JPH0554937B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"). The present invention relates to a method for processing silver halide color photographic materials capable of forming dye images with excellent storage stability. Generally, photosensitive materials undergo color development after image exposure.
It is processed through processing steps such as bleaching, fixing, stabilizing, bleach-fixing, and washing with water, but in the washing step that follows the processing with a processing solution that has fixing ability, it reacts with silver halide to form a water-soluble complex salt. The compound thiosulfate, other water-soluble silver complex salts, and preservatives such as sulfite and metabisulfite are contained in or adhered to the photosensitive material, and if the amount of washing water is small, the image storage quality may be affected. It is known to have negative effects. Therefore, in order to eliminate these drawbacks, the current situation is to use a large amount of running water to wash away the above-mentioned salts from the photosensitive material after processing with a processing solution having a fixing ability. However, in recent years, there has been a desire for a treatment process that reduces the amount of washing water and takes measures against pollution due to economic reasons such as a lack of water resources, rising sewerage charges and utility costs, and pollution reasons. Conventionally, as a countermeasure against these problems, for example, a method was proposed in West Germany patent no.
No. 2920222 and S.R. Goldwasser (SR, Goldwasser), “Water Flow
Late in immersion watching of motion picture film (Water
Flow Rate in Immersion−Washing of
Motionpicture Film)” SMPTE・Vol.64, 248
~page 253 May, (1955) etc. A processing method is also known in which preliminary washing is provided immediately after the fixing bath to reduce the amount of polluting components contained in and attached to the photosensitive material that enter the washing process, and to reduce the amount of washing water. However, these techniques are not treatment methods that do not use washing water at all. Therefore, in recent years, the depletion of water resources and rising costs for washing due to rising crude oil prices are becoming increasingly serious problems. On the other hand, there is a processing method in which stabilization processing is performed immediately after photographic processing without washing with water. For example, U.S. Patent No.
Silver stabilization treatment using thiocyanate is known, as described in No. 3335004 and the like. However, this method has the disadvantage that the formed image dye is easily converted into a leuco form because the stabilizing bath contains a large amount of sulfite, which has a large effect on the deterioration of color photographic images. Furthermore, as a method of omitting the washing process or extremely reducing the amount of washing water, there is a multi-stage countercurrent stabilization treatment technology as described in JP-A-57-8543, and as a method of JP-A-58-134636. A treatment technique using a stabilizing liquid containing a bismuth complex salt as described is known. However, although these techniques reduce the amount of stabilizing liquid replenished and reduce pollution, the storage stability of photographic images over time is extremely insufficient, and yellow stains are particularly likely to occur under high temperature and high humidity conditions. It was found that a decrease in the density of the cyan dye image was likely to occur. As a technique for improving these, a method of final treatment in the presence of a soluble iron complex salt is disclosed as described in JP-A No. 58-14834, and furthermore, as described in JP-A-57-132146 and JP-A-58-18631. A method of adding an organic chelating agent is disclosed. However, although the above technology has some effect on photobleaching (the property of a dye image not fading when exposed to light) and dark fading of cyan, it has no effect on yellow stain under high temperature and high humidity. It became clear that there was no such thing. It has also been found that the above-mentioned problem is likely to occur due to changes in the amount of replenishment of the stabilizing liquid, seasonal fluctuations, and concentration of the processing liquid due to fluctuations in the throughput. [Object of the Invention] Therefore, an object of the present invention is to provide a method for processing a photosensitive material that can form a color photographic image that is stable during long-term storage without using any washing water. Another object of the present invention is to provide a method for processing photosensitive materials that does not use any washing water and has low energy costs and low pollution loads. [Structure of the Invention] As a result of extensive research, the present inventors have developed a polymer or copolymer ultraviolet absorbing polymer latex having repeating units derived from a monomer represented by the following general formula []. After the silver halide color photographic light-sensitive material containing silver halide is subjected to color development processing, it is processed with a processing solution having fixing ability, and then processed in a stabilization processing step without substantially including a water washing step, and used in the stabilization processing step. It has been found that the above object can be achieved when the stabilizing liquid contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions. General formula [] In the formula, R ₁ represents a hydrogen atom, a halogen atom, a methyl group, or a cyano group, R ₂ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and X represents -CONH-, -COO - or a phenylene group, A represents a linking group represented by an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Y represents -COO-, -OCO
−, −CONH−, −NHCO−, −SO ₂ NH−, −
Represents NHSO ₂ -, -SO ₂ - or -O-. Further, m and n each represent an integer of 0 or 1. Q represents an ultraviolet absorbing group represented by the following general formulas [] to []. General formula [] In the formula, R ₃ and R ₄ each have a hydrogen atom and 1 carbon atom.
