as possible.

However, benzyl alcohol (lktit 1ml)
/l or less, the coloring density of magenta dye in particular is significantly reduced, and various color developer accelerators (for example, U.S. Pat. No., same, 4A ri 6.ri 03, same 2.3θ≠, ri 2
No. j, same≠, o3r,.

7! Same issue! , //F, 4 (JJ issue, British time Fj'F/
.

<J
T! -G 2hiroj No. 1, 77-A, 24tj No., same! ! -42≠j3, special public Akira! /-/2gu/2gu samer
Even when s-≠972 (compound described in the above issue) was used in combination, sufficient color density could not be obtained.

(Object of the Invention) The object of the present invention is to provide a color developing solution in which the total concentration of benzyl alcohol is significantly reduced, and also to provide a color photographic photosensitive material which can obtain sufficient color density and has excellent color fading resistance. The purpose of the present invention is to provide a processing method.

(Structure of the Invention) As a result of numerous studies, the present inventors found that μm mercazoto! - The above objective is effectively achieved by processing a silver halide color light-sensitive material containing at least one type of pyrazolone-type magenta cazoler with a color developer containing co-Izl/l of benzyl alcohol. I discovered that.

It was completely unexpected that by containing the following magenta coupler, the benzyl alcohol concentration could be reduced and its solvents, diethylene glycol and alkanolamine, could be removed.

Furthermore, none of the many known magenta couplers can be used, and none of the many known co-equivalent magenta couplers can be used, but the magenta couplers represented by the general formula C7) of the present invention can be used. This was achieved for the first time using a magenta coupler.

General formula ([) In the formula, W represents an aryl group, X represents an alkyl group, an aryl group, or a heterocyclic group, and Y represents an acylamino group, a ureido group, or an anilino group.

Next, general formula (1) will be explained in detail. W represents a phenyl group or a naphthyl group substituted with at least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, or cyano group.

The alkyl group represented by X is a straight chain with carbon number/-172,
It represents a branched alkyl group, alkenyl group, cycloalkyl group, aralkyl group, or alkynyl group, and these represent a halogen atom, hydroxy, mercapto group, cyano group,
Nitro group, carboxyl group, aryl group, alkoxy group, aryloxy group, heterooxygen group, aralkyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, silyloxy group, carbamoyloxy group, phosphoric acid group, acylamino group , sulfonamide group, alkoxycarbonylamino group, aryloxycarbonylamino group, diacylamino group, carbamoylamino group, sulfamoylamino group, aromatic heterocyclic group such as pyrazolyl, imidazolyl, triazolyl, piperidino group, morpholino group, Non-aromatic heterocyclic groups such as imide groups, pyridone, monooxo nitrogen heterocyclic groups such as saccharin, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups,
Silyl group, alkylthio group, arylthio group, hetero-thio group, sulfonyl group, alphinyl group, anilino group,
etc. may be replaced.

The aryl group represented by X is a phenyl group or a naphthyl group having t-hirot carbon atoms, and these may be substituted with the substituents mentioned in the substituents for the alkyl group in addition to the alkyl group.

Furthermore, the peterocyclic group represented by X is a j-membered to j-membered heterocyclic group containing a nitrogen atom, an oxygen atom, and a sulfur atom singly or simultaneously, and may be fused with a benzene term. Typical heteroterminal skeletons include the following.

■Mo□ 几 几L2 (In the formula, 几 represents a hydrogen atom, an alkyl group, or the same substituent as mentioned above for the substituent of the alkyl group, and 几2 represents a hydrogen atom, an alkyl group, an aryl group. group, acyl group, alkylsulfonyl group, arylsulfonyl group.) The acylamino group represented by Y represents an alkanamide group with a carbon number of l-≠2, a benzamide group with carbon atoms a6 to The group represents an alkylureido group having 1-carbon atoms or a phenylureido group having t to ≠6 carbon atoms, and the anilino group represented by Y represents a phenylamino group having 6 to ≠6 carbon atoms. These alkyl groups may have the same substituents as mentioned above for the alkyl group of X, and the phenyl group may have the same substituents as mentioned for the alkyl group of X above. The substituent may be .

Among the ≠-mercapto j-pyrazolone type cassolers represented by the general formula (1), particularly preferred couplers are those represented by the general formula (
II) and (II).

