JPH0581022B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an image forming method using a silver halide color light-sensitive material, and particularly to an image forming method in which processing time is significantly shortened. (Prior art) Generally, the processing process for silver halide color photosensitive materials involves the color development part (approximately 3 minutes) that forms a color image.
30 seconds), a bleach-fixing (or bleach-fixing) section which is a desilvering step (about 1 minute 30 seconds), a water washing section, and/or an image stabilization section (2 to 3 minutes).
By the way, in order to significantly shorten the processing time, it is clear that it is most effective to shorten all of these processing steps. (Problems to be Solved by the Invention) Conventionally, a number of techniques have been studied for the purpose of shortening color development time. Methods of increasing the pH of the developer or increasing the amount of benzyl alcohol have been known for a long time, but the effects vary markedly depending on the type of coupler used. The balance of the three colors is different, so it is not an appropriate method, and furthermore, it cannot be said to be a preferable method in terms of pollution control. In addition, various color development accelerators (for example, U.S. patent
No. 2950970, No. 2315147, No. 2496903, No.
No. 2304925, No. 4038075, No. 4119462, British Patent No. 1430998, British Patent No. 1455413, Japanese Patent Application Publication No. 15831/1983,
No. 55-62450, No. 55-62451, No. 55-62452,
No. 55-62453, Special Publication No. 51-12422, No. 55-
Even when the compound described in No. 49728 etc. was used in combination, sufficient color density could not be obtained. Also, methods of incorporating color developing agents (for example, U.S. Pat. Nos. 3,719,492, 3,342,559, 3,342,597,
Japanese Patent Publication No. 56-6235, No. 56-16133, No. 57-97531
Even if the method described in No. 57-83565 is used, it is not an appropriate method because it has the disadvantages that color development is delayed and fog is generated. In addition, methods using silver chloride emulsions (for example, the methods described in JP-A No. 58-95345, JP-A No. 59-232342, JP-A No. 60-19140, etc.) have high fog and are not suitable for practical use. None. Therefore, there are only a few suitable methods for promoting color development, and the method of increasing the development temperature is relatively effective, but conversely, deterioration of the processing solution due to air oxidation and concentration due to evaporation of the processing solution pose problems. However, in practice, there was a limit to the temperature rise. Through research conducted by the present inventors, it has been found that it is important to select and combine cyan, magenta, and yellow couplers that satisfy the contradictory characteristics of excellent color development and low fog. Next, when shortening the desilvering process, a one-bath bleach-fixing process is more advantageous than a two-bath bleach-fixing process from the viewpoint of reducing the number of processing baths. Various accelerators have been studied as a method of accelerating the bleach-fixing process. For example, compounds having a mercapto group or a disulfide group as described in U.S. Patent No. 3893858, West German Patent No. 1290812, etc.;
Examples include thiourea derivatives described in No. 3706561 and JP-A-53-32735, and polyethylene oxides described in West German Patent No. 2748430, but none have a sufficient promoting effect. In order to shorten the desilvering process, it is effective to reduce the amount of silver coated in the sensitive material. Therefore, a 2-equivalent coupler is preferable to a 4-equivalent coupler, and a coupler with excellent coloring properties is more preferable. Furthermore, if the bleach-fixing process, which has weak oxidizing power, is shortened, leucoization of the cyan dye becomes more likely to occur. For the above reasons, cyan, magenta, and yellow couplers can be selected and used to shorten the desilvering process time.
It was found that the selection of combinations, especially the cyan coupler, is important. Finally, if the washing step and/or image stabilization step is shortened, it is inevitable that the bleach-fix components will not be washed sufficiently. In this case, the image storage stability of the processed photosensitive material deteriorates. Conventionally, various antifading agents have been added to color photosensitive materials for the purpose of improving image storage stability (for example, as described in the US patent
No. 2816028, No. 3457079, No. 3698909, No.
No. 3764337, No. 3700455, etc.), these anti-fading agents become ineffective if the washing process time is less than 1 minute and 30 seconds. That is, if the iron complex present in the bleach-fix solution is insufficiently washed, the remaining iron complex reacts with the remaining coupler, resulting in a problem of increased yellow stain during dark storage. Therefore, it has been found that the selection and combination of cyan, magenta, and yellow couplers is an important item for shortening the washing process. Therefore, the object of the invention is to solve all of the above problems at the same time, and more specifically, to provide a method for forming images in processing steps in which each processing time is significantly shortened. Another object of the present invention is to provide an image forming method for a color photographic material having excellent color development properties, desilvering properties, and image storage properties. (Means for Solving the Problems) The above object of the present invention is to provide at least one type of yellow coupler represented by the following general formula (), and a yellow coupler represented by the general formula (-a), (-c) or (-d). A multilayer silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the formula (2) and at least one cyan coupler represented by the general formula () in different color-sensitive photosensitive layers,
After color development processing for 40 seconds to 2 minutes, 3 seconds to 70
This was achieved by bleaching and fixing in seconds, followed by washing with water for 30 seconds to 1 minute and 30 seconds to obtain an image. The couplers of the general formulas (), (), and () used in the present invention are each well known, but by combining these three couplers, rapid processing becomes possible.
The fact that images of excellent quality can be obtained is completely unexpected and worthy of invention.