It represents an alkyl group of ˜20 or an aryl group of 6 to 20, and R ₃ and R ₄ may be the same or different from each other, but do not simultaneously represent a hydrogen atom. Furthermore, R ₃ and R ₄ may be combined and integrated, in which case they represent an atomic group necessary to form a cyclic amino group. R ₅ is a cyano group, -COOR ₇ -,
−CONHR ₇ , −COR ₇ or −SO ₂ R ₇ ;
R ₆ represents a cyano group, -COOR ₈ , -CONHR ₈ , -COR ₈ or -SO ₂ R 8 , and R ₇ and _{R 8 each} represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Furthermore, R ₇ and R ₈ may be combined and integrated, and when combined, they represent 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,5
- Represents an atomic group necessary to form the nucleus of dioxocyclopentane or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexene. However, at least one of R ₃ , R ₄ , R ₅ , and R ₆ shall be bonded to the vinyl group via the above-mentioned linking group. General formula [] In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
Aryl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, amino group, carbon Alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms,
represents a hydroxy group, cyano group, nitro group, acylamino group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R ₉ and R ₁₀ ,
R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , or R ₁₂ and R ₁₃ may be closed to form a 5- to 6-membered ring. R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ₁₅ is a cyano group, -COOR ₁₇ , -CONHR ₁₇ , -
Represents COR ₁₇ or −SO ₂ R ₁₇ . R ₁₆ is a cyano group, -COOR ₁₈ , -CONHR ₁₈ , -
Represents COR ₁₈ or −SO ₂ R ₁₈ . R ₁₇ and R ₁₈ each represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. However, at least one of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is bonded to the vinyl group via the above-mentioned linking group. General formula [] In the formula, R ₁₉ to _{R 23} have the same meaning as R ₉ to R ₁₃ , and R ₁₉ ,
At least one of R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃
One is bonded to the vinyl group via the aforementioned X (-CONH-, -COO- or phenylene group). In a still more preferred embodiment, the object of the present invention is further effectively achieved by the stabilizing liquid used in the stabilization treatment step containing a chelating agent having a chelate stability constant of 6 or more with respect to iron ions. We also found that The present invention will be explained in detail below. In the case of a continuous process in which stabilization treatment that substantially omits the water washing process is performed directly from treatment with a fixing or bleach-fixing solution, as described above, fixing solution or bleach-fixing solution components, soluble silver complex salts and their Large amounts of decomposition products are carried into the stabilizing liquid, which primarily degrades the long-term stability of the photographic image. Therefore, in order to maintain the long-term stability of color images, it is necessary to process the photosensitive material so that no fixer or bleach-fixer components, soluble silver complex salts, or their decomposition products remain in the photosensitive material, and generally perform sufficient washing with water. In the case of stabilization treatment without washing with water, the methods used include increasing the number of tanks and replenishing a large amount of stabilizing liquid.
However, these methods contradict the objectives of cost reduction and low pollution as described above, and cannot be said to be preferable methods. On the other hand, many studies have been conducted to try to solve the above problems by changing couplers in photosensitive materials, but these efforts have mainly focused on the decrease in density of cyan images under high temperature and high humidity, and the lack of light in yellow images. Although it was effective in improving the fading property, it had no effect on the generation of yellow stain caused by light. There is also a known method of using ultraviolet absorbers to prevent photo images from discoloring and fading due to ultraviolet rays, but although they may be effective in preventing discoloration and fading of images in the short term, the ultraviolet rays may be too strong or the images may not be stored for long periods of time. In such cases, the effect is completely lost, and in fact, UV absorbers have problems such as being more likely to cause stains due to heat, UV rays, and humidity. Conventional methods completely prevent yellow stains caused by light. I couldn't do that. As a result of intensive research, the present inventors have discovered a method for effectively preventing the aging stability of dye images of photographic light-sensitive materials, particularly yellow stain caused by light. The present invention will be explained in more detail below. The ultraviolet absorbing polymer latex of the present invention is
It is a polymer or copolymer having a repeating unit derived from a monomer represented by the general formula []. General formula [] In the formula, R ₁ represents a hydrogen atom, a halogen atom, a methyl group, or a cyano group, and R ₂ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, isopropyl group, n-butyl group, etc.) or a chlorine atom,
X represents -CONH-, -COO- or a phenylene group, and A represents an alkylene group having 1 to 20 carbon atoms (e.g., methylene group, ethylene group, trimethylene group, 2-hydroxytrimethylene group, pentamethylene group, hexane group) methylene group, ethylethylene group, propylene group, decamethylene group, etc.) or an arylene group having 6 to 20 carbon atoms (e.g. phenylene group, etc.), and Y represents -
COO−, −OCO−, −CONH−, −NHCO−, −
SO ₂ NH−, −NHSO ₂ −, −SO ₂ −, or −O−
represents. Further, m and n each represent an integer of 0 or 1. Q represents an ultraviolet absorbing group represented by the following general formula [], [] or []. General formula [] In the formula, R ₃ and R ₄ each have a hydrogen atom and 1 carbon atom.