General formula (■) General formula (Iil) In the formula, Ar represents a phenyl group substituted with at least one halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cyano group, and Z is a halogen atom, or represents an alkoxy group, 几 is a hydrogen atom,
Halogen atom, alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, 7-acylamino group, alkoxycarbonyl group,
Represents an alkoxysulfonyl group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, an alkyloxycarbonylamino group, a ureido group, an acyl group, a nitro group, or a carbonyl group. represents a halogen atom, hydroxy group, amino group, alkyl group, alkoxy group, aryloxy group or aryl group, R5 is a hydrogen atom, amine group, acylamino group, ureido group, alkoxycarbonylamino group, imide group, sulfonamide basis,
represents a sulfamoylamino group, a nitro group, an alkanesulfonyl group, a carbamoyl group, an acyl group, a cyan group, an alkylthio group, and ■ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group; At least one of kL4 and 几 represents an alkoxy group, m represents an integer of 1 to 3, and n represents l-≠
represents an integer of 1 to 3, and l represents an integer of 1 to 3.

Further, R7 represents an alkyl group or an aryl group, and k
L8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an aryl group, a,
b represents an integer of l and j, respectively.

More specifically, Ar is an Arfi-substituted phenyl group, and the substituents include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), a carbon number of 1 to 22
alkyl group (e.g. methyl group, ethyl group, tetradecyl group, t-decyl group, etc.), alkoxy group having 2 to 2 carbon atoms (e.g. methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), carbon alkoxycarbonyl group of several λ to co3 (e.g., methoxycarbonyl group,
(ethoxycarbonyl group, tetradecyloxycarbonyl group, etc.) or cyan group.

To explain X in more detail, X is... a rogen atom (
(for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), or an alkoxy group having l-λ carbon atoms (for example, a methoxy group, an octyloxy group, a dodecyloxy group, etc.).

To explain kL3 in more detail, ① is a hydrogen atom, a halogen atom (for example, a chlorine atom, a hydrogen atom, a fluorine atom, etc.), an alkyl group (for example, a methyl group, a t-decyl group, a comethanesulfonamide ethyl group, a t -butanesulfonylethyl group, tetradecyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, coethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g. acetamido group, benzamide group, butanamide group, tetradecaneamide group) , α-(2,≠-di-tert-amylphenoxy)acetamide group, α-
(2,≠-di-tert-amylphenoxy)butyramide group, α-(3-pentadecylphenoxy)hexanamide group, α-(≠-hydroxy-J-tert-butylphenoxy7)tetradecanamide group, co-oxovirolidine -l-yl group, λ-oxo! -tetradecylpyrrolidin-/-yl group, N-methyl-tetradecanamide, α-(3-methanesulfonamidophenoxy)tetradecanamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octane sulfonamide group, p-dodecylbenzenesulfonamide group, N
-methyl-tet97”cansulfonamide group, etc.),
Sulfamoyl group (e.g., N-methylsulfamoyl group, N-subsilsulfamoyl group, N (J()
"decyloxy)-furovir]sulfamoyl group, N-
(4'-(2,44-di-1ert-7milfe,noxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl s
(Example tt, f, N-methylcarbamoyl group, N-octadecylcarnogmoyl, 4, N-' [Hiro-(ko, Hiro-
di-tert-amylphenoxy)phthyl]carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-1-cuccinimide group, N
-phthalimide group, co, j-dioxo-/-oxazolidinyl group, 3-dodecyl-λ,! -dioxo7-hydantoynyl L3-CN-acetyl-N-)"decylamino)succinimide group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxysulfonyl group, base/l/oxycarbonyl group,
), alkoxysulfonyl groups (e.g., methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, nato), aryloxysulfonyl groups (e.g., phenoxysulfonyl group, λ, 4t-
Sheet-tert-amylphenoxysulfonyl group, na(!
: ), alkali/sulfonyl groups (e.g. methanesulfonyl group, octanesulfonyl group, coethylhexanesulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (Horomiba, benzenesulfonyl group, F
-/nylbenzenesulfonyl group, etc.), alkylthio group (e.g., ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, co(co, 4L-dit)
ert-amylphenoxy)ethylthio group, etc.), arylthio group (e.g. phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino group (e.g. eva, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyl oxycarbonylamino group, etc.), ureido group (e.g., N-methylureido group, N-phenylureido group, N,N-dimethylureido group, N-methyl-N-dodecylureido group, N
-hexadecylureido group, N,N-dioctadecylureido group, etc.), acyl group (e.g. acetyl group, benzoyl group, octadecanoyl group, p-dodecaneamide (nzoyl group, etc.), nitro group, or carboxy However, among the above substituents, the number of carbon atoms defined as an alkyl group is /-112, and the number of carbon atoms defined as an aryl group is 6 to μt.

