JPH0450580B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a silver halide color photographic light-sensitive material, and more specifically, a method for producing a silver halide color photographic light-sensitive material that improves deterioration of photographic properties and storage stability of the light-sensitive material, and has excellent formalin resistance. Regarding. In recent years, as new building materials, furniture, resin products, adhesives, clothing, etc. that emit harmful gases such as formaldehyde have come into widespread use in daily life, there have been more opportunities for photographic materials to come into contact with these harmful gases. There is. In general, internal silver halide color photographic light-sensitive materials have multiple silver halide emulsion layers that are sensitive to different regions of the spectrum and contain couplers that react with oxidation products of color developing agents to form dyes. That is, it is usually composed of a silver halide emulsion layer sensitive to blue light, green light, and red light and containing a yellow coupler, a magenta coupler, and a cyan coupler, respectively, on a support. There is. After exposure, yellow magenta and cyan dye images are formed in each of these silver halide emulsion layers by color development. In such a multilayer color photographic light-sensitive material, the best color image can be obtained only when each of the silver halide emulsion layers maintains a balance in terms of sensitivity and contrast. It is desirable that the photographic properties of the photographic light-sensitive material remain unchanged even during a long storage period before and after exposure and before development. If placed in a formaldehyde gas atmosphere prior to processing, the coupler will react with the formaldehyde and be consumed, producing undesirable reaction products, such as reducing color density and gamma, causing color staining, Alternatively, serious deterioration of photographic characteristics such as increased fogging may occur. Deterioration in photographic performance due to reaction with formaldehyde gas occurs with all couplers, but yellow couplers and magenta couplers are more susceptible than cyan couplers, but magenta couplers in particular are most affected. be done. In order to prevent such deterioration of photographic properties due to reaction with formaldehyde, it has been proposed to use, for example, a compound that is reactive with aldehyde and renders it harmless (hereinafter referred to as an aldehyde scavenger). ing. For example, Japanese Patent Publication No. 34675/1989 describes the use of compounds such as dimedone, N,N'-ethylene urea, and 2,3-dihydroxynaphthalene;
No. 53434 discloses acyclic ureas, and Japanese Patent Publication No. 51-23908 discloses hydantoin, allantoin derivatives, etc. However, certain formaldehyde-reactive compounds, when coexisting with silver halide emulsions and certain yellow couplers, have serious effects such as deteriorating the photographic performance of light-sensitive materials during coating stagnation and deteriorating the physical properties of coating solutions. It turned out that it had some drawbacks. Therefore, the first object of the present invention is to provide a method for producing a silver halide color photographic light-sensitive material that has excellent formaldehyde resistance and improved storage stability. It is an object of the present invention to provide a method for producing a silver halide color photographic light-sensitive material in which no change in fog occurs during the stagnation period of a coating solution containing a preparation containing an emulsion. A third object of the present invention is to provide a method for producing a silver halide color photographic material that does not cause fluctuations in the viscosity of a coating solution when a prepared coating solution containing a silver halide emulsion stagnates. be. As a result of various studies regarding the above, the present inventors prepared and stored a photographic coating solution, and then applied it.