~20 alkyl groups (e.g. methyl, ethyl,
n-butyl group, n-hexyl group, cyclohexyl group, n-decyl group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group group, N,N-diethylaminopropyl group, cyanoethyl group, phenethyl group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3
-(2,4-di-t-amylphenoxy)propyl group, ethoxycarbonylmethyl group, 2-(2-
hydroxyethoxy)ethyl group, 2-furylethyl group, etc.), or an aryl group having 6 to 20 carbon atoms (such as tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-
amyl phenyl group, naphthyl group, etc.), and R ₃ and R ₄ may be the same or different from each other, but do not represent a hydrogen atom at the same time. Furthermore
R ₃ and R ₄ may be combined, in which case a cyclic amino group (e.g. piperidino group, morpholino group,
represents an atomic group necessary to form a pyrrolidino group, hexahydroazepino group, piperazino group, etc.). R ₅ is a cyano group, −COOR ₇ −, −CONHR ₇ , −
COR ₇ or -SO ₂ R ₇ , R ₆ is a cyano group, -COOR ₈ , -CONHR ₈ , -COR ₈ or -SO ₂
R ₈ represents an alkyl group having 1 to 20 carbon atoms, and _an aryl group having 6 to ₂₀ carbon atoms,
The alkyl group and aryl group represented by R ₃ or R ₄ have the same meaning. Furthermore, R ₇ and R ₈ may be combined and integrated, and when combined, R 7 and R 8 may be combined into a 1,3-dioxocyclohexane ring (for example, dimedone, 1,3-
dioxo-5,5-diethylcyclohexane, etc.),
1,3-diaza-2,4,6-trioxocyclohexane ring (e.g. barbituric acid, 1,3-dimethylbarbituric acid, 1-phenylbarbituric acid, 1-methyl-3-octylbarbituric acid, 1-ethyl-3-octylbarbituric acid,
1-ethyl-3-octyloxycarbonylethylbarbituric acid, etc.), 1,2-diaza-3,5
-Dioxocyclopentane ring (e.g. 1,2-diaza-1,2-dimethyl-3,5-dioxocyclopentane, 1,2-diaza-1,2-diphenyl-3,5-dioxocyclopentane, etc. ), or a 2,4-diaza-1-alkoxy-3,5-dioxocyclohexene ring (e.g., 2,4-diaza-1-ethoxy-4-ethyl-3,5-dioxocyclohexene, 2,4-diaza-1-ethoxy-4-ethyl-3,5-dioxocyclohexene, represents an atomic group necessary to form diaza-1-ethoxy-4-[3-(2,4-di-t-amylphenoxy)propyl]-3,5-dioxocyclohexene, etc.). Furthermore, at least one of R ₃ , R ₄ , R ₅ and R ₆
One is assumed to be bonded to the vinyl group via the above-mentioned linking group. In the general formula [], preferably R ₃ and R ₄ each represent an alkyl group having 1 to 20 carbon atoms, R ₅ represents a cyano group or -SO ₂ R ₇ , and R ₆ represents a cyano group or -COOR ₈ represents. R ₇ and R ₈ each represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Particularly preferably R ₃ and R ₄ in the general formula []
represents an alkyl group having 1 to 6 carbon atoms, and R ₅ is -
It represents SO ₂ R ₇ and R ₆ represents -COOR ₈ . R ₇ is an optionally substituted phenyl group (e.g. phenyl group,
tolyl group, etc.), and R ₈ represents an alkyl group having 1 to 20 carbon atoms. General formula [] In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₅ each represent a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an alkyl group having 1 to 20 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-amyl group, t-amyl group, n-octyl group, t-octyl group, methoxyethyl group, ethoxypropyl group,
hydroxyethyl group, chloropropyl group, benzyl group, cyanoethyl group, etc.), aryl group having 6 to 20 carbon atoms (e.g. phenyl group, tolyl group, mesityl group, chlorophenyl group, etc.), alkoxy group having 1 to 20 carbon atoms (e.g. Methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, 2-
Ethylhexyloxy group, methoxymethoxy group,
methoxyethoxy group, ethoxyethoxy group, etc.),
Aryloxy group having 6 to 20 carbon atoms (e.g. phenoxy group, 4-methylphenoxy group, etc.), alkylthio group having 1 to 20 carbon atoms (e.g. methylthio group, ethylthio group, propylthio group, n-octylthio group, etc.), carbon Arylthio group of number 6 to 20 (e.g. phenylthio group, etc.), amino group, carbon number 1
-20 alkylamino groups (e.g. methylamino group, ethylamino group, benzylamino group, dimethylamino group, diethylamino group, etc.), carbon number 6 -
20 arylamino groups (e.g., anilino group, diphenylamino group, anisidino group, toluidino group, etc.), hydroxyl group, cyano group, nitro group, acylamino group (e.g., acetylamino group, etc.), carbamoyl group (e.g., methylcarbamoyl group) ,
dimethylcarbamoyl group, etc.), sulfonyl group (e.g., methylsulfonyl group, phenylsulfonyl group, etc.), sulfamoyl group (e.g., ethylsulfamoyl group, dimethylsulfamoyl group, etc.),
Sulfonamide group (e.g., methanesulfonamide group, etc.), acyloxy group (e.g., acetoxy group, benzoyloxy group, etc.), or oxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, etc.)
represents R ₉ and R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ or
R ₁₂ and R ₁₃ may be closed to form a 5- or 6-membered ring (eg, methylene dioxo group, etc.). _R14 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g.
