JPH0429139A - Silver halide color photographic sensitive material improved in fastness of dye image - Google Patents

Abstract

PURPOSE:To additionally prevent color dyeing without lowering a photographic sensitivity by incorporating the solid fine particle dispersion of specific compds. into the above photosensitive material. CONSTITUTION:The solid fine particle dispersion of at least one kind of the compds. expressed by formula I is incorporated into this photosensitive material as color staining preventive agent. In the formula, X denotes the solubilizable group which imparts the mobility to the extent that the group can be run to the outside o the photosensitive material system; R denotes a hydrogen atom, acyl group, alkoxycarbonyl group; two R may be the same or different; (n) denotes 1 to 4 integer. The content of the compds. is preferably 1.0X10<-4> to 1.0X10<-6> mol/m<2> per layer in the case of use of the compds. as a color fogging preventive agent in emulsion layers and is preferably 1.0X10<-3> to 1.0X10<-5> mol/m<2> per layer in the case of use as a color clouding preventive agent in intermediate layers. The degradation is sensitivity is obviated in this way and the excellent effect of preventing color staining and the resistance of the color images to light are both obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material containing a color stain inhibitor.

(Prior Art) When a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion is developed using a color developer such as paraphenylene diamine, color developer oxides are produced during development. However, it is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs in which dyes migrate into adjacent image forming layers and form undesirable dyes. Also, during color development, oxidation of the developing agent, fogging of the emulsion, etc.
It is known that the phenomenon of "color fog" occurs.

In the following, this "color turbidity" and "one-color capri" will be collectively referred to as "r-color contamination."

Conventionally, methods using various hydroquinones have been proposed in order to prevent color staining. For example, regarding the use of monolinear alkyl hydroquinones, US Pat.
No. 728,657, JP-A-47-106329, etc., and the use of mono-branched alkylhydroquinone is described in U.S. Pat. -156.483
No. 49-106.329.

Furthermore, the use of sulfonamide phenols as a color stain preventive agent has been proposed in JP-A-59-5247 and JP-A-59-19.
It is described in No. 2.246, No. 59-222.836, etc.

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain even higher quality color photographs, new color stain preventive agents have been developed that can more effectively prevent color stains without reducing photographic sensitivity. is strongly desired. However, none of the above-mentioned conventional color stain inhibitors could meet this new demand.

(Objective of the Invention) The object of the present invention is to provide a silver halide color photograph containing a color stain preventing agent that can further prevent color staining without reducing photographic sensitivity and that can be added to thin-layered photosensitive materials. Our purpose is to provide photosensitive materials.

(Structure and operation of the invention) The object of the present invention is to provide a silver halide color characterized by containing at least one solid fine particle dispersion of a compound represented by the following general 2[N] as a color stain preventive agent. This is accomplished using photographic materials.

General formula [I] p H [wherein, R may be the same or different. n represents an integer of 1 to 4. ] In the general formula [I], the solubilizing group represented by X includes an ionizable hydroxyl group, a carboxyl group, an amino group,
Examples include sulfamino groups, sulfonamide groups, ionizable salts thereof, ester groups, and ether groups. Moreover, these groups may be bonded via a linking group. Typical linking groups include oxy group, thio group, carbonyl group, carbonyloxy group, oxycarbonyl group,
Examples include an amino group, a carbamoyl group, an aminocarbonyl group, a ureido group, and a sulfamoyl group. R
Examples of the group represented by include a hydrogen atom, an acyl group (for example,
acetyl, benzoyl) or an alkoxycarbonyl group (eg, ethoxycarbonyl), and the two R's may be the same or different.

Typical examples of compounds used in the present invention are shown below, but the invention is not limited thereto.

0■ υ and UL; t13 (I4) These compounds are disclosed in, for example, JP-A-61-169.845.
No. 62-103,053 and the like.

The color stain preventive agent represented by general formula (1) is introduced into constituent layers such as emulsion layers and intermediate layers in the form of a solid fine particle dispersion. The solid particle dispersion can be produced using known techniques, such as by precipitating or reprecipitating the color stain inhibitor in the form of a dispersion, or by using known milling techniques (ball milling, sand milling, colloid milling, etc.). I can do it. The average diameter of the color stain inhibitor particles in the dispersion is 0.01 μm or more10
It is not more than μm, preferably not less than 0.05 μm and not more than 5 μm.

The color stain preventive agent according to the present invention is a type of halogen that forms a color image through oxidative coupling between an aromatic primary amine developer (for example, a phenylenediamine derivative or an aminophenol derivative) and a color-forming coupler in a color development process. Silver chemical color photographic materials (e.g. color paper,
color negative film, color rehearsal film, etc.)
It is highly effective in preventing color staining.