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【formula】

【formula】

【formula】

[C] In the above general formulas (), (), (), R ₁₄ , R ₁₅ ,
R ₁₆ represents a hydrogen atom or a substituent, R ₂ represents a group that can be substituted for a phenylene group, and n is 0 to 5
and when n is 2 or more, R ₂ may be the same or different, R ₃ represents a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R ₄ is a hydrogen atom, Even if it represents a halogen atom, a substituted or unsubstituted aliphatic, aromatic, heterocyclic, or acylamino group, and R ₃ and R ₄ are nonmetallic atomic groups forming a 5- or 6-membered nitrogen-containing heterocycle. Often, Y ₁ , Y ₂ and Y ₃ represent groups that can be separated by a coupling reaction with an oxidized aromatic primary amine developing agent. The present invention will be explained in more detail below. General formula (), (-a), (-c), (-d)
,
In (), R ₁₄ , R ₁₅ , R ₁₆ and R ₃ are linear or cyclic aliphatic groups preferably having 1 to 32 carbon atoms (e.g., methyl group, butyl group, hexadecyl group, cyclohexyl group, propenyl group). , 2-octadecenyl group, propargyl group, etc.), aromatic group (e.g., phenyl group, naphthyl group, etc.), or heterocyclic group (e.g., 2-pyridyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group) These also include the aforementioned aliphatic groups, aromatic groups, heterocyclic groups, alkoxy groups (e.g., methoxy group, 2-methoxyethoxy group), aryloxy groups (e.g., phenoxy group, 2,4-di-tert
-amylphenoxy group, 2-chlorophenoxy group, etc.), carboxyl group, acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group) , butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group,
benzoylamino group, etc.), silyl group (trimethylsilyl group, etc.), silyloxy group, silylamino group, carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (e.g., dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group),
Aliphatic sulfonamide group (e.g. methanesulfonamide group), aromatic alkonamide group (e.g.
phenylsulfonamide group), sulfamoyl group,
Alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), mono- or dialkylamino group, sulfamide group (e.g. dipropylsulfamoylamino group, etc.) ,
Imide groups (e.g., succinimide group, hydantoinyl group, etc.), ureido groups (e.g., phenylureido group, dimethylureido group, etc.), aliphatic sulfonyl groups (e.g., methanesulfonyl group, etc.), aromatic sulfonyl groups (e.g., phenylsulfonyl group, etc.) aliphatic or aromatic thio groups (e.g., ethylthio group, phenylthio group, etc.),
It may be substituted with a substituent selected from a hydroxy group, a cyano group, a thiocyanato group, a nitro group, a halogen atom, etc. (hereinafter referred to as "substituent permissible for R ₁₄ , R ₁₅ , R ₁₆ "). Furthermore, when there are two or more substituents, they may be the same or different. R ₂ is, for example, specifically a halogen atom, an acylamino group, a sylphonamide group, and R ₁₄ , R ₁₅ ,
Represents permissible substituents for R ₁₆ . When n=2 or more, R ₂ may be the same or different. Y ₁ , Y ₂ and Y ₃ are coupling separation re (hereinafter referred to as
(referred to as "leaving group"), where the leaving group is oxygen,
Coupling activated carbon and aliphatic groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups via nitrogen, sulfur or carbon atoms. groups, halogen atoms, carboxyl groups, aromatic azo groups, etc., and the aliphatic, aromatic, or heterocyclic groups contained in these leaving groups are substituted with the permissible substitutions in R ₁₄ , R ₁₅ , and R ₁₆ . It may be substituted with a group, and when two or more of these substituents are present, they may be the same or different, and these substituents further substituents that are permissible for R ₁₄ , R ₁₅ , and R ₁₆ . may have. Specific examples of coupling-off groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), carboxyl groups, alkoxy groups (e.g. ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group). , methylsulfonyl ethoxy group, etc.),
Aryloxy groups (e.g. 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy groups (e.g. acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), fatty acids group or aromatic sulfonyloxy group (e.g. methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylamino group (e.g. dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or aromatic sulfonamide group (e.g. (methanesulfonamide group, p-toluenesulfonamide group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic group, aromatic or heterocyclic thio group (e.g. ethylthio group, phenylthio group, tetrazolylthio group, etc.), carbamoylamino group (e.g. N-methylcarbamoylamino group, N-
phenylcarbamoylamino group, etc.), carbamoyloxy group (e.g., N-dimethylcarbamoyloxy group, etc.), 5- or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl group, pyrazolyl group,
triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo-1-pyridyl group, etc.), imide groups (e.g., succinimide group, hydantoinyl group, etc.), aromatic azo groups (e.g., phenylazo group, etc.), and these The group further includes R ₁₄ ,
R ₁₅ and R ₁₆ may be substituted with permissible groups. Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators. Preferred combinations of leaving groups in each general formula will be described later. Q represents a substituted or unsubstituted N-phenylcarbamoyl group. The substituents of the phenyl group of the N-phenylcarbamoyl group are the above-mentioned R ₁₄ , R ₁₅ , R ₁₆
can be arbitrarily selected from the group of permissible substituents for R ₁₄ , R ₁₅ , R ₁₆ when is an aromatic group,
When there are two or more substituents, they may be the same or different. Next, preferred substituents in general formula () will be described. Preferred examples of Q include the following general formula (-A).

