JPH06118551A - Manufacture of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fluctuation of sensitivity at the time of manufacture and an effect of humidity at the time of exposure by incorporating a specified compound in the photosensitive material and mixing a hydrophilic colloid dispersion containing a color developing coupler with the rest components of a coating fluid and starting coating without stagnation. CONSTITUTION:The silver halide color photographic sensitive material has one photosensitive silver halide emulsion layer containing the color developing coupler and a nonphotosensitive hydrophilic colloidal layer, and contains at least one kind of compound selected from formulae I and II and the like, and it is formed by coating with a coating fluid prepared by mixing the hydrophilic colloid dispersion containing the color developing coupler with the rest component of the coating fluid and then, starting coating without stagnating by >=10min. In formulae I and II, R1 is H, lower alkyl, or aryl; X is halogen, nitro, or the like; M<1> is an H or alkali metal atom or the like; and m is an integer of 0-5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which has a small sensitivity variation during production and is less affected by humidity during exposure. The present invention relates to a manufacturing method.

[0002]

BACKGROUND OF THE INVENTION Product homogenization has recently been strongly desired.
In particular, there is a strong demand for color photographic paper, and it is desired that the photographic paper has less variation in sensitivity. That is, it is desired that the sensitivity variation is small in manufacturing photographic paper.

Color photographic paper has been spectrally sensitized with various sensitizing dyes, and various sensitizing dyes have been studied in order to reduce sensitivity variations, but no sufficient effect has been obtained.

JP-A-63-296046, JP-A-61-90154, JP-A-2-2
No. 94634 discloses a method in which a hydrophilic colloidal dispersion of a hydrophobic photographic additive is prepared, and then rapidly mixed with the rest of the coating components and coated, but the effect on the sensitivity fluctuation is observed, but it is sufficient. However, there is a phenomenon in which the sensitivity fluctuates when the humidity changes in fog light (hereinafter referred to as humidity dependency), and its improvement is desired.

The above-mentioned manufacturing method represents that the hydrophilic colloidal dispersion of the hydrophobic photographic additive and the remaining coating components are stagnant in a solution state, and mixed and coated just before coating. However, because the silver halide in the remaining coating components fluctuates during stagnation, the sensitivity fluctuation during manufacturing is not sufficient,
It is considered that humidity dependency is large, and improvement thereof is desired.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a silver halide color photographic light-sensitive material which has a small sensitivity variation during production and is less affected by humidity during exposure.

[0007]

It has been found that the above objects of the present invention can be achieved by the following structures.

A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion-containing layer containing a color-forming coupler and a non-light-sensitive hydrophilic colloid layer on a support. 10 minutes or more after mixing the hydrophilic colloid dispersion liquid containing at least one compound selected from the following general formulas (I) to (IV) in the material and containing the color coupler and the remaining coating liquid components A method for producing a silver halide color photographic light-sensitive material, characterized in that coating is carried out without stagnation.

[0009]

[Chemical 5]

In the formula, R ₁ is a hydrogen atom, a lower alkyl group,
Represents an aryl group.

[0011]

[Chemical 6]

In the formula, R ₂ is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, or (R ₆ ).
(R ₅ )> N-C (= O)-, (R ₆ ) (R ₅ )> N-C (= S)-
₅ and R ₆ each represent an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group or an alkylsulfonyl group, and R ₃ and R ₄ may be bonded to each other to form an aromatic ring. Good.

R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

[0014]

[Chemical 7]

In the formula, X is a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, -COR ₇ ,-.
N <(R ₈ ) (R ₉ ), -SO ₃ M ² , R ₇ is a hydrogen atom, -OM ² ,
Lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group,-
N <(R ₁₀ ) (R ₁₁ ) is represented. R _8, R ₉ are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR _12, -S
O ₂ R ₁₂ may be the same or different, and R ₁₀ and R ₁₁ each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group, and they may be the same or different. R ₁₂ represents a lower alkyl group, an aryl group or an aralkyl group, M ¹ and M ² represent a hydrogen atom, an alkali metal atom and an atomic group necessary for forming a monovalent cation, and m represents 0 to 0. When it represents an integer of 5 and m is 2 to 5, X may be the same group or a plurality of the above groups may be combined.