The compounds according to the invention may be used in combination with various color stain inhibitors, such as hydroquinone derivatives, aminophenol derivatives, ascorbic acid derivatives, etc.

Specific examples are U.S. Patent Nos. 2,360,290 and 2,3
No. 36,327, No. 2,403,721, No. 2,41
No. 8.613, No. 2,675,314, No. 2,701
, No. 197, No. 2,704.713, No. 2.728.
No. 659, No. 2,732,300, No. 2,735,3
No. 65, JP-A No. 50-92,988, JP-A No. 50-92,
No. 989, No. 50-93, 928, No. 50-110.
No. 337, No. 52-146.235, Special Publication No. 5023
．． It is described in No. 813, etc.

The color stain prevention agent according to the present invention can be added as a color fog prevention agent to an emulsion layer containing a photographic coupler and a photosensitive silver halide, and can be added as a color fog prevention agent to an emulsion layer and an emulsion layer. It can be added to the intermediate layer placed between them.

When the compound according to the present invention is used as a color antifoggant in an emulsion layer, -1.0X10-' to 1, OX per layer.
It is preferable to use it at 10" mol/%, and when used in the intermediate layer as a color turbidity preventive agent, 1.0" mol/% is used per layer.
OX 10-3~1. OX 1. O-'mof/rr
Although it is preferable to use r, it is not limited thereto. Furthermore, it can be added to both the intermediate layer and the emulsion layer to prevent color fog and color turbidity.

The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but the present invention is particularly suitable when a color photographic paper intended for direct viewing is used. The effect is effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used. has a structure in which a suitable number and order of layers are laminated on a support, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
Growth may be performed by sequentially and simultaneously adding H and pAg while controlling them. Conversion methods may be used to change the silver halide composition of the grains after growth.

When producing the silver halide of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts,
Metal ions can be added and incorporated into the particles and/or on the particle surfaces, and by placing them in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained.6 When removing the salts,
This can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more silver halide emulsions that have been separately formed.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening for the purpose of preventing fog during storage or photo processing and/or maintaining stable photographic performance,
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of light-sensitive materials using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminephenol derivatives, etc.) during color development processing to form a dye. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral enhancers and sterilizing agents, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or DI that releases a development inhibitor during development and improves image sharpness and image graininess.
An R coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction. (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination. Although a coupling reaction is carried out with an oxidized product of an aromatic primary amine developer, a colorless coupler that does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 56-30127, U.S. Patent No. 2,87
No. 5,057, No. 3,253,924, No. 3.265
, No. 506, No. 3.408.194, No. 3,551,
No. 155, No. 3,55L No. 156, No. 3,664,8
No. 41, No. 3,725,072, No. 3,730,72
No. 2, No. 3,89L445, No. 3,900,483, No. 3,929,484, No. 3,933,500,
3.973.968, 3,990,896, 4,012,259, 4,022,620, 4
, No. 029,508, No. 4,057,432, No. 4.
i06,942, 4,133,958, 4,2
No. 69,936, No. 4,286,053, No. 4,30
No. 4,845, No. 4,314,023, No. 4,336
, No. 327, No. 4,356,258, No. 4,386,
No. 155, No. 4,401.752, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and closed acylacetonitrile couplers can be preferably used. A specific example of a magenta coupler that can be advantageously used is disclosed in Japanese Patent Application No. 1983.
No. 464882, No. 58-167326, No. 58-2
No. 06321, No. 58-214863, No. 58-21
No. 7339, No. 59-24653, Special Publication No. 40603
No. 1, No. 40-6035, No. 45-40757, No. 47-27411, No. 49-37854, JP-A-5
No. 0-13041, No. 51-26541, No. 5]-3
No. 7646, No. 51-105820, No. 524212
No. 1, No. 53-123129, No. 53-125835
No. 53-129035, No. 54-48540,
No. 56-29236, No. 56-75648, No. 57
-17950, 57-35858, 57146
No. 251, No. 59-99437, British Patent No. 1,25
No. 2,418, U.S. Patent No. 2,600,788, U.S. Patent No. 3
, No. 005,712, No. 3,062,653, No. 3,
No. 127,269, No. 3,214,437, No. 3.2
No. 53.924, No. 3,311,476, No. 3,41
No. 9,391, No. 3,519,429, No. 3,558
, No. 319, No. 3,582,322, No. 3,615,
No. 506, No. 3,658,544, No. 3,705,8
No. 96, No. 3.725.067, No. 3,758,30
No. 9, No. 3,823,156, No. 3,834,908
No. 3,891,445, No. 3,907,571, No. 3.926.631, No. 3,928,044,
No. 3,935,015, No. 3,960,571, No. 4,076.533, No. 4,133,686, No. 4
, No. 237, 217, No. 4,241,168, No. 4,
No. 264,723, No. 4,301,235, No. 4,3
10,623, etc.