[In the formula, G ₁ represents a halogen atom or an alkoxy group which may have a substituent, and G ₂ represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent. R ⁵ represents an alkyl group which may have a substituent. ] As the substituent for the alkoxy group or alkyl group of G ₂ and R ⁵ in the general formula (-A), for example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group,
Heterocyclic group (e.g. N-morpholino group, N-piperidino group, 2-furyl group, etc.), halogen atom,
Typical examples include a nitro group, a hydroxy group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group. Preferred leaving groups Y ₁ are shown below () to ()
It includes groups represented by the general formula.

embedded image R ₆ represents an optionally substituted aryl group or heterocyclic group.

【formula】

[Formula] R ₇ and R ₈ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group , represents an unsubstituted or substituted phenyl group or a heterocyclic ring, and these groups may be the same or different.

[C] W ₁ is in the formula

[Formula] represents a nonmetallic atom required to form a 4-, 5-, or 6-membered ring. In the general formula (), preferably () ~
Examples include ().

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[Chemical formula] In the formula, R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group,
Represents an aryl group, alkoxy group, aryloxy group or hydroxy group, R ₁₁ , R ₁₂ and R ₁₃
each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W ₂ represents an oxygen or sulfur atom. Next, details will be given in general formulas (-a), (-c), and (-d). In the general formulas (-a), (-c), and (-d), a multimer is defined as a multimer containing two or more of the general formulas (-
It means those having groups represented by a), (-c), and (-d), and includes bis-forms and polymer couplers. Here, the polymer coupler is a homopolymer consisting only of monomers (preferably those having a vinyl group, hereinafter referred to as vinyl monomers) having moieties represented by general formulas (-a), (-c), and (-d). It may be a polymer, or a copolymer may be made with a non-color-forming ethylene monomer that does not couple with the oxidation product of the aromatic primary amine developer.

【formula】

【formula】

[Formula] General formulas (-a), (-c), (-d)
R ₁₄ , R ₁₅ and R ₁₆ are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups,
Alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group,
Silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group,
Alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group represent. Y ₂ is a group as described above, and among them, a halogen atom or an aryloxy group is preferable. The case where R ₁₄ , R ₁₅ , R ₁₆ or Y ₂ becomes a divalent group and forms a bis body is also included. Furthermore, when the moiety represented by the general formula (-a), (-c), or (-d) is present in the vinyl monomer, R ₁₄ , R ₁₅ or R ₁₆ represents a mere bond or linking group, Through this, general formulas (-a), (-c), (-
d) The represented moiety and the vinyl group are bonded. More specifically, R ₁₄ , R ₁₅ and R ₁₆ are hydrogen atoms, halogen atoms (e.g. chlorine atoms, etc.), alkyl groups (e.g. methyl groups, propyl groups, t-
Butyl group, trifluoromethyl group, tridecyl group, 3-(2,4-di-t-amylphenoxy)
Propyl group, 2-dodecyloxyethyl group, 3-
Phenoxypropyl group, 2-hexylsulfonyl-ethyl group, scropentyl group, benzyl group,
etc.), aryl groups (e.g. phenyl group, 4-t
-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group,
etc.), heterocyclic groups (e.g., 2-furyl group, 2-
thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.) ), aryloxy groups (e.g. phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy groups (e.g. 2-benzimidazolyloxy group, etc.), acyloxy groups (e.g. acetoxy group) , hexadecanoyloxy group, etc.),
Carbamoyloxy group (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), Acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2,4
-di-t-amylphenoxy)butyramide group,
γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide group, etc.), anilino group (e.g., phenylamino group, 2- Chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-
dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-{α-(3-t
-butyl-4-hydroxyphenoxy)dodecaneamide}anilino group, etc.), ureido group (e.g.
phenylureido group, methylureido group, N,N
dibutylureido group, etc.), imide group (e.g.
N-succinimide group, 3-benzylhydantoynyl group, 4-(2-ethylhexanoylamino)
phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, -Butoxy-5-
t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
), heterocyclic thio groups (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g. , phenoxycarbonylamino group, 2,4-di-tert-
butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5 -t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecyl group) carbamoyl group, N-{3-(2,4-di-tert-amylphenoxy)propyl}carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-
amylphenoxy)acetyl group, benzoyl group,
), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group , N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g. octanesulfinyl group, dodecyl group) Sulfinyl group, phenylsulfinyl group,
), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl group, 3-
pentadecyl phenyloxycarbonyl group, etc.)
represents. When R ₁₄ , R ₁₅ , R ₁₆ or Y ₂ becomes a divalent group to form a bis body, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (for example, a methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, etc.), substituted or unsubstituted phenylene group (e.g. 1,4
-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO -R ₂ -CONH- group (R ₂ is substituted or unsubstituted,
Represents an alkylene group or a phenylene group. R ₁₄ when the compound represented by general formula (-a), (-c), (-d) is in the vinyl monomer,
The linking group represented by R ₁₅ or R ₁₆ is an alkylene group (substituted or unsubstituted alkylene group, such as methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (e.g.