To describe 几 in more detail, R4 is a no-rogen atom (
For example, chlorine atom, bromine atom, etc.), hydroxy group, amino group (substituted or unsubstituted 1-mino group, N-alkylamine group, N,N-dialkylamino group, N-anilino group, N-alkyl- N-arylamino group, represents a heteroaryl amino group, such as 1N-butylamino group, N,N
-dibutylamino 4, N, IQ-diacyl amino group, N
-piperidino group, N, N-bis(2-dodecyloxyethylamino 5, JN-cyclohexylamino group, N-
Phenylamino 4, N *N-bis(,2-hexane sulfonylethyl) amino group, S > alkyl group (represents a straight chain, branched chain alkyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, for example,
Methyl group, butyl group, octyl group, dodecyloxy group,
benzyl group, cyclopentyl group, coptansulfonylethyl group, 3-phenoxypropyl group, etc.), alkoxy group (e.g. methoxy group, butoxy group, benzyloxy group, coethylhexyloxy J1 dodecyloxy group, λ-methanesulfonylethyl group) group, coptansulfonylethyl group, inpropiseoxy &, x-chloroethyl group, 3-(co2μm di-tert-amylphenoxy)propyl group, λ-(N-methylcarbamoyl)ethoxy group, cyclopentyloxy group, coethoxytetra Decylox 7 groups, p, 4A, Hiroshi, 3.J, 2..2-
Hebutafluorophthyloxy M, 3- (N-futhyl n,
Carpamoya) zorobyloxy group, 3-CN, N-dimethylcarbamoyl) zorobyloxy group, goomethanesulfonylbutoxy group, coethanesulfo/amide ether group\, etc.), aryloxy group (e.g., phenoxy 7 group, 2
．． II-dichlorophenoxy group, etc.) or an aryl group (substituted or unsubstituted phenyl group, α- or β-naphthyl group having t to 3 g of carbon atoms, for example, phenyl group, α
- or β-su7tyl group, Hiro-chlorophenyl group, 4'
-4-butylphenyl group, methanesulfonamidophenyl group, co≠-dimethylphenyl group, WJ), lL5 is a hydrogen atom, an amino group (substituted or unsubstituted amino group, N
-alkylamino group, N, N-dialkylamino group, N
-anilino4, N-alkyl-N-arylamino group,
Represents a heteroaryl amine group, such as N-butylamino group, N,N-jethylamino group, N-(co(co, gooey tert-amylphenoxy)ethylcyamino group, N
, N-dibutylamino group, N-piperidino group, N, N-
Bis-(2-dodecyloxyethyl)amino group, N-cyclohexylamino group, N,N-di-hexylamino group, N-phenylamino group, co,≠-di-tert-amylphenylamino group, N-( +2-chloro-!-tetradecanamidophenyl)amino group, N-methyl-N-phenylamino group, N-(corbiridyl)amine group, etc.)
, acylamino group (e.g., acetamido group, benzamide group, tetradecanamide group, (2,≠-di-ter
t-amylphenoxy)acetamide group, cochloropenzamide group, 3-pentadeshabenzamide group, j
-(j-methanesulfonamidephenoxy)dodecaneamide group, j-(j-chloro1gophenoxy)tetradecanamide group, etc.), ureido group (e.g., methylureido group, phenylureido group, l-cyanophenylureido group, etc.), alkogyacarbonylamino groups (e.g., methoxycarbonylamino group, dodecyloxycarbonylamino group, coethylhexyloxycarbonylamino group, etc.), imide groups (e.g., N-succinimide group,
N-7 talimide group, N-hydantoinyl group,! ,! −
dimethyl-co#hiro-di-dioxoxazol-yl group, 'N-(J-octadecenyl)succinimi group, etc.)
, sulfonamide group (e.g. methanesulfonamide group, octanesulfonamide group, benzenesulfonamide group, ≠-chlorobenzenesulfonamide group, Hiro-dodecylbenzenesulfonamide group, N-methyl-N-benzenesulfonamide group, ≠- dodecyloxybenzenesulfonamide group, hexadecane sulfo/amide group, etc.),
Sulfamoylamino group (e.g., N-octylsulfamoylamino group, N,N-disolopyrsul7amoylamino group, N-ethyl-N-phenylsulfamoylamino group, N-(<z-fthylox7)sulfamoylamino group, famoylamino group, etc.), nitro group, alkoxycarbonyl group (
For example, methoxycarbonyl group, butoxycarbonyl group, dotesyloxycarbonyl group, benzyloxycarminyl group, etc.), carbamoyl group (Horomiba, N-octylcarbamoyl group, N,N-diythylcarbamoyl M, N
yenylcarbamoyl group, N = (J-(J, u-tert-amylphenoxy)furoyl]carbamoyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, hexanoyl group, coethylhexanoyl group) ,
cochlorobenzoyl group, etc.), cyano group, alkylthio group (e.g. dodecylthio group, coethylhexylthio group, benzylthio group, cooxocyclohexylthio group, co(ethyltetrazocaate)thio group, co(
(dodecylhexanoate) thio group, 3-phenoxyzolopylthio group, codedecanesulfonylethylthio M, etc.) tjsi! I, 几, are hydrogen atoms, hydroxy groups, or R.