[0016]

[Chemical 8]

In the formula, R ₁₂ represents an unsubstituted or substituted alkylene group, Y represents a hydrogen atom, a halogen atom, a nitro group,
A hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, -COR ₁₄ , -N <(C ₁₅ ) (C ₁₆ ), and -SO ₃ M ³ ; R ₁₄ represents hydrogen fiberboard, -OM ^3, lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aralkyl group, -N <a _{(C 17) (C 18)} . R ₁₅ ,
R ₁₆ represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COR ₁₉ , or —SO ₂ R ₁₉ , which may be the same or different, and R ₁₇ and R ₁₈ are each a hydrogen atom. , A lower alkyl group, an aryl group and an aralkyl group, which may be the same or different, R ₁₉ represents a lower alkyl group, an aryl group or an aralkyl group, and
³ represents a hydrogen atom, an alkali metal atom, and an atomic group necessary for forming a monovalent cation. n is 0 or 1 to (6
-P) represents an integer, and p represents an integer of 1 to 6. n, p
When 2 is 2 or more, each of the above groups may be combined.

The present invention will be described in more detail below.

[0019]

[Chemical 9]

In the formula, R ₁ represents a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, etc.) or an aryl group (eg, phenyl group, 4-chlorophenyl group, etc.).

[0021]

[Chemical 10]

In the formula, R ₂ is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (methyl, ethyl,
tert-butyl, octadecyl, 2-hydroxyethyl, 2-
Carboxyethyl, 2-cyanoethyl, sulfobutyl, N,
N-diethylaminoethyl), a substituted or unsubstituted cyclic alkyl group (eg cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl), a substituted or unsubstituted alkenyl group (allyl, methylallyl), a substituted or unsubstituted aralkyl group ( Benzyl, p-methoxybenzyl, o-chlorobenzyl, p-iso-propylbenzyl),
A substituted or unsubstituted aryl group (phenyl, naphthyl,
o-methylphenyl, m-nitrophenyl, 3,4-dichlorophenyl), heterocyclic group (2-imidazolyl, 2-furyl, 2-thiazolyl, 2-pyridyl), (R ₆ ) (R ₅ )> NC (= O)-,
_{(R 6) (R 5)} > N-C (= S) - represents, R _5, R ₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, chloromethyl, 2-hydroxyethyl , Tert-butyl, octyl), substituted or unsubstituted cyclic alkyl groups (eg cyclohexyl, 2-oxocyclopentyl),
A substituted or unsubstituted aryl group (eg phenyl, 2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl, 4-aminophenyl, 3-acetamidophenyl), cyano group, heterocyclic group (eg 2- Imidazolyl,
2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio groups (eg methylthio, 2-cyanoethylthio,
2-ethoxycarbonylthio), substituted or unsubstituted arylthio groups (eg phenylthio, 2-carboxyphenylthio, p-methoxyphenylthio), substituted or unsubstituted alkylsulfoxy (eg methylsulfoxy, 2-hydroxyethylsulfo) Xy), a substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl, 2-bromoethylsulfonyl), and R ₃ and R ₄ may combine with each other to form an aromatic ring.

R ₅ and R ₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, iso-propyl, 2-cyanoethyl, 2-butoxycarbonylethyl),
A substituted or unsubstituted aryl group (eg phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichlorophenyl, 3-acetamidophenyl), a substituted or unsubstituted aralkyl group (eg benzyl, phenethyl, p- iso-propylbenzyl, o-chlorobenzyl, m-methoxybenzyl).