As the cyan dye-forming coupler, known naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1,543,040, Japanese Patent Publication No. 36894/1982, and Japanese Patent Application Laid-open No. 59838/1989.
No. 50-137137, No. 51-146828, No. 53-105226, No. 54-115230,
No. 56-29235, No. 56-104333, No. 5
No. 6-126833, No. 57-133650, No. 57
-155538, 57-204545, 58-
No. 118643, No. 59-31953, No. 59-31
No. 954, No. 59-59656, No. 59-12434
No. 1, No. 59-166956, U.S. Patent No. 2,369
, No. 929, No. 2.423.730, No. 2.434.
No. 272, No. 2.474.293, No. 2,698,7
No. 94, No. 2.772.162, No. 2,801.17
No. 1, No. 2,895,826, No. 3,253.924
No. 3,311.476, No. 3.458.315, No. 3,476.563, No. 3,591.383,
3,737.316, 3.758.308, 3,767.411, 3,790,384, 3
．． No. 880.661, No. 3.926.634, No. 4,
No. 004,929, No. 4,009,035, No. 4.0
No. 12.258, No. 4,052.212, No. 4,12
No. 4.396, No. 4,134,766, No. 4.138
, No. 258, No. 4.146.396, No. 4,149.
No. 886, No. 4.178.183, No. 4,205.9
No. 90, No. 4,254.212, No. 4,264.72
No. 2, No. 4.288,532, No. 4,296.199
No. 4,296.200, No. 4,299,914, No. 4,333,999, No. 4,334.011,
These are described in 4.386.155, 4,401,752, 4,427,767, etc.

As a colored coupler, for example, British Patent No. 937,
No. 621, No. 1,035.959, No. 1,255.1
No. 11, JP-A-48-22028, JP-A No. 52-4212
1, Japanese Patent Publication No. 38-22335, Japanese Patent Publication No. 44-2016, Japanese Patent Publication No. 44-15754, U.S. Patent No. 2.449.96
No. 6, No. 2,521.908, No. 2,543.691
No. 2,801.171, No. 2,983,608, No. 3.005.712, No. 3,034,892,
3,061.432, 3.419.391, 3,476.560, 3,476.563, 3
, No. 481.741, No. 3,519,429, No. 3,
No. 583,971, No. 3,622.328, No. 3,6
No. 84,514, No. 4,004,929, No. 4.0
No. 70.191, No. 4,138,258, No. 4.13
No. 8.264, No. 4.163.670, No. 4,292
, No. 400, No. 4,369.248, etc. can be used.

As a DIR coupler, for example, British Patent No. 953.4
No. 54, U.S. Patent No. 3,227.554, U.S. Patent No. 3,61
No. 5,506, No. 3,617,291, No. 3,701
．． No. 783, No. 3,933,500, No. 4,095,
No. 984, No. 4,149,886, No. 4,286.0
No. 54, No. 4,359,521, JP-A-52-909
No. 32, No. 56116029, No. 57-151944
and U.S. Patent No. 4.248.96.
No. 2, No. 4.409.323, JP-A-57-1542
No. 34, No. 58-162949, No. 58-20515
No. 0, No. 59-195643, No. 59-206834
The timing DIR couplers described in Japanese Patent Application No. 59-206836, Japanese Patent No. 59-210440, and Japanese Patent No. 60-7429 can be preferably used.

Examples of DIR compounds include those described in US Pat. No. 3,632.
No. 345, No. 3,928.041, No. 3,938.9
No. 96, No. 3,958,993, No. 3,961.95
No. 9, No. 4,046.574, No. 4,052.213
Compounds described in JP-A-52-65433, JP-A-52-130327, JP-A-57-128335, etc. can be preferably used.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water type emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and /or a water-soluble organic solvent is used and dissolved, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, using a stirrer, homogenizer, colloid mill, flow jet mixer,
It may be emulsified and dispersed using a dispersion means such as an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of 1°C or higher is used.

Anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasound. Surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion layer of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the color light-sensitive material during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, increases the addibility, and sticks the photosensitive materials together. A matting agent can be added for the purpose of prevention.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent can be added to the light-sensitive material using the silver halide emulsion of the present invention for the purpose of preventing static electricity.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in colloid layers.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, the other layers are a baryta layer or an α-olefin polymer, etc., a flexible reflective support such as paper laminated with paper, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
one or more substrates to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties directly or on the surface of the support. It may be applied via a coating layer.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposures shorter than 1 microsecond, such as 100 microseconds to 1 microsecond using cathode ray tubes and xenon flashlights.
Microsecond exposures can be used, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention by color development as known in the art.

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. In addition, these compounds generally have a concentration of about 0.1 g to about 30 g for the color developer 11;
Preferably about 1 g to about 1.5 g for color developer 11
Use at a concentration of

Examples of aminophenol-based developers include O-aminophenol, P-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers are N, N
It is a '-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-P-phenylenediamine salt monosalt, N-)thyl-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-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 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, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. This color developer p
The H value is usually 7 or higher, 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 bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper 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 complexes of organic 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] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalokenizing agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite,
Sulfites such as potassium metabisulfite and sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, water p consisting of various salts such as ammonium oxide
One or more types of H buffering agent may be included.

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 a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited to the examples.

(Method for preparing solid fine particle dispersion) Water (740d), surfactant (Aerosol OT)
;34,2 g) and zirconia beads (4325 g) with a particle size of 2 mm were placed in a 2500 d bottle with a screw cap, and exemplified compound (1) (150 g) was added to the bottle.
was added and milled for 7 days. Add a gelatin aqueous solution to the obtained dispersion so that the dispersion and gelatin are each 6%.
It was adjusted to become an aqueous solution.

Example 1 60 g of cyan coupler (C-1) was dissolved in a high boiling point organic solvent (D
A solution of BP) and ethyl acetate was added to an 8% aqueous gelatin solution containing a dispersion aid (dodecylbenzenesulfonic acid sodium salt) and dispersed with a homogenizer. The obtained dispersion was finished to 1500 d and kept at 40°C for 3 hours. Apply this dispersion to a 3% aqueous gelatin solution for coating.
In addition to 0InIl, 400g of red-sensitive silver chlorobromide emulsion
(containing 80% molar silver bromide) was added to prepare a coating solution for a red-sensitive emulsion layer.

This coating solution was kept at 40°C for 2 hours.

Coating solutions for each layer were prepared in the same manner, and coated on a polyethylene-coated paper support at a coating speed of 100 m/min to have the following composition.

1st layer: Blue-sensitive emulsion layer The yellow coupler (Y-1) was 8 μ/dllz, and the blue-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) was converted to silver. 3■/d+e”-, high boiling point organic solvent (DBP) at 3■/dm2 and gelatin at 16mg/dm2.
Apply the coating to a coating amount of dm".

2nd layer: Intermediate layer hydroquinone derivative (HQ-1) at 0.45■/dm
2. High boiling point solvent (DBP) at 1.8 B/dm! And gelatin was applied at a coating amount of 4μ/dm''.

3rd layer: Green-sensitive emulsion layer Magenta coupler (M-1) was added at 4 μ/dII12, image stabilizer 5T-1 was added at 4 μ/dm2, green-sensitive silver chlorobromide emulsion (
Containing 20 mol% of silver chloride and 80 mol% of silver bromide) in terms of silver is 4 / dlTlz, and high boiling point organic solvent (DBP) is 4
Apply mg/dm2 and gelatin at a coating amount of 16 µ/dn”.

4th layer: Intermediate layer UV absorber (UV, -1) 3mg/dm2, UV absorber (Ul-2) 3■/dI112, high boiling point organic solvent (DBP) 4■/ds+'', comparative compound (Hydroquinone derivative) (HQ-2) was coated at a coating amount of 0.45 μ/d” and gelatin was coated at a coating amount of 14 μ/d11”.

5th layer: red-sensitive emulsion layer containing cyan coupler (C-1) at 4■/d11! , a high boiling point organic solvent (DBP) of 4 ■/da'', a red-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride and 80 mol% silver bromide) converted to silver of 3 ■/da'', and Coat the gelatin so that the coating amount is 14 μ/da”.

6th layer: Intermediate layer ultraviolet absorber (UV-3) 41g/da", D
BP to 2■/d+w" and gelatin to 6■/d+o"
Apply the coating so that the coating amount is .

7th layer: protective layer Apply gelatin to a coating amount of 9■/dm.

(Compound used for sample preparation) DBP? dibutyl phthalate HQ-1 H3 UV-1 H UV-2 H l CI! .

image stabilizer T-1 comparative compound HQ-2 0 ■ UV-3 0 ■ This sample was designated as Sample 1.