A photographic coating comprising, on a support, a silver halide emulsion, a two-equivalent type yellow coupler represented by the following general formula [], and at least one formaldehyde-reactive compound represented by the following general formulas [A] to [D]. A method for producing a silver halide color photographic light-sensitive material in which at least one photosensitive layer is coated on a photosensitive coating solution, the method comprising: coating at least one halogenated silver halide color photographic material with the above-mentioned 2-equivalent yellow coupler immediately before coating the photographic coating solution; It has been found that the above object can be achieved by a method for producing a silver halide color photographic light-sensitive material in which a photographic coating solution is prepared by adding silver halide to a silver emulsion. General formula [] In the formula,
is a hydrogen atom or a halogen atom, R is an alkyl group or an aryl group, R ₁ is a halogen atom or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a sulfonamide group, a sulfamoyl group, an acylamino group, a carbamoyl group, or an ester group. represent. General formula [A] In the formula, X ₁ and X ₂ are oxygen atoms or imino groups,
R ₃ and R ₄ represent a hydrogen atom, an acyl group, or an alkyl group, R ₅ and R ₆ represent a hydrogen atom, a hydroxyl group, an amino group, an alkyl group, or an alkoxy group, and R ₅ and R ₆ are connected to each other for 5 to 6 A member-saturated carbocyclic nucleus may be formed. However, R ₃ and R ₄ are not methyl hydroxide, and when X ₁ and X ₂ are both oxygen atoms, and R ₅ and R ₆ are both groups other than amino, or R When ₅ and R ₆ are linked to form a 5- to 6-membered saturated carbocyclic nucleus, at least one of R ₃ and R ₄ is a hydrogen atom. General formula [C] In the formula, X ₅ is an oxygen atom or an imino group, R ₁₀ and R ₁₁ are a hydrogen atom, an acyl group or an alkyl group,
R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each represent a hydrogen atom, hydroxy, amino group, alkyl group or alkoxy group, and R ₁₂ and R ₁₃ and R ₁₄ and R ₁₅
may be linked to each other to form a 5- to 6-membered saturated carbocyclic nucleus. However, R ₁₀ and R ₁₁ are not methyl hydroxide, and when X ₅ is an oxygen atom and R ₁₂ and R ₁₃ and R ₁₄ and R ₁₅ are both groups other than an amino group, R ₁₂ and R ₁₃ and R ₁₄ and
When linked with R ₁₅ to form a 5- to 6-membered saturated carbon ring nucleus, at least one of R ₁₀ and R ₁₁ is a hydrogen atom. General formula [B] In the formula, X ₃ and X ₄ are oxygen atoms or imino groups,
R ₇ and R ₈ represent a hydrogen atom, an acyl group, or an alkyl group, and R ₉ represents an imino group or an alkyl group. However, when R ₇ and R ₈ are not methyl hydroxide, and when X ₃ and X ₄ are both oxygen atoms and R ₉ is an alkyl group,
At least one of R ₇ and R ₈ is a hydrogen atom. ) General formula [D] In the formula, X ₆ is an oxygen atom or an imino group, R ₁₆ and R ₁₇ are each a hydrogen atom or an alkyl group,
A is -NH( _CH2 ) _n -NHCO- (However, the nitrogen atom of A bonds with the carbonyl group of general formula [D]. m represents an integer of 1 or 2) or -
NHCO- (However, the nitrogen atom of A is the general formula [
D] is bonded to the carbonyl group. It has been known for some time that a formaldehyde-reactive compound can be added to a silver halide emulsion containing a yellow coupler, as disclosed in, for example, Japanese Patent Publication No. 23908/1983. however,
Although it was unexpected, some kind of
It has been found that only in coating solutions in which a specific formaldehyde-reactive compound is added to a silver halide emulsion containing an equivalent yellow coupler, changes occur in the photographic performance of the emulsion and the physical properties of the coating solution during stagnation of the coating solution. This is especially true in recent years, where high-speed coating and long-term continuous coating are generally used to improve productivity in the manufacturing process of silver halide color photographic materials, and the stagnation time of the prepared emulsion coating solution is long. If this tendency occurs, it must be said that it is a truly serious drawback that various performance deteriorations occur due to stagnation of the prepared emulsion coating solution as described above. According to the present invention, when at least 2 equivalents of yellow coupler is added immediately before coating a photographic coating solution containing a silver halide emulsion as described above, the photographic performance of the emulsion can be improved due to stagnation of the coating solution prepared as described above. The silver halide color photographic light-sensitive material produced in this manner has excellent formaldehyde resistance. The present invention will be explained in more detail below. The 2-equivalent yellow coupler used in the present invention can be represented by the above general formula []. In the above general formula [], preferably the alkyl group of R is a tert-butyl group, and the aryl group is a phenyl group. group, o-methoxyphenyl group or p-methoxyphenyl group. Also
R ₁ is preferably a halogen atom, such as a chlorine atom or a fluorine atom. Further, Y is preferably a hydrogen atom, and X is preferably a detachable group selected from the groups shown in (a) to (f) below. (a) -O.CO.R ₁₈ [In the formula, R ₁₈ represents an alkyl group, an alkenyl group, a phenyl group or a terpenyl group. ] (b) -O-R ₁₉ [In the formula, R ₁₉ represents an alkyl group, an aryl group or a heterocyclic group. ] [In the formula, Z ₁ represents a group of nonmetallic atoms required to form a saturated or unsaturated 4-, 5-, or 6-membered ring. ] [In the formula, Z ₂ represents a group of nonmetallic atoms required to form a saturated or unsaturated 4-, 5-, or 6-membered ring. ] [In the formula, Z ₃ represents a group of nonmetallic atoms required to form a saturated or unsaturated 4-, 5-, or 6-membered ring. ] (f) -S-R ₂₀ [wherein R ₂₀ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. ] Typical examples of these groups that can be separated during color development are listed below. 1.−OCOCH ₃ 7.−OCOCH ₁₀ H ₂₁ Next, typical examples of the yellow coupler according to the present invention will be given, but the present invention is not limited thereto. Next, the formaldehyde scavengers according to the present invention represented by the above general formulas [A] to [D] are preferably represented by the general formulas [A], [B] and [C], with [A] being particularly preferred. Specific examples are given below, but the invention is not limited thereto.