[0024]

[Chemical 11]

In the formula, X is a halogen atom (eg chlorine atom, bromine atom, fluorine atom), nitro group, hydroxy group, cyano group, lower alkyl group (eg methyl, ethyl, iso-propyl, tert-butyl), lower An alkoxy group (eg methoxy, butoxy, 2-methoxyethoxy),
Aryl groups (eg phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (eg allyl, 1-butenyl), sulfonyl groups (eg methylsulfonyl, benzenesulfonyl), aralkyl groups (eg benzyl, p-iso). - propyl benzyl, o- _{methylbenzyl), - COR 7, -N <} (R 8) (R 9), - represents SO ₃ M ^2,
R ₇ is a hydrogen atom, —OM ² , a lower alkyl group (eg methyl, butyl), an aryl group (eg phenyl, 4-chlorophenyl, 3-nitrophenyl), an aralkyl group (eg benzyl, p-iso-propylbenzyl, o) -Methylbenzyl), lower alkoxy groups (eg methoxy, butoxy,
2-methoxyethoxy), aryloxy (eg phenoxy, naphthoxy, 4-nitrophenoxy), aralkyloxy group (eg benzyloxy, p-chlorobenzyloxy), and -N <(R ₁₀ ) (R ₁₁ ). R ₈ and R ₉ are each a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, 2-ethylhexyl), an aryl group (eg, phenyl, naphthyl,
2-methoxyphenyl, 3-acetamidophenyl), aralkyl groups (eg benzyl, o-chlorobenzyl), -CO
R ₁₂ and —SO ₂ R ₁₂ may be the same or different, and R ₁₀ and R ₁₁ are each a hydrogen atom, a lower alkyl group (eg, methyl, iso-propyl, 2-cyanoethyl),
Represents an aryl group (eg, phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl) or an aralkyl group (eg, benzyl, p-chlorobenzyl), which may be the same or different, and R ₁₂ is a lower alkyl group. (Eg ethyl, 2-methoxyethyl, 2-hydroxyethyl),
Represents an aryl group (eg, phenyl, naphthyl, 4-sulfophenyl, 4-carboxyphenyl), M ¹ and M ² are a hydrogen atom, an alkali metal atom and a group of atoms necessary for forming a monovalent cation (eg, ammonium cation). , Phosphonium cation), m represents an integer of 0 to 5, and m
Is 2 to 5, X may be the same group or a plurality of the above groups may be combined.

[0026]

[Chemical 12]

In the formula, R ₁₂ represents an unsubstituted or substituted alkylene group (for example, an ethylene group, a propylene group, a methylethylene group, etc., and as the substituent, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, A lower alkoxy group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, etc.), and an alkylene group having 1 to 6 carbon atoms is particularly preferable. Y is a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom, fluoro atom), nitro group, hydroxy group, cyano group, lower alkyl group (eg methyl, ethyl, iso-propyl, tert-butyl), lower alkoxy group (Eg methoxy, butoxy, 2-methoxyethoxy), aryl groups (eg phenyl, naphthyl,
2-methoxyphenyl, 3-acetamidophenyl), alkenyl group (eg allyl, 1-butenyl), sulfonyl group (eg methylsulfonyl, benzylsulfonyl), aralkyl group (eg benzyl, p-iso-propylbenzyl, o-methylbenzyl) ), −COR ₁₄ , −N <(C ₁₅ ) (C ₁₆ ),
Represents —SO ₃ M ³ , R ₁₄ represents a hydrogen atom, —OM ³ , a lower alkyl group (eg, methyl, butyl), an aryl group (eg, phenyl, 4-chlorophenyl, 3-nitrophenyl), an aralkyl group (eg, benzyl, p-iso-propylbenzyl, o-
Methylbenzyl), lower alkoxy groups (eg methoxy, butoxy, 2-methoxyethoxy), aryloxy (eg phenoxy, naphthoxy, 4-nitrophenoxy), aralkyloxy groups (eg benzyloxy, p-
Chlorobenzyloxy), and -N <(C ₁₇ ) (C ₁₈ ). R
₁₅ and R ₁₆ are each a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, 2-ethylhexyl), an aryl group (eg, phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), an aralkyl group (eg, benzyl, o- Chlorobenzyl), —COR ₁₉ and —SO ₂ R ₁₉ , which may be the same or different, and R ₁₇ and R ₁₈ are each a hydrogen atom or a lower alkyl group (eg methyl, iso-propyl, 2 -Cyanoethyl), aryl groups (eg phenyl,
4-ethoxycarbonylphenyl, 3-nitrophenyl),
Aralkyl groups (e.g. benzyl, p- chlorobenzyl) represents, or different and the same as each other, R ₁₉
Is a lower alkyl group (eg ethyl, 2-methoxyethyl,
2-hydroxyethyl), aryl groups (eg phenyl,
Naphthyl, 4-sulfophenyl, 4-carboxyphenyl)
And M ³ represents a hydrogen atom, an alkali metal atom (eg sodium, potassium) and an atomic group (eg ammonium cation, phosphonium cation) necessary for forming a monovalent cation. n represents 0 or an integer of 1 to (6-p), and p represents an integer of 1 to 6. When n and p are 2 or more, each of the above groups may be combined.

