JP2005345689A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having suitability to digital exposure and analog exposure, excellent in pressure resistance during high-speed processing in a sheet shape, and excellent also in suitability to coating. <P>SOLUTION: The silver halide color photographic sensitive material has a yellow image forming layer, a magenta image forming layer and a cyan image forming layer, and the difference ΔLogE (LogEd-LogEa) between exposure energy (LogEd) giving a maximum point gamma γmd of each color image obtained by development after exposure for an exposure time of 10<SP>-6</SP>s per pixel and exposure energy (LogEa) giving a maximum point gamma γma of each color image obtained by development after exposure for an exposure time of 0.5 s per pixel is ≤0.15. The silver halide color photographic sensitive material contains a vinylsulfone-based hardening agent dissolved in a compound of formula (I) and added. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material for producing a color print by exposure and development based on new digital information.

  In recent years, opportunities for handling images as digital data are rapidly increasing with the improvement of computing power of computers and progress of network technology. Image information converted into digital data using a scanner or the like can be edited and processed on a computer, and data such as characters and illustrations can be added relatively easily. Examples of hard copy materials for creating hard copies based on such digitized image information include sublimation thermal transfer printing, melt thermal transfer printing, ink jet printing, electrostatic transfer printing, thermoautochrome printing, halogen Examples include silver halide photographic light-sensitive materials. Among them, silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) have high sensitivity, excellent gradation, and excellent image storage stability. Therefore, it is actively used today for producing a high-quality hard copy because it has very superior characteristics compared to other printing materials.

  Image information converted into digital data using a scanner, etc. can be edited and processed on a computer, and data such as characters and illustrations can be added relatively easily. For example, people, landscapes, still life, etc. Opportunities are increasing for handling images that include a mixture of images (hereinafter referred to as “scene images”) and character images (especially thin and small black character images) based on the photographic data. For this reason, in image output based on digital data, it is necessary to satisfy the two requirements simultaneously that a scene image is more natural and a character image is reproduced without blurring.

  In recent years, the resolution of image input devices such as digital still cameras and film scanners has been remarkably increased. In order to output images that take advantage of the high-quality image data, the high resolution of the output device (digital exposure machine) It is also being considered. Recently, various digital exposure machines have been commercialized, but many types of digital image exposure apparatuses that perform such exposure are currently on sale, and new developments in combination with advances in exposure light sources, control devices, etc. Many digital image exposure apparatuses have been developed. Among these digital image exposure apparatuses, an apparatus using a light source having a sharp light source wavelength distribution, such as a laser or LED, is becoming mainstream as an exposure light source.

However, with the widespread use of various digital image exposure devices, various types of image devices have been released by various companies, but the types of lasers and LEDs mounted are not uniform, and the exposure wavelength and exposure are different for each exposure device. The time is also different, so the digital exposure time is significantly different from the conventional analog exposure of the negro system, and there is a difference in the exposure time of 10,000 to 100,000 times from 10 ⁻⁷ seconds to 10 ⁻² seconds. For this reason, tolerance for the exposure time has been greatly demanded. Furthermore, digital exposure machines are susceptible to heat due to the nature of the equipment, and therefore durability against temperature and humidity during exposure is also more strongly required than image formation by conventional analog exposure apparatuses. . In addition, with the spread of minilabs, there are some photo shops that offer a service that takes less than 35 minutes from receiving customer orders to finishing prints, and shortening the processing time. There is a strong demand from the market to provide beautiful images, especially digitally, even if the processing time is shortened.

  In response to the above problems, various proposals have been made that define the composition and characteristic values of silver halide color photographic light-sensitive materials. For example, silver halide color photographic light-sensitive materials having excellent applicability to exposure time and environment during exposure. Materials have been proposed (see, for example, Patent Document 1). According to the method described in Patent Document 1, a high image is always stably obtained with respect to changes in exposure time and environmental changes such as temperature and humidity during exposure.

  On the other hand, in a system using these silver halide color photographic light-sensitive materials, the silver halide color photographic light-sensitive material is loaded in a light-shielding magazine for storing silver halide color photographic light-sensitive materials in a rolled state. It is pulled out of the magazine and conveyed during exposure and development. Conventionally, a silver halide color photographic light-sensitive material is exposed to light and developed without being cut in the form of a roll, and is cut into a desired length after the development to obtain a print for each sheet, so-called Color prints were created by the roll conveyance method. On the other hand, in recent years, a color printing system employing a sheet conveying method in which a silver halide color photographic light-sensitive material is preliminarily cut into a size corresponding to one printed sheet to form a sheet and then subjected to exposure and development has been put into practical use. Yes. In this transport method, the silver halide color photographic light-sensitive material cut into a sheet can be transported without uneven scanning exposure by employing a transport roller pair and a transport method using a belt conveyor. The sheet-like silver halide color photographic light-sensitive material is subjected to development processing after being exposed. In the development processing step, the light-sensitive material is transported by a pair of transport rollers as a sheet.

  As a result of continuing examination of the silver halide color photographic light-sensitive material described in Patent Document 1, the present inventor used a high-speed conveyance type automatic developing machine in the above-described sheet form after performing digital exposure. In the development process, it was found that pressure fog due to contact with a transport roll or the like is likely to occur.