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(48)H ₂ NCONHCH ₂ CH ₂ NHCONH ₂ (49) CH ₃ HNCONHCH ₂ CH ₂ NHCONH ₂ (50) H ₂ NCONHCH ₂ NHCONH ₂ (51) H ₂ NCONH ₂ (52) H ₃ CHNCONHCH ₃ (53) CH ₃ HNCONH ₂ These compounds include, for example, butylene of
The Chemical Society of Japan,
Volume 39, pp. 1559-1567, pp. 1734-1738 (1966
It can be easily synthesized according to the method described in Hemitsche Berichte, Vol. 54B, pp. 1802-1833, pp. 2441-2479 (1921). According to the present invention, the effects of the present invention can be obtained by adding the above-mentioned 2-equivalent yellow coupler, for example as an oil-protected colloidal dispersion, to a silver halide emulsion containing a formaldehyde-reactive compound immediately before coating. ,Preferably,
It is desirable to add both the coupler colloid dispersion and the formaldehyde-reactive compound solution to the silver halide emulsion immediately before coating.
It is more effective to mix the two liquids and add them at the same time than to add the two liquids separately. Specifically, for example, it is possible to achieve the effects of concentrating the coating liquid and reducing the number of mixing devices. In the present invention, the term "immediately before application" refers to a period of time within which the effects of the present invention can be obtained, but it usually means within several minutes, preferably several seconds to several tens of seconds, before application of the preparation solution. The amount of the 2-equivalent yellow coupler used in the present invention is 10 ^-3 mol to 5.0 mol, preferably 10 ^-2 mol to 5.0 mol, per mol of silver halide. On the other hand, the amount of the formaldehyde-reactive compound added is from 10 ^-3 mol to 1 mol of silver halide.
10 ² mol, preferably 10 ⁻² mol to 10 mol. The method for dispersing the 2-equivalent yellow coupler according to the present invention includes a so-called alkaline aqueous dispersion method,
Various known methods can be used, such as a solid dispersion method and an oil-in-water emulsion dispersion method. As the oil-in-water emulsion dispersion method, a conventionally known method for dispersing hydrophobic additives such as couplers can be applied. Further, in the present invention, the 2-equivalent yellow coupler according to the present invention may be used in combination with any other 2-equivalent coupler or 4-equivalent coupler,
Furthermore, it may be used in combination with a so-called DIR type coupler that releases a compound that inhibits development in an imagewise manner during development. Regarding the above DIR compounds, for example, US Pat.
3227550, 3938996, 3227554, 4010035, British Patent No. 953454, etc., or U.S. Patent No.