Specific examples of the compounds represented by the general formulas (I) to (IV) are shown below, but the invention is not limited thereto.

[Exemplified Compound]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

Some of these compounds are commercially available from Sanai Petroleum Co., Ltd., but it can be warned with reference to the following documents and patents.

(1) Henry Recueil des travaux chiniq
ues des Rays-Bas 16 235 (2) Mass. Chemisches Zentral batt 1899 I 179 (3) E. Schmidt .Berichte der Deutchen Chemischen
Gesellschaft. 52 397 (4) E. Schmidt.ibit. 55 317 (5) Henrry Chemiches Zentralblatt 1897 II 338 (6) JP-A-62-231955 In the present invention, hydrophilic colloid means various photographic constituent layers of a light-sensitive material. Binders contained in the coating liquid used for coating, that is, sol of synthetic hydrophilic polymers such as agar including gelatin, natural hydrophilic polymer such as colloidal albumin and derivative gelatin, cellulose derivative, polyvinyl alcohol and the like. , A gel-like hydrophilic colloidal solution and a composition such as a coating solution which is used in the process of adjusting the solubility or dispersion in water used for the preparation of the coating liquid, or in the storage or preparation process, or a finished coating liquid, such as a silver halide emulsion, a coupler, It is a dispersion liquid such as a matting agent, a surfactant liquid, a dye solution and various other additives.

The amount of the compound of the present invention to be used is based on the aqueous solution which is a photographic colloidal composition and other solutions to be added.
The range of 0.001 to 0.05% by weight is preferable. However, it goes without saying that this range may be increased or decreased depending on the type of light-sensitive material, the type of aqueous solution, the storage state, and the like.

The compound of the present invention may be added as a solution dissolved in water or a solvent such as methanol, ethanol, isopropanol, acetone, ethylene glycol or a mixed solvent thereof, or dissolved in a high boiling point solvent or a low boiling point solvent. It may be added after being emulsified and dispersed using a post-surfactant.

The compounds of the present invention are preferably used not only in one kind but in a combination of two or three kinds because they are hardly influenced by humidity during exposure.

The compound of the present invention comprises each layer constituting a silver halide color photographic light-sensitive material, for example, a silver halide emulsion layer,
It may be applied to any one of an undercoat layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, etc., and is preferably a hydrophilic colloid dispersion containing a color coupler because it is hardly affected by humidity during exposure. It is preferably added to the liquid. It is also preferable to add to a plurality of layers from the same point.

In the present invention, "a hydrophilic colloid dispersion containing a color-forming coupler is mixed with the remaining coating solution components 10
“Coating without stagnation for more than one minute” means that the stagnation time until the mixture is applied is within 10 minutes, preferably within 5 minutes, and more preferably within 1 minute. The temperature at the time of stagnation of this mixture is preferably 30 ° C to 65 ° C, more preferably 33 ° C to 45 ° C.

In making the hydrophilic colloidal dispersion containing the color coupler in the present invention, the calcium content is 50%.
It is preferably dispersed in gelatin in the range of 0 to 2000 ppm, and the transmittance of a 10% aqueous solution at 420 nm is 70% or more. As a result, the sensitivity fluctuation of stagnation (manufacturing stability) is further improved and reduced, which is preferable.

In the present invention, a benzoylacetamide type coupler and a pivalylacetamide type coupler can be preferably used as the yellow coupler.

As the magenta coupler, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler,
Pyrazoloazole couplers and acylacetonitrile couplers can be preferably used.