Next, Sample 1 except that the hydroquinone derivative in the fourth layer of Sample 1 was replaced with a solid fine particle dispersion of the exemplary compound shown in Table 1.
Samples 2 to 8 were created in the same manner as above. (The exemplified compound was added in the same molar amount as Sample 1.) These samples were subjected to light wedge exposure with green light using a photosensitive needle (model KS-7, manufactured by Konica ■), and then subjected to the following treatments.

Processing process Color development phenomenon Bleach-fixing water Washing Drying Drying Processing time 3 minutes 30 seconds 1 minute 30 seconds 3 minutes 30 seconds 2 minutes Processing temperature 32.8°C 32.8°C 32.8°C 50-80°C (Color development Developer composition) N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate
4.0g hydroxylamine sulfate
2.0g potassium carbonate
25.0 g sodium chloride
0.1 g sodium bromide
0.2g anhydrous sodium sulfite
2.0g benzyl alcohol 10
．． 0 d Polyethylene glycol (average degree of polymerization 400) 3.0 m Add water to adjust to II2 and pH 10 using sodium hydroxide.
, Reishi adjustment to 0.

(Bleach-fix solution composition) Ethylenediaminetetraacetic acid iron sodium salt 60.0 g Sodium 100.0 g
Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water and 1! Adjust the pH to 7,0 using sulfuric acid.

Each sample treated above was measured using a concentration needle (KONICA KD-
7R type), the maximum yellow density (YDmax) and the maximum magenta density (MDmax) were measured, and the color mixture value (YDmax/MDmax) was calculated from these values.

Further, the color image light fastness of the same sample was evaluated in the following manner.

<Color image light resistance> The dye image formed on each sample was exposed to sunlight for 40 days using an underglass outdoor exposure table.
1,0), and D represents the concentration after exposure).

Table 1 shows the measurement results.

From the results shown in Table 1, Sample-2 to Sample-8 using the color stain preventive agent according to the present invention showed that while maintaining the color stain prevention effect,
It can be seen that the color image exhibits excellent light fastness.

Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide emulsion used in Example 1, and the magenta coupler was changed to M-2, which was added to the fourth layer. Samples (Samples 9 to 16) similar to Sample 1 of Example 1 were prepared except that the solid fine particle dispersion (4ag/dm'') of the exemplary compound of the invention was changed as shown in Table 2.

Samples 9 to 16 were exposed to a light wedge using green light according to a conventional method, and then the exposed samples were processed according to the following development process and processing solution formulation.

Development process Processing temperature Processing time Color development,
35.0±0.3'C 45 seconds bleach fixing 35.
0±0.5℃ Stabilized for 45 seconds 30-34℃ 9
Dry for 0 seconds Naturally dry at room temperature (25℃) [Color developer composition] Pure water 80
0d triethanolamine 10gN
, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene 1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-
3,5-disulfonic acid disodium salt 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g optical brightener (4,4'-diaminostilbendisulfone acid derivative) 10g potassium carbonate
Add 27g of water to bring the total volume to 1! and the pH was 10.1.
Adjust to 0.

[Bleach-fix solution composition]

Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 00m Ammonium sulfite (40% aqueous solution) 27.5m Water was added to bring the pH to 12, and the pH was adjusted to 6.0 with potassium carbonate or glacial acetic acid.
Adjust to 2.

[Stabilizing liquid composition]

5-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol
1.0g1-hydroxyethylidene-1
,1-diphosphonic acid 2.0g ethylenediaminetetraacetic acid 1.0g ammonium hydroxide (20% aqueous solution) 3.0g ammonium sulfite
3.0g Fluorescent brightener (4,4'-diaminostilbene diphosphonic acid derivative) 1.5
Add water to bring the volume to 1, and dilute with sulfuric acid or potassium hydroxide.
Adjust H to 7.0.

The color mixture value of the yellow dye and the light fastness of the magenta image were measured for each of the samples treated above in the same manner as in Example 1. Table 2 shows the results.

As can be seen from the results in Table 2, when the color stain preventing agent according to the present invention was used, excellent color stain preventing effects and color image light fastness were exhibited.

〔Effect of the invention〕

As described above, by adding at least one kind of solid fine particle dispersion of the compound represented by the general formula (1) to the layer constituting the light-sensitive material, there is no decrease in sensitivity, color stain prevention effect and color image improvement. It is possible to provide a silver halide color photographic material having excellent light resistance.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing at least one solid fine particle dispersion of a compound represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, It represents an alkoxycarbonyl group, and two R's may be the same or different. n represents an integer of 1 to 4. ]