O-aminophenyl azo couplers described in No. 3148062 are known, and any combination of these may be selected. In order to satisfy the photographic properties required for photographic light-sensitive materials, two or more of these couplers can be used together in the same layer of a photosensitive material completed by coating, or the same compound can be used in two different layers. Or it can be added to more layers. Further, as mentioned above, the formaldehyde-reactive compound according to the present invention is preferably mixed with a 2-equivalent yellow coupler and added to the silver halide emulsion immediately before coating. They can be added, for example, to protective layers, intermediate layers, filter layers or other auxiliary layers. When the formaldehyde-reactive compound according to the present invention is added to the coating solution in order to form the various constituent layers described above, it may be added after being dissolved in a solvent such as water or methanol. The silver halide color light-sensitive materials produced by the production method of the present invention include color negative films, color positive films, color reversal films, color aerial photographic films, color X-ray films, color photographic papers, and other internal silver halide color photographs. Includes all kinds of photosensitive materials. These silver halide color photographic light-sensitive materials are prepared by forming one or two coupler-containing silver halide emulsion layers on a support that has been subjected to corona discharge treatment, flame treatment, ultraviolet irradiation treatment, or subbing treatment, as required. The layers are formed by combining the above layers with an intermediate layer, a filter layer, an antihalation layer, a protective layer, etc. Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyethylene terephthalate film, polyamide film, polycarbonate film, polystyrene film, and the like. In the present invention, the hydrophilic colloids used to prepare the photosensitive emulsion of the photosensitive material include gelatin, colloidal albumin, agar, gum arabic, alginic acid, and cellulose acetate hydrolyzed to an acetyl content of 19 to 26%. , acrylamide, imidized polyacrylamide, zein, vinyl alcohol/vinyl cyanoacetate copolymer, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, etc. Included. The silver halide used in the above-mentioned silver halide color photographic light-sensitive materials includes conventional silver halide photographic emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used is included. These silver halide emulsions can be produced by various manufacturing methods including the usual manufacturing method, such as the direct mixing method, the simultaneous mixing method, or the method described in Japanese Patent Publication No. 46-7772 or the method described in U.S. Pat. No. 2,592,250. That is, forming an emulsion of silver salt grains consisting of at least a portion of the silver salt whose solubility is greater than that of silver bromide, and then at least a portion of the grains being treated with silver bromide salt or iodobromide. It can be prepared by any manufacturing method such as a so-called conversion emulsion manufacturing method such as converting it into a silver salt, or a Lippmann emulsion manufacturing method consisting of fine-grained silver halide having an average grain size of 0.1 μm or less. The silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as arylthiocarbamide, thiourea, aryl isothiocyanate, cystine, active or inactive selenium sensitizers, or active or inactive selenium sensitizers such as potassium chloroaurate, ori Noble metal sensitizers such as gold compounds such as trichloride, palladium compounds such as ammonium chloroparadate, platinum compounds such as potassium chloroplatinate, ruthenium compounds, rhodium compounds, iridium compounds, or such sensitizers. Sensitization can also be achieved using a combination of agents. This emulsion can also be sensitized with a reduction sensitizer. Furthermore, this emulsion may contain, for example, glycerin, 1,5
- dihydroxyalkanes such as pentanediol,
Ethylene bisglycolic acid ester, bisethoxydiethylene glycol succinate A water-dispersible particulate polymer compound obtained by emulsion polymerization, a wetting agent, a plasticizer, a film property improver, etc. can be contained. Coating aids such as imine compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides, bisesters of methanesulfonic acid, vinylsulfonyl type hardeners, saponins, sulfosuccinates, fluorescent brighteners, antistatic agents, etc. Various photographic additives such as antistain agents and antistain agents can be included. Furthermore, the blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide color photographic light-sensitive material according to the present invention each contain an appropriate sensitizing dye in order to impart photosensitivity to the desired wavelength range. optically sensitized. Various sensitizing dyes such as cyanine dyes, merocyanine dyes, and composite cyanine dyes can be used alone or in combination. Couplers used in the present invention include:
In addition to the above-mentioned couplers, for example, colorless couplers may be used, and so-called masking couplers having, for example, an arylazo group at the active site in the molecule may be used. Further, as couplers, yellow couplers are generally benzoylacetanilide type or pivaloylacetanilide type couplers, and magenta couplers are 3-acylamino-5-pyrazolone type or 3-anilino-5-pyrazolone type couplers. Good too. In addition, it may be a DIR coupler as mentioned above, or it may be used in combination with various couplers to improve photographic properties, and may be a so-called competing coupler, or a coupler used during development.
Compounds that release development inhibitors in response to image density, so-called development inhibitor-releasing compounds (German patent no.
No. 2362752, JP-A-49-77635, U.S. Patent No.
3632345, 3297445, and 3379529). The above-mentioned couplers that can be used in the present invention can be contained in various forms in the coating solution of the constituent layer containing the coupler. For example, Fischer type couplers are added in the form of a solution,
Further, the oil-soluble coupler may be dissolved in a coupler solvent and contained in the form of an emulsion. This coupler solvent is generally di-n
- using a water-immiscible high-boiling organic solvent such as butyl phthalate, benzyl phthalate, triphenyl phosphate, etc., with a concentration of 0.1 to 10% per part by weight of coupler;
It is used in parts by weight, particularly preferably from 0.5 to 2.0 parts by weight. Although various hardeners can be used in the silver halide color photographic light-sensitive material according to the present invention, formaldehyde-type hardeners are not desirable.