It represents the same alkyl group, alkoxy group, or aryl group as mentioned above, and at least one of the groups represents an alkoxy group.

Further, 几7 represents the same alkyl group or aryl group as described in 几4, and 几 is a hydrogen atom or 几. Halogen atoms, alkyl groups, alkoxy groups similar to those mentioned above,
Represents an aryl group.

Next, maze/represented by the general formula CI) used in the present invention
Specific examples of Takazotsu are listed below, but the invention is not limited thereto.

Tol (:t M-J α α M-li-j α −4 M-// M-tz α M-/l Δ4-/ri α M-coco U211°M-37 octi3 Magenta used in the present invention The coupler can be synthesized based on the methods described in, for example, Japanese Patent Publication No. Sho J3-3≠O≠≠, Japanese Patent Application Laid-open No. Sho! J-6211Jμ, U.S. Patent No. 3.701.713, etc. .

These couplers are generally present in an amount of 2X/(7 moles to z×io moles, preferably /
×lQ moles to jXio-'' moles are added.

Two or more of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required for photosensitive materials,
Of course, the same compound may be added to two or more different layers.

In order to introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. For example, 7-taric acid alkyl esters (dibutyl 7-talate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl 7-mole 7-ate, tricresyl phosphate, dioctyl phtyl phos 7-ate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl resuccinate, diethylase V-
)),) rifsinate esters (e.g. tributyl trimesate), or boiling point of 300C to tsooc
is dissolved in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl zoropionate, secondary butyl alcohol, methylinobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. be done. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

The benzyl alcohol used in the present invention contains from 1 to 1, preferably from 3 to A ml per color developer i.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples include p-phenylenediamine derivatives. Representative examples are shown below, but the invention is not limited thereto.

D-/N,N-diethyl-p-phenylenediamine D-2co-amino-j-diethylaminotoluene D-3,2-amino-! -(N-ethyl-N-y urilamino)toluene D-≠ goo [N-ethyl-N-(β-hydroxyethyl/I/)amine] aniline D-3-monomethyl-≠-[N-ethyl-N -(β-hydroxyethyl)amino]aniline 1)-tN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-guaminoaniline D-7N-(,2-amino-j-diethylaminophenyl ethyl) methanesulfonamide D-r N,N-dimethyl-p-7 22 diamine D-2 Hiro-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10≠-amino-3-methyl- N-ethyl-N-β
-Ethoxyethylaniline D-1/4A-amino-3-methyl-N-ethyl-N-
β-Ethoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, salivary sulfate, and p-toluenesulfonate. The above compound is disclosed in US Pat.
．． olj issue, 2.112.

λg No. 1, same, jt&, No. 27/, same 2. jdeco,
374 (No. 3.6jjp, No. 9!0, No. 3゜621
, j2! It is stated in the number etc. The amount of the aromatic-grade amine developing agent used is from about 0.1 to about 20.0 it per liter of developer solution.
y, more preferably a concentration of about o, s1 to about 10f.

As is well known, the color developer used in the present invention preferably contains hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The color developer used in the present invention preferably has a pH of ~is, more preferably de~ti, o, and may contain other known developer component compounds. can.

For example, alkaline agents, p)it agents include caustic soda, caustic potash, soda carbonate, potassium carbonate, tribasic sodium phosphate, tripotassium phosphate, potassium metaborate, borax, etc., used alone or in combination.

In addition, for the purpose of imparting laxative ability, for formulation convenience, or to increase ionic strength, it may be added to Various salts are used, such as alcohol, alkali nitrate, and alkali sulfate.

In addition, various calcium chloride agents can be used in the color developer to prevent precipitation of calcium and magnesium. Examples include polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, l-hydroxyalkylidene, l-diphosphonic acids, and the like.