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[C], etc.). Note that the vinyl group in the vinyl monomer may have a substituent. A preferred substituent is a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms. Non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (for example, methacrylic acid, etc.)
and esters or amides derived from these acrylic acids (e.g. acrylamide,
n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, t-butylacrylate, iso-butylacrylate, 2-ethylhexyl acrylate, n- Octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroxymethacrylate), methylene dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene) , vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid,
Examples include maleic anhydride, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. 2 of the non-chromogenic ethylenically unsaturated monomers used here
This includes cases where more than one species is used together. Next, preferred substituents in general formula () will be described. R ₄ is particularly preferably a hydrogen atom, a halogen atom, and a substituted or unsubstituted aliphatic atom. R ₂ is a halogen atom, −SO ₂ R ₁₇ −, −CF ₃ , −
NO ₂ , −CN, −COR ₁₇ , −COOR ₁₇ , −SO ₂ OR ₁₇ ,

【formula】

[Formula] −OR ₁₇ , −OCOR ₁₇ ,

【formula】

[Formula] O call

It is preferable to have at least one substituent selected from the formula. Here, R ₁₇ is an alkyl group (preferably 1 carbon number
~20 alkyl group), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms), a cycloalkyl group (preferably a 5- to 7-membered ring), and an aryl group, and these groups are substituted with permissible substituents in _R1. By base,
It may be replaced. Further, R ₁₈ is a hydrogen atom or a group represented by R ₁₇ . Examples of leaving groups for _Y3 include alkoxy groups, aryloxy groups, carbamoyloxy groups, carbamoylmethoxy groups, acyloxy groups, sulfonamide groups, and succinimide groups in which a halogen atom, oxygen atom, or nitrogen atom is directly bonded to the coupling position. A group is preferred. Among these, halogen atoms and aryloxy groups are preferred. Next, a method for synthesizing couplers represented by general formulas (), (), and () will be described. The compound of general formula () is disclosed in JP-A No. 54-48541,
Special Publication No. 58-10739, No. 47-27411, US Patent
No. 4326024, Research Disclosure No. 18053, Japanese Unexamined Patent Publication No. 1983-
It can be synthesized by the method described in No. 45512, JP-A-60-172982, etc. Examples of compounds and synthesis methods of couplers represented by the general formulas (-a), (-c), and (-d) above are as follows:
It is described in the documents listed below. The compound of general formula (-a) is
162548, etc., the compound of general formula (-c) is described in Japanese Patent Publication No. 47-27411, etc., and the compound of general formula (-d) is described in Japanese Patent Publication No. 59-171956 and Japanese Patent Publication No. 60-60.
172982, etc., respectively. Also, JP-A-58-42045, JP-A No. 59-214854, JP-A No. 59-214854,
The highly color-forming ballast group described in No. 59-177553, No. 59-177554, No. 59-177557, etc. can be any of the compounds of the above general formulas (-a), (-c), and (-d). also applies. A method for synthesizing the coupler represented by the general formula () is shown in JP-A-56-80045, etc. Next, the general formula (), (-a), (-c), (-
Specific examples of compounds represented by d) or () are (Y-1), (M-1) and (C-
1) Although described below, the present invention is not limited to these exemplified compounds.