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-amyl group, n-octyl group, etc.). R ₁₅ is a cyano group, -
COOR ₁₇ , −CONHR ₁₇ , −COR ₁₇ or −SO ₂ R ₁₇
, R ₁₆ is a cyano group, -COOR ₁₈ , -
CONHR ₁₈ , −COR ₁₈ or −SO ₂ R ₁₈ ;
R ₁₇ and R ₁₈ are each an alkyl group as described above,
Represents an aryl group. Furthermore, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
At least one of R ₁₆ shall be bonded to the vinyl group via the above-mentioned linking group. In the general formula [], R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom, or a carbon number 1
-20 alkyl group, C6-20 aryl group,
Alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms, hydroxy group, acylamino group, carbamoyl group, acyloxy group , represents an oxycarbonyl group, and R ₉ and
R ₁₀ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , or R ₁₂ and R ₁₃ may be ring-closed. R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ₁₅ represents a cyano group, -
COOR ₁₇ , −CONHR ₁₇ , −COR ₁₇ or −SO ₂ R ₁₇
, R ₁₆ is a cyano group, -COOR ₁₈ , -
CONHR ₁₈ , −COR ₁₈ or −SO ₂ R ₁₈ ;
R ₁₇ and R ₁₈ each represent an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Furthermore, R ₉ ,
At least one of R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is bonded to the vinyl group via the linking group described above. General formula [] In the general formula [], R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ ,
R ₂₃ has the same meaning as R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ in the general formula [], and at least one of R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₃ is mentioned above. It is assumed that the vinyl group is bonded to the vinyl group via X. Representative examples of the ultraviolet absorbing monomer of the present invention represented by the general formula [] are shown below, but the compounds of the present invention are not limited thereto. The ultraviolet absorbent monomer according to the present invention can be subjected to an emulsion polymerization reaction in the presence of a polymerization initiator to form the desired homopolymer latex or copolymer latex. Therefore, specific examples of monomers as other copolymer components used when synthesizing the copolymer latex will be described below. That is, typical monomers include vinyl esters such as vinyl acetate, vinyl butyrate, vinyl ethylthioacetate, vinyl isobutyrate, vinyl chloroacetate, vinyl neodecanoate, vinyl benzoate, and vinyl benzyl acetate, acrylamide, and meth. Acrylamide, N-methylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-
(isobutoxymethyl)acrylamide, N-(isobutoxymethyl)methacrylamide, N-(m
-hydroxyphenyl) methacrylamide, N-
(1,1-dimethyl-3-dimethylaminopropyl)acrylamide, N,N-di(cyanomethyl)acrylamide, N-methylmethacrylamide, N-(2-amino-2-methylpropyl)methacrylamide, N-(2 -hydroxypropyl)
Methacrylamide, N,N-di(cyanomethyl)
Methacrylamide, N-isopropylmethacrylamide, N,N-dimethylmethacrylamide,
N,N-dimethylacrylamide, 3-[3-(dimethylamino)propyl]acrylamide, 3-
2-(dimethylamino)ethyl]acrylamide,
3-[2-(dimethylamino)ethyl]methacrylamide, N-[3(3-chloropropionamide)
propyl] vinylamide such as methacrylamide, acrylonitrile, methacrylonitrile, 3-
Vinyl nitriles such as butene nitrile and 2-chloroacrylonitrile, vinyl ketones such as methyl vinyl ketone and diacetone acrylamide, vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride, allyl methyl ether, allyl phenyl ether, 2-chlorovinyl methyl Ether, vinyl ether such as butyl vinyl ether, methyl vinyl ether, acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, 2-dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, t-pentyl acrylate, n-pentyl acrylate, 3-pentyl acrylate , benzyl acrylate, t-butyl methacrylate, 1,1-dihydroperfluorobutyl acrylate, benzyl methacrylate, 3-oxo-n-butyl acrylate, methyl-α-bromoacrylate, t-butyl acrylate, 4-
Chlorobutyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, cyclohexyl methacrylate,
2-norbornylmethyl acrylate, 2-(p
-Toluenesulfonyloxy)ethyl acrylate, 2-norbornylmethyl methacrylate, 2
-Chloroethyl methacrylate, 2-chloroethyl acrylate, ethyl methacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 3-oxo-
n-butyl methacrylate, isopropyl methacrylate, lauryl acrylate, methyl-α-
Chloroacrylate, methyl methacrylate, 2
-Methyl-2-nitropropyl acrylate, 5
-Norbornene-2-isomethyl methacrylate, 5-(or 6-)methylmercapto-2-norbornylmethyl methacrylate, 3-methyl-
2-norbornylmethyl methacrylate, 4-methyl-2-propylpentyl acrylate, n-
Octyl acrylate, n-octadecyl acrylate, n-octadecyl methacrylate, 2-
Ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, n-octyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-methoxy-methoxyethyl acrylate, ethyl acrylate,
Propyl acrylate, 2-cyanoethyl acrylate, 2-chloro-n-propyl acrylate, dicyclopentynylacrylate, 2,2,
2-trifluoroethyl acrylate, phenyl acrylate, isopropyl acrylate, n-
Propyl methacrylate, 3-chloropropyl acrylate, n-hexyl acrylate, sec-
Butyl acrylate, 2-(methylsulfinyl)
Ethyl acrylate, 2-(ethylsulfinyl)
Mention may be made of monomers such as α,β-unsaturated acids or esters such as ethyl acrylate, 2,2-dimethylbutyl acrylate, neohexyl acrylate, 3-thiapentyl acrylate, 3-thiapentyl methacrylate, and the like. Also, 2-acrylamido-2-methylpropane-1-sulfonic acid and its sodium salt, 3
-methacryloyloxypropane-1-sulfonic acid and its sodium salt, 3-acryloyloxypropane-1-sulfonic acid and its sodium salt, 4-acryloyloxybutane-2-sulfonic acid and its sodium salt, acotinic acid,
4-Acryloyloxybutane-1-sulfonic acid and its sodium salt, 3-acryloyloxy-1-methylpropane-1-sulfonic acid and its sodium salt, citraconic acid, 3-allyloxy-2-hydroxypropanesulfonic acid and its sodium salt salt, α-chloroacrylic acid, 3-
Acryloyloxypropionic acid, itaconic acid,
Maleic acid, mesaconic acid, crotonic acid, 3-acrylamidopropane-1-sulfonic acid and its potassium salt, p-styrenesulfonic acid and its sodium salt, vinylphenylmethanesulfonic acid and its sodium salt, 3-methacryloyloxypropane -1-Methyl-1-sulfonic acid and its sodium salt, 4-methacryloyloxybutane-1-sulfonic acid and sodium salt, 2-methacryloyloxyethyl-1-sulfonic acid and sodium salt, 3-methacryloyloxypropane -1-Sulfonic acid and its salts with zinc, 2-methacryloyloxyethyl-
Hydrophilic vinyl monomers such as 1-sulfonic acid can also be used. Furthermore, U.S. Patent Nos. 3459790 and 3488708
No. 3554987, No. 4215195, No. 4215195, No.