As the cyan coupler, naphthol type couplers and phenol type couplers can be used, and among them, 2-acylaminophenol type and 2,5-di-acylaminophenol type couplers are preferable.

The light-sensitive material used in the present invention can be, for example, a negative and a positive film of a color negative, and a color photographic paper. Especially, when the color photographic paper used for direct viewing is used, the present invention can be used. The effect of is effectively exhibited.

The light-sensitive material of the present invention including this color photographic paper may be of single color or multicolor.

As the silver halide used in the light-sensitive material of the present invention, any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like which are usually used in silver halide emulsions can be used. Any thing can be used.

The silver halide grains used in the present invention are
It preferably has a silver chloride content of 90 mol% or more,
Further, the silver bromide content is 10 mol% or less, the silver iodide content is 0.5
It is preferably not more than mol%.

The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 90 mol% or less.

In a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the silver chloride content in all silver halide grains contained in the emulsion layer is 90 mol%. % Of silver halide grains above
It is at least 60% by weight, preferably at least 80% by weight.

The silver halide emulsion used in the present invention is
It is chemically sensitized by a sulfur sensitizing method, a selenium sensitizing method, a reduction sensitizing method, a noble metal sensitizing method, or the like. Further, a dye known as a sensitizing dye in the photographic industry can be used to optically sensitize a desired wavelength range.

Gelatin is preferably used as the binder used in the light-sensitive material of the present invention.

Generally, gelatin used in the photographic industry includes alkali-processed gelatin which is treated with lime or the like and acid-processed gelatin which is treated with hydrochloric acid in the manufacturing process from collagen. Manufactured from pigskin, etc.

The gelatin used in the light-sensitive material according to the present invention may be lime-processed gelatin or acid-processed gelatin, and is produced from any material such as cow bone, cow hide, pig skin, etc. Although gelatin may be used, lime-processed gelatin produced from cow bone or pig skin as a raw material is preferable, and lime-processed gelatin produced from pig skin as a raw material is more preferable in the uppermost layer.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material are hardened by using a hardener which crosslinks the binder (or protective colloid) molecule and enhances the film strength, either alone or in combination.

The hardener is preferably added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid. Is.

The protective layer of the photosensitive material, the hydrophilic colloidal layer such as the intermediate layer, are protected from the fog due to the discharge caused by the photosensitive material being charged by friction and the like, and the ultraviolet absorption for preventing the deterioration of the image by the ultraviolet light. You may include the agent.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an antiirradiation layer. In these layers and / or in the emulsion layer, it may flow out from the color light-sensitive material during the development processing,
Alternatively, a dye to be bleached may be contained.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, enhancing the writing property, and preventing sticking between the light-sensitive materials. . Also, a slip agent can be added to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the photosensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used for protection of the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property is improved, antistatic property, smoothness property is improved, emulsion dispersion, adhesion prevention (development acceleration, contrast enhancement, sensitization, etc.). Various surfactants are used for the purpose of improving photographic characteristics.

The photographic emulsion layers and other layers of the light-sensitive material of the present invention include baryta paper or paper laminated with α-olefin polymer or the like, and a paper support or synthetic paper from which the paper support and the α-olefin layer can be easily peeled off. Plastic reflective support, such as
Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide and reflective supports coated with white pigment, and rigid bodies such as glass, metal and pottery. It can be applied to etc. Also, 120-1
It is also possible to use a thin reflective support of 60 μm.

The support used in the present invention may be either a reflective support or a transparent support, a white pigment may be contained in the support for imparting reflectivity, or a white pigment may be provided on the support. You may coat the hydrophilic colloid layer containing.

As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments, and examples thereof include alkaline earth metal sulfates such as barium sulfate. Examples thereof include carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide, zinc oxide, talc and clay. Barium sulfate and titanium oxide are preferably used as the white pigment.

The light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet ray irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or in an undercoat layer (adhesiveness on the surface of the support, antistatic property, It may be applied via one or more subbing layers) to improve stability, abrasion resistance, hardness, antihalation, friction properties and / or other properties.

When coating a light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The color-developing agent used in the color-developing solution in the present invention includes known ones widely used in various color photographic processes.