As the hardening agent, particularly preferred are vinylsulfonyl type hardening agents as described in Japanese Patent Application No. 54236/1983. Among these, the most satisfactory results are obtained when, for example, 1,2-divinylsulfonylethane is used. The silver halide color photographic light-sensitive material containing the formaldehyde-reactive compound according to the present invention has the advantage that it can reduce the decrease in color density that occurs during processing using a pre-hardening bath containing formaldehyde. have
Further, the above-mentioned compound according to the present invention selectively reacts with harmful gases such as formaldehyde gas, and prevents a decrease in color density, a decrease in gamma, and an increase in fog in silver halide color photographic light-sensitive materials caused by formaldehyde gas, and It is also possible to eliminate failures such as delays in development caused by inhibition of permeation of the developer due to abnormal hardening of gelatin caused by formaldehyde. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Example 1 A high-sensitivity blue-sensitive emulsion layer and a protective layer having the following composition were coated simultaneously on a cellulose triacetate film support by a slide hopper method. 1st layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, silver iodide 7
4-hydroxy-6-methyl-1.3.3a,7
-Tetrazaindene 1.0g and 1-phenyl-
10.0 mg of 5-mercaptotetrazole was added and prepared in a conventional manner to produce a highly sensitive blue-sensitive silver halide emulsion. Further, a mixture of 80 g of yellow coupler (example coupler, Y-13), 80 g of dibutyl phthalate, and 240 ml of ethyl acetate was dissolved by heating per mole of silver halide, and the solution was added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and then added to a colloid mill. The emulsified dispersion was added to prepare a highly sensitive blue-sensitive silver halide coating solution, which was coated to a dry film thickness of 2.0 μm. This emulsion contains 240 g of gelatin per mole of silver halide. 2nd layer: Protective layer A gelatin aqueous solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane per 100 ml was coated at a rate of 1.3 g/m ² of gelatin to give a dry film thickness of 1.2 μm. Sample 1 (comparative sample) 20 g of the formaldehyde-reactive compound shown in the above-mentioned exemplified scavenger compound (2) was dissolved in water,
After it was added to the prepared silver halide coating solution, it was allowed to stagnate in a liquid state at 42° C. for 4 hours, and then coated together with the protective layer coating solution. Sample 2 (Sample according to the present invention) The prepared coating solution of Sample 1 except for the coupler dispersion was allowed to stagnate in the same manner as described above, and after stagnation, the coupler dispersion was added to this emulsion using an in-line static mixer immediately before coating. and coating was carried out in the same manner as above. Sample 3 (Sample according to the present invention) The prepared coating solution of Sample 2 except for the coupler dispersion and the above-mentioned exemplified scavenger compound (2) was stagnated in the same manner as above, and after stagnation, this coating solution was added in-line immediately before coating. Using a static mixer, the coupler dispersion and the exemplified scavenger compound (2) were added and coated in the same manner as above. Sample 4 (Sample according to the invention) Coated in the same manner as Sample 3, except that the 2-equivalent yellow coupler in Sample 3 was replaced with Exemplary Coupler Y-7, and the formaldehyde-reactive compound was replaced with a compound of Exemplary Scavenger Compound (8). I went there. Sample 4' (comparative sample) The prepared coating solution of Sample 2 except for the compound of the exemplified scavenger compound (2) was allowed to stagnate in the same manner as above, and after stagnation, this coating solution was added to the in-line static mixer immediately before coating. Exemplary scavenger compound (2) was added using the same method as above, and applied in the same manner as above. The amounts and methods of addition of each compound in each of the above samples are as shown in Table 1 below.

[Color developer composition]

4-amino-3-methyl-N-ethyl- N-(β-hydroxyethyl)-aniline Sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxylamine 1/2 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate salt) 1.20g Potassium hydroxide 1.48g Add water to make 1. [Bleach solution composition] Iron ethylenediaminetetraacetate Ammonium salt 100g Ethylenediaminetetraacetic acid 2 Ammonium salt 10g Ammonium bromide 150g 10ml glacial acetic acid Add water to make 1, and use ammonia water. Adjust to PH6.0. [Fixer composition] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1 and adjust to PH6.0 using acetic acid. do. [Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5ml Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1.