Crosslinkable monomers disclosed in No. 4247673 and the like may also be used. The polymer latex according to the present invention is produced by an emulsion polymerization method, and the solvent used in this polymerization reaction is water and a water-miscible solvent, such as methanol, ethanol, propanol, isopropanol, butanol, tetrahydrofuran,
A mixed solvent with N,N-dimethylformamide, acetone, dimethyl sulfoxide, etc. is used. Examples of polymerization initiators used in the polymerization reaction include hydrogen peroxide, t-butyl hydroperoxide, etc., and 2,2'-azobis(2-amidinopropane) hydroperoxide as a water-soluble azo type polymerization initiator. Examples include chloride, 4,4'-azobis-4-cyanovaleric acid, and the like. Furthermore, known nonionic, anionic, or cationic surfactants may be used to stabilize the latex. Next, specific examples of preferred compositions of the polymer or copolymer ultraviolet absorber used in the present invention will be shown.

[Table] Rimmer

[Exemplary compounds]

(1) 2-Methyl-4-isothiazolin-3-one (2) 5-chloro-2-methyl-4-isothiazolin-3-one (3) 2-methyl-5-phenyl-4-isothiazolin-3-one (4) 4-bromo-5-chloro-2-methyl-4-
Isothiazolin-3-one (5) 2-Hydroxymethyl-4-isothiazolin-3-one (6) 2-(2-ethoxyethyl)-4-isothiazolin-3-one (7) 2-(N-methyl-carbamoyl )-4-isothiazolin-3-one (8) 5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-isothiazoline-
3-one(9) 5-chloro-2-(2-phenylethyl)-4
-isothiazolin-3-one (10) 4-methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one (11) 1,2-benzisothiazolin-3-one (12) 2- (2-bromoethyl)-1,2-benzisothiazolin-3-one (13) 2-methyl-1,2-benzisothiazolin-3-one (14) 2-ethyl-5-nitro-1,2-benzisothiazoline -3-one (15) 2-benzyl-1,2-benzisothiazolin-3-one (16) 5-chloro-1,2-benzisothiazolin-3-one These exemplified compounds are described in U.S. Pat.
No. 2767172, No. 2767173, No. 2767174, No. 2767172, No. 2767173, No. 2767174, No.
2870015, British Patent No. 848130, French Patent No. 1555416, etc., the synthesis method and examples of application to other fields are described. There are also commercially available products such as Topside 300,
Topside 600 (manufactured by Permakem Asia),
It can be obtained under the trade names of Fine Inside J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.) and Proxel GXL (manufactured by ICI Corporation). The amount of the above compound used is 0.01 to 1 per stabilizing solution.
Can be used in the range of 50g, preferably
Adding 0.05-20g gives good results. Water-soluble metal salts include Ba, Ca, Ce, Co,
In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg,
It is a metal salt of Al or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, lylate, or acetate, or as a water-soluble chelating agent. The amount used is 1×10 ^-4 to 1× per stabilizing liquid.
10 ^-1 mol, preferably 4 x 10 ^-4 to 2
x10 ^-2 mol, more preferably in the range of 8 x 10 ^-4 to 1 x 10 ^-2 mol. Things added to the stabilizing bath of the present invention include:
In addition to the above compounds, optical brighteners, organic sulfur compounds,
Water droplet prevention agents such as onium salts, hardeners, quaternary salts, polyethylene oxide derivatives, siloxane derivatives, PH regulators such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, etc. It is optional to add various additives to improve and extend the processing effect, such as organic solvents such as methanol, ethanol, and dimethyl sulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone adjusting agents. When the method for supplying the stabilizing liquid in the stabilization treatment step according to the present invention is a multi-tank countercurrent system, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The above compounds can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives are added to the stabilization liquid supplied to the stabilization tank, and then added to the stabilization liquid to be supplied to the stabilization tank. There are various methods, such as adding it to the pre-bath of the stabilization process, or including it in the photosensitive material to be processed and making it exist in the stabilization tank.
It may be added by any method. In the present invention, the pH value of the treatment liquid in the stabilizing bath is preferably in the range of PH4 to 8. this is
If the pH is lower than 4, silver sulfide is more likely to occur, causing problems such as filter clogging. Also PH8
Above this level, limescale and microorganisms are likely to occur, so the stabilizing bath of the present invention is used within the pH range of 4 to 8. Further, the pH can be adjusted using the above-mentioned pH adjusting agent. The processing temperature during stabilization treatment is 15℃ ~ 60℃
Preferably, the temperature is in the range of 20°C to 45°C. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes, and the earlier the tank, the shorter the treatment time, and the later the tank, the longer the treatment time. is preferred. Although there is no need for any water washing treatment before or after the stabilization treatment according to the present invention, surface cleaning by rinsing with a small amount of water within an extremely short period of time within the above range, or surface cleaning with a sponge, stabilization of images, and surface cleaning of photosensitive materials. A treatment tank can be provided to adjust the physical properties.
Examples of the agent for stabilizing the image and adjusting the surface properties of the photosensitive material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds are also generally used at a concentration of about 0.1 g to about 30 g per color developer, preferably from about 1 g to about 1.5 g per color developer. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. Particularly useful primary aromatic amino color developers are N,N'-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful examples include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-
Dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-
N,N'-diethylaniline, 4-amino-N-
Examples include (2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
Alkali agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, and the like can also be optionally contained. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced during development and converts it into silver halide. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. . The most preferred organic acids used to form such metal complex salts of metal acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)N,N',N'-triacetic acid sodium salt [18] Propylenediaminetetra Sodium acetate [19] Sodium nitrilotriacetate [20] Sodium cyclohexanediaminetetraacetate The bleaching solution used contains the metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. can. As additives, in particular alkali halides or ammonium halides,
Rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to include metal salts and chelating agents. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylants, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, Sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and aluminum hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. In the processing of the present invention, silver may be recovered by a known method from processing solutions containing soluble silver complex salts, such as fixing solutions, bleach-fixing solutions, as well as stabilizing solutions.