In the present invention, the color developing process may be immediately followed by a processing solution having a bleaching ability, but the processing solution having a bleaching ability may be a processing solution having a fixing ability (so-called bleach-fixing solution). . A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching step.

[0073]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Inversion 1 A high density polyethylene was laminated on both sides of a paper pulp weighing 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anthase-type titanium oxide dispersed therein was laminated to prepare a reflective support. Sample 101, a multilayer silver halide color photographic light-sensitive material, was prepared by coating each layer having the following structure on the reflective support.

The coating solution was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.57 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of the boiling point organic solvent (DNP) and dissolved, and this solution was dissolved in 9.5 ml of 15% surfactant (SU-1).
A yellow coupler dispersion liquid was prepared by emulsifying and dispersing it in 220 m1 of a 10% aqueous gelatin solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coatings for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer.

As a hardener, the second and fourth layers (H
-1) was added to the 7th layer (H-2).

The structure is as shown in the table below.

Further, the yellow coupler dispersion and the blue-sensitive silver halide emulsion were stagnated at 37 ° C. for 6 hours, and then both solutions were rapidly mixed and then coated.

In the compounds of the general formulas (I) to (IV), 0.002 g / m ² in total was added to the layers shown in Table 3. When adding over two layers, the ratio of each layer is shown in Table 3.
Shown in.

The green and red photosensitive layers were similarly mixed and then coated.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Chemical 21]

[0085]

[Chemical formula 22]

[0086]

[Chemical formula 23]

[0087]

[Chemical formula 24]

[0088]

[Chemical 25]

(Method for preparing blue-sensitive silver halide emulsion) 40
The following (solution A) and (solution B) were simultaneously added over a period of 30 minutes to 1000 cc. Of a 2% aqueous gelatin solution kept at ℃ while controlling pAg = 6.5 and pH = 3.0. (D
(Solution) was simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to obtain 200 cc. (B liquid) Silver nitrate 10g Water added 200cc. (C liquid) Sodium chloride 102.7g Potassium bromide 1.0g Water added 600cc. (D liquid) Silver nitrate 300g Water added 600cc. After addition, Kao Atlas Co. Demolition N 5% aqueous solution and magnesium sulfate 20% aqueous solution were used for desalting, and then mixed with gelatin aqueous solution to obtain average particle size 0.85 μm, variation coefficient of particle size distribution 0.07, silver chloride content 99.5 mol. % Monodisperse cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was carried out at 50 ° C. to obtain a blue-sensitive silver halide emulsion.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
The average particle size is 0.43μ in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50μ in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

Further, the following metal compounds were added to the above (C liquid).

K ₂ IrCl ₆ 3.8 × 10 ⁻⁸ mol / mol AgX K ₄ Fe (CN) ₆ 1.2 × 10 ⁻⁵ mol / mol AgX For the above EMP-3, the following compounds were used to optimize chemistry at 60 ° C. Sensitize and red-sensitive silver halide emulsion (Em-
R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0099]

[Chemical formula 26]

The following evaluations were performed using the samples prepared above.

[Fluctuation of Sensitivity during Manufacturing] (Stagnating property) The samples prepared above (the sample prepared by rapidly mixing and coating the coupler dispersion and the remaining coating components and the sample prepared by stagnating for 6 hours and then coating) were used. Perform white wedge exposure with an exposure time of 0.1 seconds, and perform the development process shown below to test each sample with PDA-65.
The sensitivities of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer were measured using a densitometer (manufactured by Konica Corporation).

Sensitivity (S) = reciprocal of the exposure dose that gives a reflection density of 0.8, and the sensitivity between the coupler dispersion and the remaining coating components, which were rapidly mixed and coated, and the samples which were stagnated for 6 hours and then mixed and coated. The change (ΔS ₁ ) was determined and is shown in Table 3.