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embedded image These couplers are generally added in an amount of 2×10 ⁻³ mol to 5×10 ⁻¹ mol, preferably 1×10 ⁻² mol to 5×10 ⁻¹ mol, per mol of silver in the emulsion layer. Two or more of the above couplers and the like can be used in combination in the same layer in order to satisfy the characteristics required of a photosensitive material. Furthermore, couplers other than those of the present invention may be used in combination as necessary. For example, as a yellow coupler, there is a US patent.
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 3891445, West German Patent No. 1547868, West German Application Publication
No. 2219917, No. 2261361, No. 2414060, British Patent No. 1425020, Japanese Patent Publication No. 10783, No. 1978, Japanese Patent Publication No. 1978-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
No. 51-21827, No. 50-87650, No. 52-82424,
This is described in No. 52-115219, etc. As a magenta coupler, U.S. Patent No. 2600788,
Same No. 2983608, No. 3062652, No. 3127269, Same No.
No. 3311476, No. 3419391, No. 3519429, No.
No. 3558319, No. 3582322, No. 3615506, No. 3582322, No. 3615506, No.
No. 3834908, No. 3891445, West German Patent No. 1810464,
West German patent application (OLS) No. 2408665, OLS No. 2417945,
No. 2418959, No. 2424467, Special Publication No. 40-6031,
JP-A No. 51-20826, No. 52-58922, No. 49-
No. 129538, No. 49-74027, No. 50-159336, No.
No. 52-42121, No. 49-74028, No. 50-60233,
No. 51-26541, No. 53-55122, No. 55-62454,
Coupler described in No. 57-35858 etc. may be used in combination. As cyan couplers, phenolic compounds,
A naphthol compound etc. can be used in combination. Specific examples are US Patent Nos. 2369929 and 2434272.
No. 2474293, No. 2521908, No. 2772162,
Same No. 2895826, No. 3034892, No. 3311476, Same No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3758308, No. 3772002, No.
No. 3767411, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146828,
No. 52-69624, No. 52-90932, No. 55-163537
No. 56-99341, No. 56-116030, No. 56-
No. 80045, No. 56-104333, No. 57-155538, No.
No. 57-204545, No. 58-105229, No. 59-31953,
These are those described in No. 59-31954, No. 59-34536, etc. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. A coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid 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 (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or boiling point approx.
Organic solvent at 30°C to 150°C, such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Next, the processing step (image forming step) in the present invention
Let's talk about. The color development processing step in the present invention has an extremely short processing time of 40 seconds to 2 minutes. The processing time herein refers to the time from when the photosensitive material comes into contact with the color developer until it comes into contact with the bleach-fix solution, which is the next bath, and includes the transfer time between baths. The preferred processing time in the present invention is 50 seconds to
It is 1 minute 50 seconds. The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N,N-diethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p
-toluenesulfonate, tetraphenylborate, p-(t-octyl)benzenesulfonate, and the like. Examples of aminophenol derivatives include o
-aminophenol, p-aminophenol, 4
-amino-2-methylphenol, 2-amino-
These include 3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like. In addition, LFA Meson's “Photography
"Processing Chemistry", Focal Press (1966) (LFamason,
“Photographic Processing Chemistry”, Focal
Press), pages 226-229, U.S. Patent No. 2193015,
Those described in No. 2592364, JP-A-48-64933, etc. may be used. If necessary, two or more color developing agents may be used in combination. In order to shorten the development time, the concentration and pH of the developing agent are very important factors, and in the present invention, the concentration of the developing agent is about 1.0 g to about 15 g per color developer, more preferably about 3.0 g per color developer. g ~ approx. 8.0g
Use at a concentration of Further, the pH of the color developer is usually 9 or higher, most preferably about 9.5 to about 12.0.
used in Further, in the present invention, various development accelerating means can be used in combination as necessary. The processing temperature of the color developer in the present invention is:
Preferably 30° to 50°C, more preferably 33°C to 45°C
It is ℃. In addition, although benzyl alcohol is effective as a development accelerator, other US patent
No. 2648604, Special Publication No. 1971-9503, U.S. Patent No. 3171247
Various pyrimidium compounds and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 1983-9304, U.S. Patent
No. 2533990, No. 2531832, No. 2950970, No.
Nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers described in US Pat. No. 2,577,127, and thioether compounds described in US Pat. No. 3,201,242 may be used. Furthermore, in short-time development processing as in the present invention, not only a means for promoting development but also a technique for preventing development fog is an important issue. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.
Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-5
Mercapto-substituted heterocyclic compounds such as -mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are halides. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer. In addition, the color developer in the present invention may include pH buffering agents such as alkali metal carbonates, borates or phosphates; hydroxylamine, triethanolamine, OLS No. 2622950;
preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; 1-
Auxiliary developers such as phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and JP-A-58-
Aminopolycarboxylic acids represented by the compounds described in No. 195845, 1-hydroxyethylidene-1,
1'-Diphosphonic acid, Research Disclosure No. 18170 (May 1979)
organic phosphonic acid, aminotris (methylenephosphonic acid), ethylenediamine-N,N,
Aminophosphonic acids such as N′,N′-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-
No. 42730, No. 54-121127, No. 55-4024, No. 55
-4025, 55-126241, 55-65955, 55-65955, 55-126241, 55-65955,
No. 55-65956, and Research Disclosure No. 18170 (1979).
It may contain a chelating agent such as a phosphonocarboxylic acid described in May 2013). Further, the color developing bath may be divided into two or more parts as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. The silver halide color light-sensitive material of the present invention is subjected to a bleach-fixing process after a color development process. The bleach-fixing process time is as short as 30 seconds to 70 seconds, and the main process time is defined in the same manner as the color development time, and includes the transfer time between baths. Examples of bleaching agents used include organic complex salts of iron () or cobalt () (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Aminopolycarboxylic acids such as aminopolyphosphonic acids, complex salts of phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. can be used. . Among these, organic complex salts of iron (2) are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids or aminopolyphosphonic acids or salts thereof useful for forming organic complex salts of iron () are listed as follows: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-
N,N',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino- 2-propanoltetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminedipropionic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1,2,4-triacetic acid, 1,3-diaminopropanol-N,N,N',
N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N',
Examples include N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and the like. Among these compounds, iron complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. As the iron () complex salt, one or more types of ready-made complex salts may be used, or iron () salts (for example, dibasic sulfate) may be used.
iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.) and a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) in a solution. It may also be used as a ferric ion complex salt. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount. Further, the bleach solution or bleach-fix solution containing the ferric ion complex described above may contain metal ions other than iron such as cobalt and copper, complex salts thereof, or hydrogen peroxide. The amount of bleach per 1 bleach-fix solution is 0.075 ~
2.0 mol is suitable, preferably 0.1-0.5 mol. The fixing agent used in the present invention is a known fixing agent,
Namely, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Water-soluble silver halide dissolving agents such as ethylene bisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and thioureas, and these can be used singly or in combination of two or more. can be used. Furthermore, in the bleach-fixing process, a special bleach-fix 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-55-155354 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per bleach-fixing solution is 0.3~