Any development accelerator can be added to the color developer if necessary. For example, US Pat.

i7i, various pyrimidylam compounds represented by Ko≠7 and other calaonic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 4'≠-230ψ, U.S. patent Ko, No. 333.9YO, same.

531, Za No. 32, same 2. riSO, No. 270, λ,!
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 77.127, and thioether compounds described in US Pat.

Additionally, sodium sulfite, sacrificial potassium sulfate, potassium bisulfite, or sacrificial sodium sulfate, which are commonly used as preservatives, can be added.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used. Examples of the If 4'& Camellia inhibitors include benzotriazole, 6-nidrobenzimidazole, j-nitroinindazole, and! -methylbenzotriazole,
! -Nitrobenzotriazole,! - nitrogen-containing heterocyclic compounds such as chlorobenzotriazole, 2-thiazolyl-benzimidazole, cortiazolylmethylbenzimidazole, hydroxyazaindolizine and/or
Mercapto-substituted heterocyclic compounds such as -phenyl-j-mercaptotetrazole, comelcabutobenzimidazo-9, comelcazotopenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

The processing method of the present invention can be applied to any processing of general silver halide color photographic materials such as color negative film, color paper, color positive film, color reversal film, etc., but processing of color paper is particularly preferred.

The silver halide color photographic material used in the present invention is a color negative film or a color developer? -, color positive film, color reversal film, and other color photographic materials that involve a color development step, but color paper light-sensitive materials are particularly preferred.

The emulsion used in the present invention is P, Glafkides.
Author: emie et Physique Photo
graphique (published by Paul Mante1, l
(47 years), G, F'.

Photographic Ernul by Duffin
sionChemistry(Tbe Focal P
Making and Co.
ating Photographic Emulsio
rJ/4 can be produced using the method described in Tbe Focal Press (published by Tbe Focal Press, 2010). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the tjJ-soluble silver salt and the rof-soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. May be used.

It is also possible to use a method in which particles are formed under the presence of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material of the present invention.

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.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see for example “Die Gr.
und lagender Photography
chenProzesse mit 8i1berba
"Logeniden" (Akademische V
erlagsgesellschaft.

Jf) J7j~73≠The method described in the negative can be used.

Namely, the sensitization method uses sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g., total complex salts, pi, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

The true emulsion used in the present invention may contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the photosensitive abrasive, or for stabilizing photographic performance. I can do it. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercazotobenzothiazoles, mercaptobenzimidazole 7s1, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (l-
mercazotovirimidines; mercaptotriazines; thioketo compounds, such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially ≠-hydroxy Substitution (/, J, ja, 7
) tetraazaindene), pentaazaindene; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as further antifoggants or stabilizers can be added, such as benzenesulfonic acid amides.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolane dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these pigments, any nuclei commonly used for cyanine pigments can be used as basic heteroartic nuclei.

Is a useful sensitizing dye, for example, the German patent octopus? , Oto issue,
US time gfi, 23/, Aj1, same.

Iri J, No. 74L♂, same λ, jθ3, 771. No., same ko, j/ri, 001, same λ, ri 12, 32, 3
,1. ! l, rijri issue, same 3. t7 co, tri 7, same 3. t9μ, 2 Noah, same≠, θkoj, 3≠, same≠
, O! 4. J7λ, British patent l.

, 2≠No. 2.3711, Special Publication Show 4tll-/Ifi03
0%, as described in No. 12-2≠r≠≠.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, an aminostilbene compound C substituted with a tricyclic ring group, for example, U.S. Pat. t
3j, 7co No. 1), aromatic organic acid formaldehyde condensates (for example, US Pat. No. 3,7≠J, 5
10), cadmium salts, azaindene compounds, etc. U.S. Patent J, J/, t.

No. 413, 3. t1. ? , 6 Hiro No. 1, 3, 1. /7
1.2ri No. 5, 3, 1, 3! , No. 72/ is particularly useful.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcecilose, cal&-4-dimethylceyalose, and moyalose sulfates; sodium alginate; Sugar derivatives such as starch-conductors;
Various synthetic hydrophilic compounds such as single or copolymers of polyvinyl alcohol, polyhinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrazole, etc. Polymeric substances can be used.

A typical synthetic hydrophilic polymer substance is, for example, the West German patent amount @
C0L8>, 2, 3t2. yor No., U.S. Patent J, Jco 0.71/No. 31g7ri9.2゜5, Special Publication No. 1973
3-7≠61.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color transfer materials usually have a red-sensitive emulsion layer on a support,
and (1) at least one sensitive emulsion layer. The order of these layers can be selected as desired. Usually, the red-sensitive milk A11 layer contains a cyan-forming coupler, the edge-sensitive emulsion layer contains a magenta-forming coupler, and the (2)-sensitive emulsion layer contains a yellow-forming cazoler, but different combinations may be used depending on the case.

The photosensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, melonanine dyes, /anine dyes, and azo dyes. Among them, oxonol dyes; hemioxonol dyes and melonanine dyes are useful.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, US Pat. Kota O
No., same co, Hiroit, t13, same, 47j, J/Hiro no., same, 701゜127, same λ, 70≠, 773, same λ, 7 cot, tjri no., same co, No. 732.300,
Same.

731.76? No., same, 7/θ, 10/, same, t
The hydroquinone rust conductor described in U.S. Patent No. 363.227, etc. ≠3
No. 7.072, same J, 01. Gallic fermentation conductor described in No. Y, etc., US Pat. No. 733.74? No. J, J
Rit, RiOri No., Special Public Show 4tP-koo Ri No. 77, same! 2
-p-Alkoxyphenols described in Atco No. 3, US ♂fj, $32,300, same! , to 7
3, 0jtO issue, same 3. j7 hiro, t core issue, same 3,7
t≠, No. 337, JP-A-Shoj, 2-3! No. 1.33, same-j
Cole Hiro 74t34I- No., same! λ-/62ko2! p-oxyphenol rust conductor described in U.S. Patent No. 3,
There are bisphenols described in No. 700, ≠jj.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. j3.

Al11), benzophenone compounds (e.g., those described in JP-A No. Sho≠A-J7g≠), cinnamate ester compounds (e.g., those described in U.S. Patent No. 3゜701.1r),
Oj issue, 3.707.37? ), butadiene compounds (e.g., those described in U.S. Pat. I can do it. Furthermore, US Patent 3. ≠Tata, 7&
Those described in No. 1, No. 11, Kaisho Sa-≠f, and No. 131 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used.

These ultraviolet absorbers may be mordanted to certain extents.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion. Specific examples of fluorescent brighteners are #! F co, 63 co, 7θ1, 3,2ty, rao, (ifJ3,31?, 10
No. 2, British Patent 112.07? No., same/, J/ri, 7t
It is stated in issue 3 etc.

The photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains dye-forming couplers, that is, oxidation with aromatic primary amine developers (e.g., phenylene diamine derivatives, aminophenol derivatives, etc.) during color development processing. A compound that can develop color upon coupling may also be used. For example, as a magenta coupler! - pyrazolone cazolers, pyrazolobenzimidazo-M couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoyacetanilide 6,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either g-equivalent or co-equivalent to the silver ion.

It may also be a colored coupler having a color correction effect or a coupler (so-called 1)I coupler or DAR coupler that releases a development inhibitor or development accelerator upon development.

In addition to DIkL cazolers, there are also colorless DIs in which the coupling reaction product is colorless and releases a development inhibitor.
It may also contain a coupling compound.

In addition to the coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

Two or more of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required for photosensitive materials,
Of course, the same compound may be added to different co-layers or more.

, as a magenta coupler, it is necessary to contain a compound represented by the general formula, but other U.S. patents,
too,'ytr issue, same λ, ri r3゜toy issue, same 3
．． 0 Otsu λ, 4jλ No. 3,127.269, 3.
3//, $7z issue, same 3゜hiroli, 3ri1 issue, same J,
jt, /ri, ≠ Kota issue, same 3,! ! tl,,3/ri issue,
Same 3. ! 12. J Coco, same 3. tip, rot number, same 3. t3 Hiro, Ri01, same 3. tri/, Hiro≠J issue, West German patent i, tto, pap issue, West German time "'f out JmCO
LS) No. 2,4101.441, same, ≠17. tag j
No. 2゜≠it, vs. ri No. 2, Hiroko Hiro, Hiro 67, Special Publication No. 11O-403r, No. 2012
No. 4, same! λ-try Coco, μtar λ133, #F-74 (0, 27, 30-/J 33, tco axi2i, Hiro Turf 4!).

No. 11, same 3j-2233j, same j / -24j≠7
Same issue! The couplers described in No. 3-jJ'/2 may be used in combination.

As yellow couplers, compounds of the benzoylacetanilide and pivaloylacetanilide series are advantageous. Specific examples of yellow couplers that can be used are in U.S. Patent 2.1.
72r, No. 017, No. 3, 2At, No. 104, No. 72r!
, 4AOI, lli No. 1, same 3゜jj/, 113, same 3. ! Tco, No. 322, No. 3.7 Koj, No. 072, No. 3
, 1ri lgo]! No., West German patent/, j≠7. It No. 1, West German Application Publication Co.