For example, electrolysis method (described in French Patent No. 2299667), precipitation method (described in JP-A-52-73037, German Patent No. 2331220), ion exchange method (described in JP-A-51-17114) The method described in German Patent No. 2548237) and the metal substitution method (described in British Patent No. 1353805) can be effectively used. The photosensitive material that can be applied to the present invention uses an internal development method (U.S. Pat.
2376679, see specification No. 2801171), as well as
External development method in which a coloring agent is contained in the developer (U.S. Patent No. 2252718, U.S. Patent No. 2592243, U.S. Patent No.
2590970).
Further, as the coloring agent, any coloring agent generally known in the art can be used. Cyan coloring agents include those based on a naphthol or phenol structure and forming indoaniline dyes through coupling; magenta coloring agents include those having a 5-pyrazolone ring with an active methylene group as a glide structure; yellow coloring agents Examples include benzoylacetanilide, pivalylacetanilide with active methylene chain,
Those having an acylacetanilide structure, etc., with or without a substituent at the coupling position can be used. Thus, as the coloring agent, both so-called 2-equivalent type couplers and 4-equivalent type couplers can be applied. As the silver halide emulsion that can be used, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used. It can be something. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. Silver halide emulsifiers include stabilizers, sensitizers, hardeners,
It may contain conventional photographic additives such as sensitizing dyes and surfactants. The support may be anything such as polyethylene coated paper, triacetate film, polyethylene terephthalate film, white polyethylene terephthalate film, etc. The processing method of the present invention can be applied to photosensitive materials such as color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and color reversal paper. [Examples] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Reference example: On a paper support laminated with polyethylene,
The following layers were sequentially coated from the support side to prepare silver halide color photographic material samples Nos. 1 to 10. Layer 1 1.2 g/m ² gelatin, 0.32 g/m ² (silver equivalent,
(same below) blue-sensitive silver chlorobromide emulsion and 0.50g/
0.80 g/m ² dissolved in m ² of dioctyl phthalate
A layer containing the following yellow coupler (Y-1). Layer 2 Intermediate layer consisting of 0.7 g/m ² gelatin. Layer 3 The following magenta coupler (M- ¹ ) was added to 0.62 g/m ² dissolved in 1.25 g/m 2 gelatin, 0.22 g/m ² green-sensitive silver chlorobromide emulsion and 0.30 g/m ² dioctyl phthalate. Containing layer. Layer 4 Intermediate layer consisting of 1.2 g/m ² gelatin. Layer 5 0.45 ^g of ^the following cyan coupler ⁽ C
-1) A layer containing. Layer 6 UV absorber dissolved in 1.0 g/m ² of gelatin and 0.20 g/m ² of dioctyl phthalate (Table 1
). Layer 7 Layer containing 0.5 g/m ² of gelatin. Note that sodium 2,4-dichloro-6-hydroxy-s-triazine was used as a hardening agent in layers 2 and 4.
and 0.017 per gram of gelatin in and 7, respectively.
g. Next, these samples were subjected to wedge exposure using a conventional method, and then subjected to the following development treatment. Standard processing steps (processing temperature and processing time) [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 38℃ 1 minute 30 seconds [3] Stabilization treatment or 25-30℃ 3 minutes washing treatment [4] Drying 75-80℃ for about 2 minutes Processing liquid composition

[Preparation method of monomers (5) and (40)]

3.0 g of monomer (5) or (40) was mixed and dissolved in 24.0 g of dioctyl phthalate and 6.0 g of ethyl acetate at 65°C, and then 1.0 g of triisopropylnaphthalene soda salt and 5% Gel solution were heated to 50°C.
It was added to 100 c.c. and dispersed with a colloid mill.

[Color development tank liquid]

Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -Aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostyl benzsulfonic acid derivative 1.0g Potassium hydroxide 2.0g Water was added to make 1. [Color developer replenisher ] Benzyl alcohol 20ml Ethylene glycol 20ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g Polyphosphoric acid (TPPS) 3.0g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) -Aniline sulfate 7.0g Fluorescent brightener (4,4'-diaminostyl benzsulfonic acid derivative 1.5g Potassium hydroxide 3.0g Water was added to bring the total volume to 1. [Bleach-fix tank solution] Ethylenediaminetetraacetic acid 2nd Iron ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Water was added to bring the total volume to 1, and the pH was adjusted to 7.10 with potassium carbonate or glacial acetic acid. Bleach-fix replenisher A] Ferric ethylenediaminetetraacetate ammonium dihydrate 260g Potassium carbonate 42g Add water to bring the total volume to 1.The pH of this solution is
It is 6.7±0.1. [Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Water was added to bring the total volume to 1. The pH of this solution is
It is 4.6±0.1. Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution and the following stabilizing solution, and add the above color developer replenisher and bleach-fix replenisher A and B every 3 minutes while processing the color paper. A running test was conducted while replenishing a predetermined amount of stabilizing replenisher. The amount of replenishment is 324 ml per 1 m ² of color paper to the color developing tank, and the amount of bleach-fixing replenisher A and B to be refilled to the bleach-fixing tank.