The amount is preferably 3 moles, more preferably 0.5 to 1.5 moles. The pH range of the bleach-fix solution in the present invention is preferably 5 to 9, more preferably 6.5 to 7.5. If the pH is lower than this, the desilvering performance will improve, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. When the reverse pH is higher than this, desilvering is delayed and stains are more likely to occur. In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary. Additionally, the bleach-fix solution of the present invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide). A rehalogenating agent may be included. If necessary, one or more inorganic substances with PH buffering capacity such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. acid,
Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added. Furthermore, in addition to the above-mentioned additives that can be added to the bleach-fix solution, preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine,
Hydrazine, a bisulfite salt of an aldehyde compound (eg, acetaldehyde sodium bisulfite), and the like can be contained. Furthermore, various fluorescent bleaches, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained. Further, a bleach accelerator may be used in the bleach-fix solution and its pre-bath, if necessary. Specific examples of useful bleach accelerators are described in US Pat. No. 3,893,858, German Patent No. 1,290,812.
No. 2059988, JP-A-53-32736, No. 53-
No. 57831, No. 37418, No. 53-65732, No. 53-
No. 72623, No. 53-95630, No. 53-95631, No. 53
−104232, No. 53-124424, No. 53-141623,
No. 53-28426, Research Disclosure
Compounds having a mercapto group or disulfide group as described in No. 17129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-B No. 45-8506, JP-A-52 −20832
No. 53-32735, thiourea derivatives described in U.S. Pat.
Polyethylene oxides described in JP-A No. 966410 and JP-A No. 2748430; polyamine compounds described in JP-A No. 45-8836; and other JP-A Nos. 49-42434 and JP-A-49-49-
No. 59644, No. 53-94927, No. 54-35727, No. 55
Compounds described in No. 26506 and No. 58-163940 and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
-95630 is preferred. The silver halide color light-sensitive material of the present invention is washed with water after bleach-fixing. In the present invention, instead of the usual "water washing treatment", a simple treatment method may be used in which only a so-called "stabilization treatment" is performed without providing a substantial water washing step. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above. The washing time in the present invention is 30 seconds to 1 minute 30 seconds, preferably 40 seconds to 1 minute 10 seconds. The washing time here refers to the time from when the photosensitive material comes into contact with the washing water until it reaches the drying zone, which is the final step. If the washing process is a multi-stage countercurrent washing process with two or more tanks, it represents the total washing time from contact with the washing water in the first tank until reaching the drying zone. So-called “stabilization treatment” instead of regular water washing
The above definition also applies when doing so. In order to shorten the washing process, the above-mentioned combination of couplers is essential, but the amount of washing water and the washing temperature are also important from a practical standpoint. It is difficult to specify the amount of water for washing because it depends on the number of baths in multistage countercurrent washing and the amount of pre-bath components brought into the photosensitive material.
In the present invention, it is sufficient that the bleach-fixing solution component in the final washing bath is 1×10 ^-4 or less. For example, in the case of 3-tank countercurrent water washing, approximately 1000 ml per 1 m ² of photosensitive material
It is preferable to use 5000 or more, more preferably 5000 or more.
ml or more. Washing temperature is 15℃~45℃, more preferably 20℃~
It is 35℃. In the washing process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericides and antibacterial agents that prevent the growth of various bacteria, algae, and molds (for example, ``Journal of Antibacterial and Antibiotics'');・Antifungal Agents”
(J.Antibact.Antifung.Agents) vol.11, No.5,
Compounds described on pages 207 to 223 (1983) and compounds described in "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi), metal salts such as magnesium salts and aluminum salts,
Alkali metal and ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Alternatively, compounds described in "Photographic Science and Engineering" by West, vol. 6, pages 344-359 (1965) may be added. It is particularly effective to add chelating agents, fungicides, and anti-bacterial agents. The washing step may be performed using multi-stage countercurrent washing with two or more tanks (for example, 2 to 9 tanks) to save washing water. Furthermore, a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 may be performed instead of the usual water washing process. In this case,
The bleach-fix component in the final bath may be 5×10 ^-2 or less. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g. borate, metaborate, borax, phosphate,
Representative examples include carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole series, isothiazole series, halogenated phenols, sulfanilamide, benzene) Triazole, etc.), surfactants, fluorescent brighteners, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane PH regulator for the processing machine in order to improve image storage stability. The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of developer precursors include indoaniline compounds described in U.S. Pat. No. 3,342,597, U.S. Pat.
) and Schiff base-type compounds described in US Pat. No. 15159 (November 1976), aldol compounds described in US Pat. No. 13924, metal salt complexes described in US Pat. No. 3,719,492,
There are urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, and JP-A-56-
No. 59232, No. 56-67842, No. 56-83734, No. 56
−83735, No. 56-83736, No. 56-89735, No.
No. 56-81837, No. 56-54430, No. 56-106241,
No. 56-107236, No. 57-97531 and No. 57-
Various salt-type precursors described in No. 83565 and the like can also be used in the present invention. The silver halide color light-sensitive material of the present invention uses various types of 1-phenyl-3 to promote color development.
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A No. 57-144547, and JP-A No. 57-144547.
No. 57-211147, No. 58-50532, No. 58-50536,
It is described in No. 58-50533, No. 58-50534, No. 58-50535, No. 58-115438, etc. Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs. Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary. The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. able to make. As this silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used; and silver chloride are preferred. Average grain size of silver halide grains (grain diameter for spherical or approximately spherical grains, grain diameter for cubic grains,
The grain size (expressed as an average based on the projected area) is preferably 2μ or less, and particularly preferably 0.4μ or less. The particle size distribution may be narrow or wide, but the narrower the better. The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal thereof. Further, the particles may be tabular grains having an average aspect ratio (diameter of projected area to grain thickness) of 5 or more. Alternatively, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is uniform inside,
Also, those with a layered structure with different interior and exterior,
It may be of a so-called convergence type as described in British Patent No. 635,841 and US Pat. No. 3,622,318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles,
benzotriazoles, aminotriazoles, etc.); mercapto compounds {e.g. mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
mercaptopyrimidines, mercaptotriazines, etc.}; thioketo compounds such as oxadolinthione; azaindenes {e.g., triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraaza A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
Those described in No. 3982947 and Japanese Patent Publication No. 52-28660 can be used. Known antifading agents can be used in the photographic material used in the present invention. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Specific examples of hydroquinone derivatives are US patents
No. 2360290, No. 2418613, No. 2675314, No.
No. 2701197, No. 2704713, No. 2728659, No. 2701197, No. 2704713, No. 2728659, No.
No. 2732300, No. 2735765, No. 2710801, No. 2732300, No. 2735765, No. 2710801, No.
No. 2816028, British Patent No. 1363921, etc., and gallic acid derivatives are described in U.S. Patent No. 3457079,
3069262, etc., and those of p-alkoxyphenols are described in U.S. Patent No. 2735765, U.S. Pat.
3698909, Japanese Patent Publication No. 49-20977, and Japanese Patent Publication No. 52-6623, and those of p-oxyphenol derivatives are described in U.S. Pat.
No. 3574627, No. 3764337, JP-A-52-35633,
Nos. 52-147434 and 52-152225, and bisphenols are disclosed in U.S. Patent No. 3700455.
There is a description in the issue. The image forming method of the present invention is particularly suitable for rapid processing of color paper. (Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 Multilayer silver halide color photosensitive materials 1 to 13 were prepared by coating the following first layer (bottom layer) to seventh layer (top layer) on a paper support laminated on both sides with polyethylene.
was applied.