21 Ri, Ri No. 17, 2.261.31.1, 2.
4c/IA, No. 00A, UK 11V License/, 4A2j, 0
．． No. 20, Tokuko Akira! /-10713, JP-A-4A7-
No. 26133, same≠! -737≠7, same jl-10J
tit issue, 10-4341/, same jO-/2331
No. 1, same! 0-1304A≠-No., same! l-coit core issue, same jtO-176,! TO No. 1211
No. 24, No. 52-IIR code, etc. Ic.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

Specific examples include U.S. Patent No. 36, Jikota No. 2, u
34, No. 272, same, 447F, λri No. 3, same 2.
! 1. /, No. 901, same, ryz, r2 No., same 3.
θ3≠, male octopus, same J, 31/, ≠7, same 3
Mamoru SR, 3it issue, same 3. ≠76°, No. 743, same 1.
11r, 3.97/issue, 3,191.313, same j
, No. 747.4A//, Dohiro.

OO≠, Octopus 2, West German patent application (OL8) J.

Reference l≠, ZSO issue, same co, ψj hiro, 322 issue, time opening t1
8at-Zri No. 131, same j/-2403≠, same 41
1-40! ! No., same jt/-1ut No. 121, same 12-
1. Y62 No., same! λ-ta θri No. 3, same! 7-/j
1! No. 31, same! 7-2011j4Aj.

As a colored coupler, for example, U.S. Patent 3°417
&,,! No. 140, 2. ! 2/, Deor issue, same J,
No. 0311.192, Special Publication Sho up-20/l, No. 3
No. j-2233j, Kou Kou / / No. 3011, No. ≠-3ha 11/, Japanese Patent Application Publication No. Shoj/- Kobu θ34A specification, No. J Kou Kou / No. 2/ No. 9, Seidoku 1r1 - Application (ULS) J, +/f, rijFIK description (7) can be used.

1) As an I coupler, for example, U.S. Pat.
7,! j≠ issue, same 3. t/7, 2ri No. 1, same J, 7
0/, No. 713, No. 3, 7 Rio, Jtp No., No. 3
, No. 432.3tljt, West German patent application (OLS),
μ/≠, Oot issue, same co, Hiro! II, No. 30, same λ
, Hiroj≠, No. 32, UK patent 13. ≠j≠ issue!
Japanese Patent Publication No. 32-4942≠, Shikota No. 12233j,
Those described in Tokko Shoj/-/l, /Hiroshi/No. can be used.

1) In addition to the IR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon exposure to the skin. ≠≠J No. 3,37, No. 522, West German Patent Application (OLS) 2.4A/7,
ri l≠ issue, JP-A-Sho, t2-13271, →-[Kai-Sho r
Those described in No. 3-yiit can be used.

The above coupler can also be used as a citron containing two or more yuzu in the same layer.

The same compound may be contained in two or more different layers.

These couplers are generally present in amounts ranging from coxl0-3 moles per mole of silver in the emulsion layer. x 10-" moles, preferably /X/0" moles, 3 l, jXlo" moles are added.

Example 1 A multilayer silver halide color photosensitive material was coated by coating the following first layer (is: lower layer) to seventh layer (uppermost layer) on a paper support laminated on both sides with polyethylene.

12-(cohydroxy-3-8ec-butyl-z-
t-i tylphenyl) benzotriazole screen 2 dibutyl phthalate screen 32-[α-(λ, dag--t-amylphenoxy)
butanamide)-1,4-dichloro-j-methylphenol +42. J-G t-octylhydroquinone side dish 5 Trioctyl phosphate bone 6 α-piparoyl-α-(2, Gudioxo-J,
j-dimethyloxolidin-3-yl)-cochloro-
j-(α-(2,41--di-t-amylphenoxy)
butanamide] acetanilide In addition, as a gelatin hardening agent for each layer, l-oxy-3, j-
Dichloro-8-) riazine sodium salt was used.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps. 1 Processing process Wet layer Time color development 33°0 3 minutes 30 seconds Bleach-fixing at 33°C 7 minutes 30 seconds Water washing λv~31/L0C3 revolution Drying ro 0c Announcement The components of the processing solution are as listed in F.