[Table] As is clear from Table 2 above, Samples 2, 3, and 4 according to the present invention were found to have a higher degree of variation in fog due to stagnation of the prepared emulsion and a variation in the viscosity of the coating solution, compared to Sample 1 outside the present invention. It was found that it has an excellent improvement effect on. Example 2 A highly sensitive multilayer color negative film was prepared by repeating the following multilayer coating and drying process on a cellulose triacetate base using the slide hopper method. 1st step: The first layer is an antihalation layer containing black colloidal silver (dry film thickness 1 μm) based on pre-subtracted cellulose triacetate, and the second layer is 2,5-di-tert-
Two layers of gelatin intermediate layer (dry film thickness: 1 μm) containing octylhydroquinone were simultaneously coated at a coating speed of 100 m/min, and after drying, the film was wound onto a roll. 2nd step 1-hydroxy-N-{γ-(2,4-di-tert-amylphenoxy)-butyl}-2-naphthamide as a cyan coupler per mole of silver halide as a third layer on the coating base of the first step. 6.8× ^10-2
mole, 1-hydroxy- as a colored coupler
N-{δ-(2,4-di-tert-amylphenoxy)-butyl}-4-(2-ethoxycarbonylphenylazo)-2-naphthamide 1.7×10 ^-2 mol,
2-(1-phenyl-5-tetrazolylthio)-4-(2,4-di-
a red-sensitive silver iodobromide emulsion layer containing 4 x 10 ^-3 mol of tert-amylphenoxyacetamide)-1-indanone (silver iodobromide emulsion containing 8 mol% silver bromide, dry film thickness 6μ); As a fourth layer, an intermediate layer having the same composition as the second layer was simultaneously coated at a coating speed of 100 m/min, dried, and then wound up. Third step As a fifth layer on the coated base after completing the second step, 1-(2,4,6-trichloro)phenyl-3 is used as a magenta coupler per mole of silver halide.
-[3-(2,4-di-tert-amylphenoxy)
Acetamide] benzamide-5-pyrazolone
5.8×10 ^-2 mol, 1- as a colored coupler
(2,4,6-trichlorophenyl)-3-[3-
(Octatecenylsuccinimide)-2-chloro]anilide-4-(γ-naphthylazo)-5-pyrazolone 1.7×10 ^-2 mol and 2-(1-phenyl-5-tetrazolylthio) as a development inhibitor-releasing substance -4-(2,4-di-tert-amylphenoxyacetamide)-1-indanone in a low-sensitivity green-sensitive silver iodobromide emulsion layer containing 7 x 10 ^-5 mol (iodobromide containing 8 mol% silver iodide) Silver bromide emulsion, dry film thickness 3.5μ) The same compounds as the magenta coupler, colored coupler, and development inhibitor releasing substance in the fifth layer were used as the sixth layer at 1.1×10 ^-2 mol per mol of silver halide, respectively.
A highly sensitive green-sensitive silver iodobromide emulsion layer (silver iodobromide emulsion containing 6 mol of silver iodide, dry film thickness 2.5 μm) containing 5×10 ⁻³ mol and 2×10 mol and the seventh layer as the seventh layer. A total of 4 layers were simultaneously layered at a coating speed of 100 m/min: an intermediate layer with the same composition as the second layer, and a gelatin layer (dry film thickness 1μ) containing yellow colloidal silver and 2,5-di-tert-octylhydroquinone as the 8th layer. After coating and drying, it was rolled up. 4th step A silver iodobromide emulsion (average grain size 1.4μ; containing 7.5 mol% silver iodide) as the 9th layer is chemically sensitized with gold and sulfur sensitizers on the coated base that has completed the 3rd step. 4-hydroxy-6-methyl-1,
1.0 g of 3.3a,7-tetrazaindene was added and prepared in a conventional manner to produce a highly sensitive blue-sensitive silver halide emulsion. Further, per mole of silver halide, a mixture of 160 g of dibutyl phthalate and 480 ml of ethyl acetate was added to 200 g of yellow coupler Y-8, and dissolved by heating. After adding it to the inside and emulsifying and dispersing it in a colloid mill,
This dispersion from which ethyl acetate had been removed was added to the above-mentioned highly sensitive blue-sensitive silver halide emulsion to prepare a preparation solution. The 10th layer is 2-[3-cyano-3-(n
-dodecylaminocarbonyl)allylidene]-1
- A dispersion obtained by adding a mixture of 2 g of di-2-ethylhexyl phthalate and 2 ml of ethyl acetate to 2 g of ethylpyrodiline, heating and dissolving it, and dispersing this in an aqueous gelatin solution containing 0.6 g of sodium triisopropylnaphthalene sulfonate. was prepared as a coating solution for the intermediate layer. For the 11th layer, 4g of gelatin per 100ml, 1,
A coating solution for the protective layer containing 0.2 g of 2-bisvinylsulfonylethane was simultaneously coated in three layers together with the coating solutions for the 9th and 10th layers at a coating speed of 100 m/min and dried. After drying, the emulsion thickness of the 9th layer was approximately 5 μm, the intermediate layer thickness of the 10th layer was 1.5 μm, and the protective layer thickness of the 11th layer was 0.8 μm. 25 g of the exemplary scavenger compound (1) dissolved in water was added to the preparation solution of the high-sensitivity silver halide emulsion of the ninth layer, and the solution was stagnated at 40° C. for 5 hours. The 11th layer and the 3rd layer were applied simultaneously and dried. (Sample No. 5) In the same process of preparing the ninth layer coating solution, 50 g of the exemplified scavenger compound (1) was added to the high-sensitivity silver halide emulsion without adding the coupler dispersion. After stagnating in a solution state at 40° C. for 5 hours, the yellow coupler dispersion was mixed with an in-line static mixer immediately before coating, followed by multilayer coating and drying. (Sample No.