【table】

[Table] The coating solution for the first layer was prepared as follows. That is, the yellow coupler 100 shown in Table 1
Dissolve g in a mixture of 166.7 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, and add 1
% sodium dodecylbenzenesulfonate aqueous solution
This emulsified dispersion was then mixed with 1450 g of a blue-sensitive silver chlorobromide emulsion (80% Br) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions for the other layers were prepared in the same manner. The hardening agent for each layer is 2,4-
Dichloro-6-hydroxy-s-triazine sodium salt was used. The following spectral sensitizers were used for each emulsion. Blue-sensitive emulsion layer: 3,3'-di-(γ-sulfopropyl)-selenacyanine sodium salt (2×10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer: 3,3'-di-( γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 x 10 ^-4 mol per 1 mol of silver halide) Red-sensitive emulsion layer; sulfopropyl)-9-methyl-thiadicarbocyanine sodium salt (2.5x per mole of silver halide)
(10 ^-4 mol) The following dyes were used as anti-irradiation dyes in each emulsion layer. Green-sensitive emulsion layer;

[ka] red-sensitive emulsion layer;

[Chemical structure] The chemical structures of the compounds in the above table are as follows.

【formula】

【formula】

【formula】

【formula】

[ka]

【formula】 The coupler combinations used are shown below.

[Table] In addition, 4-equivalent couplers (Y-A, Y-B, M-
When using B, M-C), the amount of silver coated was twice the indicated amount. comparison coupler

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Chemical formula] Samples 1 to 12 were exposed through an optical wedge and then processed in the following standard processing step A. Processing step A Temperature Time Color development 33°C 3'30'' Bleach-fixing 33°C 1'30'' Washing 24-34°C 3' Drying 80°C 1' The components of each processing solution are as follows. Color developer A Water 800ml Diethylenetriaminepentaacetic acid 3.0g Benzyl alcohol 15ml Diethylene glycol 10ml Sodium sulfite 2.0g Potassium bromide 0.5g Potassium carbonate 30.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4- Aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Fluorescent brightener (stilbene type) 1.0g Add water 1000ml PH 10.10 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 150ml Sodium sulfite 18g Iron ethylenediaminetetraacetate ( ) ammonium
55g Ethylenediaminetetraacetic acid/2Na 5g Add water to 1000ml PH 6.70 Next, a rapid processing process with some changes in the processing conditions and composition of the color developer was designated as B, and the same process was performed for sample 1.
~12 were processed. In processing step B, the temperature of the color developer is 37° C., and the processing time is 1 minute and 40 seconds. Further, both the bleach-fixing process and the water washing process were performed in one minute. Color developer B Water 800ml Diethylenetriaminepentaacetic acid 3.0g Benzyl alcohol 15ml Diethylene glycol 10ml Sodium sulfite 2.0g Potassium bromide 0.5g Potassium carbonate 30.0g N-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-4- Aminoaniline sulfate 5.5g Hydroxylamine sulfate 4.0g Fluorescent brightener (stilbene type) 1.0g Add water 1000ml PH 10.25 For each sample, the photographic properties obtained in processing step A (standard processing) were used as the standard. The value of change in photographic properties (△Dmin, △Dmax) in rapid processing step B is
Shown in the table.