Each was 25ml. The amount of bleach-fix solution added to the stabilizing solution per 1 m ² of color paper was 50 ml. [Stabilizing solution (same as replenisher)] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 1.0g Ammonium hydroxide (28% aqueous solution) 3.0g 1-hydroxyethylidene-1,1 '-diphosphonic acid 2.0g Water was added to bring the mixture to 1, and the pH was adjusted to 6.5 with sulfuric acid. For stabilization treatment, use the stabilization treatment bath of the automatic processor 2
The tank is a stable tank that allows continuous processing, and a two-tank countercurrent system is used in which replenishment is performed from the final tank (second layer) and overflow flows into the previous tank. Continuous processing was carried out until the total amount of bleach-fixing replenishers A and B was three times the capacity of the bleach-fixing replenisher tank, to obtain the following stabilized solution in a condensed state. Samples Nos. 11 to 15 listed in Table 2 were treated with the stabilizer in the same manner as in Example 1, and the yellow stain in the unexposed areas was measured. The results are shown in Table-2.

〔Effect of the invention〕

According to the present invention, the storage stability of a dye image obtained by processing a light-sensitive material, particularly the generation of yellow stain due to light, is improved, and washing water is not required for processing the light-sensitive material. Example 3 A multilayer color photosensitive material was prepared on a cellulose triacetate film support, consisting of each layer having the composition shown below. 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (gelatin layer) 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide (silver iodide: 4.0 mol%) Average grain size 0.4 μm Silver coating amount: 0.6 g/m ² Sensitizing dye (below)...for 1 mole of silver 6×10 ^-5 sensitizing dye (below)...for 1 mole of silver Cyan coupler (below)... 0.038 mol per mol of silver 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide (Silver iodide: 5.5 mol% Average grain size 1.0μ
m)...Silver coating amount: 1.7 g/ ^m2 Sensitizing dye...3.5 x 10 ^-5 mol per mol of silver Sensitizing dye...1.0 x 10 ^-5 mol per mol of silver Cyan coupler (see below) )...0.015 mol per mol of silver 5th layer: Intermediate layer 6th layer same as the 2nd layer: 1st green-sensitive emulsion layer Silver iodobromide (Silver iodide: 6.0 mol% Average grain size 0.5μ
m) ... Silver coating amount 1.5 g/m ² Sensitizing dye (below) ... 3.3 x 10 ^-5 mol per mol of silver Sensitizing dye (below) ... 1.1 x 10 ^- to 1 mol of silver ⁵ mol Magenta coupler (see below) ...0.035 mol per mol of silver 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide (Silver iodide: 7.0 mol% Average grain size 1.0μ
m) ... Silver coating amount 1.5 g/m ² Sensitizing dye... 2.65 x 10 ^-5 mol per mol of silver Sensitizing dye... 0.89 x 10 ^-5 mol per mol of silver Magenta coupler (see below) ) ...0.02 mol per mol of silver 8th layer: Yellow filter layer Gelatin layer containing yellow colloidal silver in gelatin aqueous solution 9th layer: 1st blue-sensitive emulsion layer Silver iodobromide (silver iodide: 5.6 mol) % Average particle size 0.5μ
m)...Silver coating amount: 1.5 g/m ² Yellow coupler (below)...0.25 mol per 1 mol of silver 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide: 7.0 mol% average) Particle size 1.20μ
m)... Silver coating amount 0.90 g/m ² Yellow coupler (below)... 0.06 mol per 1 mol of silver 11th layer: 1st protective layer Silver iodobromide (Silver iodide: 1 mol % Average grain size 0.01μ
m) ... Silver coating amount 0.2g 0.01 mol of UV absorber dispersed with dioctyl phthalate and gelatin per 1 mol of silver Table (3)
Gelatin layer 12th layer containing an emulsified dispersion of: Second protective layer Trimethyl methacrylate particles (diameter 1.5 μm)
Gelatin layer containing In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. Sensitizing dye: anhydro-5,5'-dichloro-
3,3'-(γ-sulfopropyl)-9-ethyl-
Thiacarbocyanine hydroxide pyridium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4',5'-
Dibenzothiacaboanine hydroxide triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetradichloro-1,1'-diethyl-3,3'-di-
{β[β-(γ-sulfopropoxy)ethoxy]}
Ethylimidazolocarbocyanine hydroside sodium salt cyan coupler magenta coupler Yellow coupler (comparison) After photographing the photosensitive material using a Konica FS-1 camera (manufactured by Konishiroku Photo Industry Co., Ltd.), white stepwise exposure was applied using a KS-7 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). Then, processing was carried out continuously in an automatic processor according to the following steps. The automatic developing machine used was a modified hanging Filtum automatic developing machine type H4-220W-2 manufactured by Noritsu Koki Co., Ltd. Processing process (38℃) Number of tanks Processing time Color development 1 tank 3 minutes 15 seconds Bleaching 2 tanks 6 minutes 30 seconds Fixing 1 tank 6 minutes 30 seconds Stabilization treatment or 2 tanks 4 minutes 20 seconds Washing process Stabilization 1 tank 2 minutes 10 seconds The composition of the color developing solution used is as follows. Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 5g Potassium bromide 0.1g Potassium iodide 2mg Hydroxyamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N-
(β-hydroxylethyl)aniline sulfate
4.8g potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20g
Adjust the pH to 10.06 using % sulfuric acid. The composition of the color developer replenisher used is as follows. Potassium carbonate 40g Sodium hydrogen carbonate 3g Potassium sulfite 7g Sodium bromide 2.5×10 ^-3 mol Hydroxylamine sulfate 3.1g 4-amino-3-methyl-N-ethyl-N-
(β-hydroxylethyl)aniline sulfate
6.0g Potassium hydroxide 2g Add water to make 1, potassium hydroxide or 20
Adjust the pH to 10.12 using % sulfuric acid. The composition of the bleaching solution used is as follows. Iron ammonium ethylenediaminetetraacetate 100g Disodium ethylenediaminetetraacetate 10g Ammonium bromide 150g Glacial acetic acid 10ml Add water to make 1, and adjust to PH5.8 using aqueous ammonia or glacial acetic acid. The composition of the bleach replenishment solution used is as follows. Iron ammonium ethylenediaminetetraacetate 120g Disodium ethylenediaminetetraacetate 12g Ammonium bromide 178g Glacial acetic acid 21ml Add water to make 1, and adjust to PH5.6 using aqueous ammonia or glacial acetic acid. The composition of the fixer used is as follows. Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate
0.5g Sodium carbonate 10g Add water to make 1. The composition of the fixing replenisher used was as follows. Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate
0.8g Sodium carbonate 14g Add water to make 1. [Stabilizing solution (same as replenisher)] 5-chloro-2methyl-4-isothiazoline-
3-one 0.05g 2-octyl-4-isothiazolin-3-one
1.0g of water was added to make the solution 1, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. The composition of the stabilizing solution used is as follows. Formalin (37% aqueous solution) 2ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 5ml water to make 1. The composition of the stable replenishment solution used is as follows. Formalin (37% aqueous solution) 3 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7 ml water to make 1. For stabilization treatment, use the stabilization treatment bath of the automatic processor 2
The tank is a stable tank that allows continuous treatment, and a two-tank countercurrent system is used in which replenishment is performed from the final tank (second tank) and overflow flows into the previous tank. Continuous processing was carried out until the total amount of stabilizing replenisher used was three times the capacity of the stabilizing treatment tank, and the yellow stain in the unexposed areas of the photosensitive materials shown in Table (3) was measured. The results are shown in Table-3. The amount of each treatment solution replenished in the running test was adjusted and replenished as follows. Color development replenishment solution is color negative film 100
15.0 ml per cm ² of color developing bath is replenished, bleach replenishment solution is replenished to 18 ml bleach bath per 100 cm ² of color negative film, fixing replenishment solution is replenished 7 ml per 100 cm of color negative film to fixing bath, stabilizing solution The stabilizing bath was supplemented with 7 ml per 100 cm ² of stability replenishment solution and 11 ml per 100 cm of color negative film. In addition, 150 ml of water was poured into the washing bath per 100 cm ² of color negative film.

[Table] As is clear from Table 3, when the polymer latex ultraviolet absorber of the present invention was used for stabilization treatment in the running treatment of color negative film (sample No. 19), yellow stain was clearly large. It has been greatly improved.

Claims (1)

[Scope of Claims] 1. Color-forming silver halide color photographic light-sensitive material containing a polymer or copolymer ultraviolet absorbing polymer latex having a repeating unit derived from a monomer represented by the following general formula [] After development, processing is performed with a processing solution having fixing ability, followed by a stabilization processing step that does not substantially include a water washing step, and the stabilization solution used in the stabilization processing step has a high chelate stability with respect to iron ions. 1. A method for processing a silver halide color photographic material, comprising a chelating agent having a constant of 6 or more. General formula [] In the formula, R ₁ represents a hydrogen atom, a halogen atom, a methyl group, or a cyano group, R ₂ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and X represents -CONH-, -COO - or a phenylene group, A represents a linking group represented by an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and Y represents -COO-, -OCO
−, −CONH−, −NHCO−, −SO ₂ NH−, −
Represents NHSO ₂ -, -SO ₂ - or -O-. Further, m and n each represent an integer of 0 or 1. Q represents an ultraviolet absorbing group represented by the following general formulas [] to []. General formula [] In the formula, R ₃ and R ₄ each have a hydrogen atom and 1 carbon atom.
It represents an alkyl group of ˜20 or an aryl group of 6 to 20, and R ₃ and R ₄ may be the same or different from each other, but do not simultaneously represent a hydrogen atom. Furthermore, R ₃ and R ₄ may be combined and integrated,
In that case, it represents an atomic group necessary to form a cyclic amino group. R ₅ is a cyano group, −COOR ₇ −, −
CONHR ₇ −, −COR ₇ or −SO ₂ R ₇ ,
R ₆ represents a cyano group, -COOR ₈ , -CONHR ₈ , -COR ₈ or -SO ₂ R 8 , and R ₇ and _{R 8 each} represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Furthermore, R ₇ and R ₈ may be combined and integrated, and when combined, 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,
Represents an atomic group necessary to form the nucleus of 5-dioxocyclopentane or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexene. However, at least one of R ₃ , R ₄ , R ₅ , and R ₆ shall be bonded to the vinyl group via the above-mentioned linking group. General formula [] In the formula, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
Aryl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, amino group, carbon Alkylamino group having 1 to 20 carbon atoms, arylamino group having 6 to 20 carbon atoms,
represents a hydroxy group, cyano group, nitro group, acylamino group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R ₉ and R ₁₀ ,
R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , or R ₁₂ and R ₁₃ may be closed to form a 5- to 6-membered ring. R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ₁₅ is a cyano group, -COOR ₁₇ , -CONHR ₁₇ , -
Represents COR ₁₇ or −SO ₂ R ₁₇ . R ₁₆ is a cyano group, -COOR ₁₈ , -CONHR ₁₈ , -
Represents COR ₁₈ or −SO ₂ R ₁₈ . R ₁₇ and R ₁₈ each represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. However, at least one of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is bonded to the vinyl group via the above-mentioned linking group. General formula [] In the formula, R ₁₉ to _{R 23} have the same meaning as R ₉ to R ₁₃ , and R ₁₉ ,
At least one of R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃
One is assumed to be bonded to the vinyl group via the aforementioned X.