6) Furthermore, in the process of preparing the coating solution for the ninth layer, only the high-sensitivity silver halide emulsion was allowed to stagnate under the same conditions as above, and then the coupler dispersion and the aqueous solution of the exemplified scavenger compound (1) were added. The mixed solution was added to the high-sensitivity silver halide emulsion using an in-line static mixer immediately before coating, followed by multilayer coating and drying in the same manner. Sample No. 5 (referred to as sample No. 7) is a comparative sample other than the present invention, and both No. 6 and No. 7 are samples according to the present invention. Similarly, in the process of preparing the coating solution for the ninth layer, only the aqueous solution of the exemplary scavenger compound (1) was added immediately before coating, and multilayer coating was similarly performed and dried. (Sample No. 8 for comparison) The amounts and methods of addition of each compound in each of the above samples are as shown in Table 3 below.

[Table] After exposing each of the above samples to light in the same manner as in Example 1, the photographic properties were evaluated by color development treatment and the results are shown in Table 4 below.

[Table] As is clear from Table 4 above, Samples 6 and 7 according to the present invention have higher sensitivity of the blue-sensitive layer and lower fog than other comparative samples, and are effective in improving photographic properties. I understand. Furthermore, after exposing Samples 5 to 7 using an intensity scale sensitometer, the following treatments were performed. Processing-1: Place a liquid containing 300 c.c. of 35% glycerin aqueous solution at the bottom and place it in a sealed container filled with air to balance it with the liquid at 30°C.
Samples were kept for 3 days. Treatment-2: 35% glycerin aqueous solution 300 c.c.
A liquid containing 6 c.c. of a 40% formaldehyde aqueous solution was placed at the bottom, and the sample was held at 30° C. for 3 days in a closed container filled with air equilibrated with this. Treatment-3: The sample was kept in a thermostat at 55°C for 5 days. The maximum magenta color density was measured (measured at a wavelength of 547 nm) for the sample that had been subjected to the color development process, and compared to the sample that had not come into contact with formaldehyde gas that had undergone treatment-1, the sample that had undergone treatment-2 had been in contact with formaldehyde gas. The degree to which the maximum magenta color density decreases was investigated. The results are shown in Table 5 below. In the table, the maximum magenta color density represents the value obtained by subtracting the mask green density from the maximum green density.

[Table] From the above table, it can be seen that Samples 6 and 7 according to the present invention have superior formalin resistance to magenta images compared to the comparative sample.

[Table] Also from Table 6 above, samples 6 and 7 according to the present invention
It was found that the heat resistance and photographic properties were also superior to the comparative samples. Example 3 Exemplary scavenger compounds (22), (23), (38), (41), (44), (47) and (50) were used in place of exemplary scavenger compound (2) of sample 3 in Example 1. )
Samples 3a, 3b, 3c, and
3d, 3e, 3f and 3g were made. Regarding Samples 3a to 3g, the viscosity of the prepared emulsion coating solution and the photographic properties of each sample after exposure and color development were examined in the same manner as in Example 1. The results are shown in Table 7 together with Sample 3.