ΔS _l = (S _b −S _a ) / S _a × 100 (%) S _a : Sensitivity of a sample obtained by rapidly mixing the coupler dispersion and the remaining coating components S _b : 6 Sensitivity of sample obtained after lagging time (processing step) Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 27 seconds 81ml Bleach fixing 35.0 ± 0.5 ℃ 27 seconds 54ml Lins 30-34 ℃ 90 seconds 150ml Dry 60-80 ° C 30 seconds Development tank liquid Pure water 800 ml Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate 6.5g N, N-diethylhydroxylamine 3.5g Disulfonic acid ethylhydroxylamine 3.5g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 2. 0g Potassium carbonate 30.0g Add water to bring the total volume to 1 liter and adjust to pH = 10.10.

Color developing solution replenishing solution Pure water 800 ml Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.5 g N, N-diethylhydroxyl Amine 6.0 g Ethylhydroxylamine disulfonate 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30.0 g Adjust to 1 liter and pH = 10.60.

Bleach-fixing replenisher diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 200 ml 5-Amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite ( 40% aqueous solution)
Add 50 ml water to make the total volume 1 liter, and adjust the pH to 6.5 with aqueous ammonia or glacial acetic acid.

Bleach-fixing tank liquid Diethylenetriamine pentaacetic acid ammonium ferric dihydrate 50g Diethylenetriamine pentaacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml 5-Amino-1,3,4-thiadiazole-2-thiol 1.0g Ammonium sulfite ( 40% aqueous solution) 25 ml Add water to make the total volume 1 liter, and adjust the pH to 7.0 with aqueous ammonia or glacial acetic acid.

Stabilization tank solution and replenishing solution Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightening Agent (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g PVP (Polyvinylpyrrolidone) 1.0g Ammonia water (25% ammonium hydroxide solution) 2.5g Ethylenediaminetetraacetic acid 1.0g Ammonium sulfite (40% solution) ) Add 10 ml water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

[Humidity Dependence during Exposure] The sample prepared above was left in an atmosphere of 20 ° C., 10% RH and 20 ° C., 75% RH for 1 hour, and then white wedge exposure was performed by an ordinary method with an exposure time of 0.1 seconds. ,
The development processing shown below was performed, and the sensitivities of the blue photosensitive layer, the green photosensitive layer, and the red photosensitive layer of each sample were determined using a PDA-65 densitometer (manufactured by Konica Corp.).

Sensitivity (S) = reciprocal of exposure dose that gives reflection density 0.8 Then, for each sample, the sensitivity change (ΔS ₂ ) between 20 ° C., 10% RH and 20 ° C., 75% RH was calculated and shown in Table 3. Show.

ΔS ₂ = (S ₇₅ −S ₁₀ ) / S ₁₀ × 100 (%) S ₇₅ : Sensitivity during exposure at 20 ° C. and 75% RH S ₁₀ : Sensitivity during exposure at 20 ° C. and 10% RH

[0111]

[Table 3]

[0112]

[Chemical 27]

As shown in Table 3, when the hydrophilic colloidal dispersion containing the color coupler and the remaining coating components are coated within 10 minutes after mixing, the sensitivity is apt to be affected by humidity during exposure, resulting in large sensitivity fluctuation. I understand. Sample number 8,13,16,18,
19,21,22,23,25,26 and the like, by coating within 10 minutes after mixing the hydrophilic colloid dispersion containing the compound of the present invention and containing a color coupler and the remaining coating components, the humidity at the time of exposure It becomes difficult to be affected by the above, and it is understood that the stagnation (manufacturing stability) is further improved.

Further, it was found that the compound of the present invention was added to a plurality of layers to make it less susceptible to the influence of humidity during exposure (sample numbers 13, 16, 18, 19, 21).

Example 2 A sample was prepared in the same manner as in Example 1, but a plurality of compounds of the present invention were used as shown in Tables 4 and 5. The evaluation was performed in the same manner as in Example 1. The compound of the present invention was added to the remaining coating components for the layer containing the color coupler,
The other layers were added to the coating solution. However,
For sample Nos. 30, 31, 35, 36, 37 and 38, the compound of the present invention was added to a hydrophilic colloidal dispersion containing a color coupler only in the fifth layer.

[0116]

[Table 4]

[0117]

[Table 5]

As can be seen from Tables 4 and 5, the combined use of the compounds of the present invention makes it more difficult to be affected by humidity during exposure.