Color liquid water f 00 @1 Sodium tetrapolyphosphate 2.OY Benzyl alcohol Table 1 Diethylene glycol Table 1 Sodium sulfite λ,oy Potassium bromide 0.If Sodium carbonate 30.0f N-ethyl-N-(β -Methanesulfonamidoethyl) -3 -Methyl-Hiro-aminoaniline sulfonate j, Of Hydroxylamine sulfate 44.Of Add water i
oθ0w1 pH (koz 0<:) 10. o.

Bleach-fix solution water ≠Oθ River Ammonium thiosulfate (70% dissolved *> Izomt Sodium sulfite lzaV Ethylenediaminetetraacetic acid iron (11) Ammonium ssy Ethylenediaminetetraacetic acid, 2Na!? Add water
1000.1 pH (-2j'C) 6.70 After processing with various color developers with varying concentrations of benzyl alcohol and diethylene glycol, the green light reflection density of each sample was measured. The relative sensitivity is the benzyl alcohol concentration of each photosensitive material! #Sensitivity in case of Ie/l is io
It was decided as o.

The results obtained are shown in Table 1.

When using magenta couplers magenta couplers A, C, C, D, E, the color photosensitive material was coated with the amount of silver in the green sensitive layer set to o, 3u 17 m2.

From the results shown in Table 1, according to the present invention, even at a benzyl alcohol concentration of 2 to 1 ml, sensitivity and color development equivalent to those at a benzyl alcohol concentration of 10 tttl/II or more are obtained, whereas in the comparative example, As the concentration of pendyl alcohol decreases, the sensitivity and coloring properties decrease significantly.

Example 2 In the same manner as color developers F and G in Example 1, color developers without diethylene glycol were prepared as 1/, H and ■, respectively. A-1 was left sealed for 2 weeks at ≠θ0C. As a result, oily stains were found in the color developing solution in H and ■, but it was transparent in A to G.

Therefore, it has been found that the solvent is not necessary in the color developer having a concentration of benja alcohol of 0 to 1/l in the present invention, and a color developer with a low pollution load has been obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendments Showa ``''' s:, '7] Bamboo 8 Director General of the Japan Patent Office 1, Indication of the Case 1999, Patent Application No. 4'''' 3, Person making the amendment Relationship to the incident Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd., Form 10-1 4. Subject of amendment We will submit a revised version ff1 (no change in content) of the specification 5 and the details of the amendment.

Showa J, April 1999/Otsuji Patent Office Commissioner's Letter 1, Indication of the Case, Showa SR, Patent Application No. 2411417/
No. 2, Name of the invention Processing method for silver halide color light-sensitive materials 3, Relationship to the case of the person making the amendment Person of the patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the Statement of Amendment ITf114F will be amended as follows. .

fi+ 1st/page 16th line r R, J "R6" and correct it.

Procedural amendment dated March 11, 1938, 1, Case description Showa SR, Patent Application No. 1447/No. 2
・Title of the invention Processing method for silver halide color light-sensitive materials 3, Relationship with the case of the person making the amendment Six patent applications Subject of the amendment ``Detailed explanation of the invention'' column of the specification & Amount of content of the amendment Specification No. Insert the following structural formula after the structural formula of M-JJ on page 31.

[M-3t M-J M-san〇 5OtNIICH2C) Door) CHs (2) Magenta coupler in Table 1 on page 63 of the circular [(-IOJ “M-1/J and correct it.

(3) Insert Example 3 below between line 17 and line II of page 6≠ of the same 8th page.

[A multilayer silver halide color photosensitive material was prepared by coating in the same manner as in Example 1. However, the couplers used are as follows.

Cyan coupler-t C-co α (C-/ and C-co each used at 0.21 f/m”) Yellow coupler Y-/Magenta coupler shown in Table 2.

After exposure using an optical wedge, the above photosensitive material was processed using color developing solution D or G in Table 1. However, the color development time was 2 minutes and 30 seconds, 3 minutes, and 3 minutes and 30 seconds.

After treatment, the green reflection density of each sample was measured. The relative sensitivity is shown in Table 2 as a relative value as the benzyl alcohol concentration/j- of each sample and the value y1 (ioo) at a oak development time of 3 minutes and 30 seconds.

Claims (1)

[Scope of Claims] A silver halide color light-sensitive material containing at least one type of ≠-mercazotoh!-pyrazolone-type magenta cazole represented by the following general formula (()) is prepared by adding 1 to 1 part of benzyl alcohol to the silver halide color light-sensitive material.
1. A method for processing a silver halide color photosensitive material, comprising processing with a color developer containing ml/11. General formula (1) (wherein, W represents an aryl group, X represents an alkyl group, aryl group, or heterocyclic group, and Y represents an acylamino group, ureido group, or anilino group).