[Table] From Table 7, exemplary scavenger compounds (22),
Samples using (23), (38), (41), (44), (47), and (50) showed similar effects as samples using exemplary scavenger compound (2). Example 4 Example Scavenger Compound (1) of Sample 6 in Example 2 was mixed with the same amount of Example Scavenger Compound (22), (23), (38), (41), (44), (47) and ( 50)
High-sensitivity multilayer color negative film samples No. 6a, 6b, 6c, 6d, 6e, 6f and
6g was produced. After exposure, each sample was subjected to color development treatment in the same manner as in Example 1, and its photographic properties (sensitivity and fog) were evaluated. Further, after exposure using an intensity scale sensitometer in the same manner as in Example 2, processing-1 and processing-
2 and Treatment-3 were performed. Formalin resistance and heat resistance of the sample subjected to color development treatment were evaluated using the same measuring method as in Example 2. These results, including Sample 6, are shown in Table 8.

[Table] Table 8 shows exemplary scavenger compounds (22),
(23), (38), (41), (44), (47) and (50) are
This shows that it has the same effects as the exemplified scavenger compound (1) in terms of photographic properties, formalin resistance, and heat resistance.

Claims (1)

[Claims] 1. A photographic coating solution is prepared and stored, and then applied,
A photosensitive layer containing a silver halide emulsion, a 2-equivalent yellow coupler represented by the following general formula [], and at least one formaldehyde-reactive compound represented by the following general formulas [A] to [D] is provided on a support. A method for producing a silver halide color photographic light-sensitive material for coating, the method comprising: adding at least the above-mentioned 2-equivalent yellow coupler to the silver halide emulsion immediately before coating the photographic coating liquid; 1. A method for producing a silver halide color photographic light-sensitive material. General formula [] (wherein,
Y is a hydrogen atom or a halogen atom, R is an alkyl group or an aryl group, R ₁ is a halogen atom or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a sulfonamide group, a sulfamoyl group, an acylamino group, a carbamoyl group, or an ester represents a group. ) General formula [A] (In the formula, X ₁ and X ₂ are oxygen atoms or imino groups, R ₃ and R ₄ are hydrogen atoms, acyl groups or alkyl groups, and R ₅ and R ₆ are hydrogen atoms, hydroxyl groups,
It represents an amino group, an alkyl group, or an alkoxy group, and R ₅ and R ₆ may be connected to form a 5- to 6-membered saturated carbocyclic nucleus. However, when R ₃ and R ₄ are not methyl hydroxide, and when X ₁ and X ₂ are both oxygen atoms, and R ₅ and R ₆ are both groups other than amino groups, Alternatively, when R ₅ and R ₆ are linked to form a 5- to 6-membered saturated carbocyclic nucleus, at least one of R ₃ and R ₄ is a hydrogen atom. ) General formula [B] (In the formula, X ₃ and X ₄ are oxygen atoms or imino groups, R ₇ and R ₈ are hydrogen atoms, acyl groups, or alkyl groups, and R ₉ is imino groups or alkyl groups. However, R _{7 and} is never methyl hydroxide, and when X ₃ and X ₄ are both oxygen atoms and R ₉ is an alkyl group, at least one of R ₇ and R ₈ is a hydrogen atom.) General formula [C] _{( In the formula , _ _}
Represents hydroxy, amino group, alkyl group or alkoxy group, and further includes R ₁₂ , R ₁₃ and R ₁₄ .
and R ₁₅ may be mutually linked to form a 5- to 6-membered saturated carbocyclic nucleus. However, when R ₁₀ and R ₁₁ are not methyl hydroxide, and X ₅ is an oxygen atom, and R ₁₂ and R ₁₃ and R ₁₄ and R ₁₅ are both groups other than an amino group, or R ₁₂ and R ₁₃ and
When R ₁₄ and R ₁₅ are linked to form a 5- to 6-membered saturated carbon ring nucleus, at least one of R ₁₀ and R ₁₁ is a hydrogen atom. General formula [D] [In the formula, X ₆ is an oxygen atom or an imino group, R ₁₆ and R ₁₇ are each a hydrogen atom or an alkyl group, A is -NH(CH ₂ ) _n -NHCO-
The nitrogen atom of is bonded to the carbonyl group of general formula [D]. m represents an integer of 1 or 2) or -NHCO- (provided that the nitrogen atom of A is bonded to the carbonyl group of general formula [D]). ]