It was also found that when the compound of the present invention was added to the colloidal dispersion containing the color coupler, the influence of the added layer on the humidity change during exposure was reduced (Sample Nos. 28 to 31, 32 to 32). 38).

Example 3 Similar to Example 2, when the compound of the present invention was added to a colloidal dispersion containing a yellow coupler and a colloidal dispersion containing a magenta coupler, the same effect was obtained.

Example 4 A sample was prepared in the same manner as in Example 1, except that gelatin used in the colloidal dispersion containing each color forming coupler was used as shown in Tables 6 and 7. The compounds of the present invention were all used in the sixth layer.
2 mg / m ^{2 was} added. The results are shown in Tables 6 and 7.

[0122]

[Table 6]

[0123]

[Table 7]

As is clear from Tables 6 and 7, the gelatin used in the colloidal dispersion containing the color coupler has a calcium content of 500 ppm to 2000 ppm and a 10% aqueous solution having a transmittance of 420 nm of 70% or more. It can be seen that stagnation (manufacturing stability) is further improved by the dispersion.

[0125]

According to the present invention, it is possible to provide a method for producing a silver halide color photographic light-sensitive material in which sensitivity fluctuation during production is small and humidity is less affected by exposure.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one photosensitive silver halide emulsion-containing layer containing a color-forming coupler and a non-photosensitive hydrophilic colloid layer on a support, wherein the silver halide color is The photographic light-sensitive material contains at least one compound selected from the following general formulas (I) to (IV), and after mixing the hydrophilic colloid dispersion liquid containing a color coupler and the remaining coating liquid components, 10 A method for producing a silver halide color photographic light-sensitive material, which is characterized in that coating is performed without stagnation for more than a minute. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, a lower alkyl group or an aryl group. ] [Chemical 2] [In the formula, R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group,
Aralkyl group, an aryl group, a heterocyclic _{group, (R 6) (R 5} )> N-C
(= O) -, (R 6) (R 5)> N-C (= S) - represents, R _5, R ₆ are each an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkyl It represents a sulfoxy group or an alkylsulfonyl group, and R ₃ and R ₄ may combine with each other to form an aromatic ring. R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. ] [Chemical 3] [In the formula, X is a halogen atom, a nitro group, a hydroxy group,
Cyano group, a lower alkyl group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl _{group, -COR 7, -N <(R} 8)
(R ₉ ), —SO ₃ M ² , R ₇ is a hydrogen atom, —OM ² , lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group, —N <(R
₁₀ ) (R ₁₁ ) is represented. R _8, R ₉ are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR _12, -SO ₂ R ₁₂
Which may be the same or different from each other, R
₁₀ and R ₁₁ each represent a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group, which may be the same or different, and R ₁₂ represents a lower alkyl group, an aryl group or an aralkyl group, and M ¹ , M ² represents a hydrogen atom, an alkali metal atom and an atomic group necessary for forming a monovalent cation, m represents an integer of 0 to 5, and when m is 2 to 5, X is the same group. Alternatively, a plurality of the above groups may be combined. ] [Chemical 4] [In the formula, R ₁₂ represents an unsubstituted or substituted alkylene group, Y represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group,
An aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, -COR ₁₄ , -N <(C ₁₅ ) (C ₁₆ ), -SO ₃ M ³ , R ₁₄ is hydrogen base paper, -OM ³ , a lower alkyl group, An aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group, an aralkyloxy group and -N <(C ₁₇ ) (C ₁₈ ) are represented. R ₁₅ , R ₁₆
Each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COR ₁₉ , or —SO ₂ R ₁₉ , which may be the same or different, and R ₁₇ and R ₁₈ are each a hydrogen atom,
It represents a lower alkyl group, an aryl group or an aralkyl group, which may be the same or different from each other, R ₁₉ represents a lower alkyl group, an aryl group or an aralkyl group, and M ³ represents a hydrogen atom, an alkali metal atom or 1 Represents a group of atoms necessary to form a valent cation. n is 0 or 1 to (6-p)
Represents an integer of 1, and p represents an integer of 1 to 6. When n and p are 2 or more, each of the above groups may be combined. ]