[Table] From the above results, the present invention and sample No. 8 are the only combinations that exhibit sufficient color development even in rapid processing and do not increase fog. Furthermore, the following examples were conducted in order to strictly evaluate the performance. (Example 2) Samples 1 to 12 of Example 1 were treated with the following rapid treatment step C and treatment solution assuming a running equilibrium state of rapid treatment. Processing step C Temperature Time ^* Color development 37℃ 1 minute 40 seconds Bleach fixing 33℃ 1 minute 00 seconds Washing 1 30℃ 20 seconds Washing 2 30℃ 20 seconds Washing 3 30℃ 20 seconds Drying 80℃ 1 minute 00 seconds *However, bathing Including 10 seconds of travel time between. Color developer; Example 1 Same as color developer B Bleach-fixer Ammonium thiosulfate (70%) 200ml Sodium sulfite 18g Iron () ammonium ethylenediaminetetraacetate
65g Ethylenediaminetetraacetic acid/2Na 5g 350ml of the above color developer Add water 1000ml PH 7.00 Wash with water 1 Add 10ml of the above bleach-fix solution per 1 water and wash with water 2 Add 10ml of the solution from washing 1 above per 1 water and wash with water 3 Wash with the above water Add 10ml of solution 2 per 1 water.For each of Samples 1 to 12, change in photographic properties obtained in processing step C (△
Dmin, △Dmax) are shown in Table 3. At the same time, Table 3 also shows the results of measuring the amount of residual silver in the treated samples in treatment steps A and C using fluorescent X-rays. Table 3 also shows the change in yellow stain when the treated samples in treatment steps A and C were left at 80° C./70% RH for 6 days.

[Table] As is clear from the results in Table 3, in the present invention, even in rapid processing (processing step C), sufficient color density, desilvering property (3 mg/cm ² or less), and image storage property ( It can be seen that a reduction in yellow stain can be obtained. In addition, in Sample 8, poor color recovery of the cyan dye occurred, making it unsuitable. (Example 3) In the same manner as in Example 2, the following rapid processing step D
Samples 1 to 12 of Example 1 were treated with the and treatment liquid.

[Table] Color developer: Example 1 Same as color developer B Bleach-fix solution: Same as Example 2 bleach-fix solution. Rinse solution; 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution) 2.5ml 1,2,3-benzotriazole 1.0g ammonium alum 0.5g Add water to bring the pH to 1, and adjust the pH to 7 with aqueous ammonia. I made it 4. Rinse 1: Add 100% of the above bleach-fix solution to the above rinse solution.
ml/added. Rinse 2: Add 10% of the above bleach-fix solution to the above rinse solution.
ml/added. Rinse 3: Add 1 part of the above bleach-fix solution to the above rinse solution.
ml/added. For each of Samples 1 to 12, changes in photographic properties in processing step A versus rapid processing step D and yellow stain concentration after 6 days at 80°C/70% RH are shown in Table 4 in the same manner as in Example 2. Ta.

[Table] As is clear from the results in Table 4, the present invention exhibits sufficient color development without increasing fog,
Furthermore, there is little increase in yellow stain after treatment. (Example 4) Samples 13 to 23 were similarly prepared using the couplers shown in Table 5 in place of the sample used in Example 2, and the other samples were prepared in the same manner as in Example 2. Ta. The results obtained are shown in Table 6. As is clear from the results in Table 6, it can be seen that in the present invention, sufficient color density, desilvering properties, and image preservability (reduction in yellow stain) can be obtained even in rapid processing (processing step c). . (Example 5) Samples 101 to 109 were prepared in the same manner by changing the magenta coupler M-B of sample No. 7 used in Example 2 to the magenta coupler shown in Table 7. The test was carried out as in Example 2. The results obtained are shown in Table 8. As is clear from the results in Table 8, it can be seen that in the present invention, sufficient color density, desilvering properties, and image preservability (reduction in yellow stain) can be obtained even in rapid processing (processing step c). .

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[Table] (Effects of the present invention) As is clear from the results shown in Tables 3 and 4 above, according to the present invention, sufficient color density can be obtained without increasing fog even when rapid processing is performed, and It has good desilvering properties and also good storage stability after treatment.

Claims (1)

[Claims] 1. At least one type of yellow coupler represented by the following general formula () and general formulas (-a), (-
A multilayer halogenated compound containing at least one magenta coupler represented by c) or (-d) and at least one cyan coupler represented by the general formula () in photosensitive layers with different color sensitivities, respectively. A silver color photographic material is color developed for 40 seconds to 2 minutes, then bleached and fixed for 30 seconds to 70 seconds, and then washed with water for 30 seconds to 1 minute and 30 seconds to obtain an image. A method for forming images on color photosensitive materials. [Formula] [Formula] [Formula] [Formula] [Formula] In the above general formulas (), (), (), R ₁₄ , R ₁₅ ,
R ₁₆ represents a hydrogen atom or a substituent, R ₂ represents a group that can be substituted for a phenylene group, and n is 0 to 5
and when n is 2 or more, R ₂ may be the same or different, R ₃ represents a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R ₄ is a hydrogen atom, Even if it represents a halogen atom, a substituted or unsubstituted aliphatic, aromatic, heterocyclic, or acylamino group, and R ₃ and R ₄ are nonmetallic atomic groups forming a 5- or 6-membered nitrogen-containing heterocycle. Typically, Y ₁ , Y ₂ and Y ₃ represent groups that can be separated by a coupling reaction with an oxidized aromatic primary amine developing agent, and Q represents a substituted or unsubstituted N-phenylcarbamoyl group.