As a result of examining the above problems, it has been found that it is extremely effective to use a vinylsulfone hardener as a hydrophilic binder hardener constituting the silver halide color photographic material. However, this vinyl sulfone hardener has poor solubility in water and has a problem of causing precipitation when stored in a solution state. It has the problem of easily inducing repelling failure and impairing the quality of the image to be formed. It has both digital exposure and analog exposure suitability, and is resistant to pressure in an automatic processor that conveys at high speed in the form of a sheet. There is an urgent need for the development of a method that is compatible with aptitude.
JP 2003-207874 A

  The present invention has been made in view of the above-mentioned problems, and its purpose is to have a silver exposure suitability for digital exposure and analog exposure, excellent pressure resistance during high-speed processing in a sheet form, and excellent coating suitability. A color photographic light-sensitive material is provided.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer each containing a photosensitive silver halide on a support, 10 ⁻ per pixel. After exposure with an exposure time of ⁶ seconds, development processing was performed, and exposure was performed with an exposure amount (LogEd) giving the maximum point γ (γmd) of each obtained color image and an exposure time of 0.5 seconds per pixel. Thereafter, the difference ΔLogE (LogEd-LogEa) from the exposure amount (LogEa) giving the maximum point γ (γma) of each color image obtained after development processing is 0.15 or less, and the vinylsulfone-based dura A silver halide color photographic light-sensitive material containing an agent, wherein the vinyl sulfone hardener is dissolved and added by a compound represented by the following general formula (I).

[Wherein, X represents a substituted or unsubstituted alkylene, and Y represents a hydroxyl group or a hydrogen atom. However, at least three of Y are hydroxyl groups at the same time. ]
(Claim 2)
2. The silver halide color photographic material according to claim 1, wherein the vinyl sulfone hardener is a compound represented by the following general formula [HI].

[In formula, R < ¹ >, R < ⁴ > and R < ⁷ > represent an alkylene group and an arylene group, respectively. R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ represent —O—, —S—, — (C═O) —, —CH (OH) —, —NHCO— or —CONH—. m1 and m2 each represents 0 or 1; ]
(Claim 3)
The R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ^{9 in the} general formula [HI] are each a hydrogen atom, an alkyl group or a hydroxyl group. Silver halide color photographic light-sensitive material.

(Claim 4)
The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, comprising a surfactant represented by the following general formula (SI) or (S-II).

[Wherein, R ² represents an alkyl group or alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation, and may be the same as or different from M. n represents 1 or 2. ]

[Wherein R ³ represents an alkyl or alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. p represents 1 or 2. ]

  According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material that has suitability for digital exposure and analog exposure, is excellent in pressure resistance during high-speed processing in a sheet form, and is excellent in coating suitability.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

As a result of intensive studies in view of the above problems, the present inventor has found that a yellow color image forming layer, a magenta color image forming layer, and a cyan color image forming layer containing photosensitive silver halide are each provided on the support. In a silver halide color photographic light-sensitive material having a layer, exposure is performed with an exposure time of 10 ⁻⁶ seconds per pixel, followed by development processing, and an exposure amount (LogEd) that gives the maximum point γ (γmd) of each obtained color image ) And an exposure amount (LogEa) that gives the maximum point γ (γma) of each color image obtained after exposure with an exposure time of 0.5 seconds per pixel and development processing, ΔLogE (LogEd− LogEa) is 0.15 or less, contains a vinyl sulfone hardener, and the vinyl sulfone hardener is dissolved and added by the compound represented by the general formula (I). A silver halide color photographic light-sensitive material characterized by the above, having a digital exposure and analog exposure suitability, excellent pressure resistance during high-speed processing in the form of a sheet, and excellent coating suitability As a result, the present invention has been found.

  Details of the present invention will be described below.

In the silver halide color photographic light-sensitive material of the present invention, an exposure amount giving the maximum point γ (γmd) of each color image obtained after exposure with an exposure time of 10 ⁻⁶ seconds per pixel and development processing. (LogEd) and the exposure amount (LogEa) that gives the maximum point γ (γma) of each obtained color image after developing with an exposure time of 0.5 seconds per pixel and developing, ΔLogE ( One feature is that (LogEd-LogEa) is 0.15 or less.

  First, the exposure amount difference ΔLogE that gives the maximum point γ of each color image forming layer will be described.

In the present invention, ΔLogE means that each dye forming layer is exposed to 10 ⁻⁶ seconds and 0.5 seconds, and then developed, and the respective characteristic curves at a density of 0.8 are superimposed. In this case, the difference (ΔLogE) in the exposure amount position between the maximum points γ is 0.15 or less.

“Point γ” as used in the present invention means “T. H. As described in James "The Theory of the Photographic Process", 4th edition, page 502,
Point γ = dD / dLogE (D represents density, E represents exposure amount)
And represents a differential value of an arbitrary point on a characteristic curve (D-LogE curve) having a vertical axis—density D and a horizontal axis—exposure amount, and the maximum point γ indicates a point where the point γ becomes a maximum. .

The present inventors have found that ΔLogE when the characteristic curves are superimposed at a density point of 0.8 is important for specifically forming a character image and a scene image beautifully, and this ΔLogE is 0.15. Even when the exposure time is 10 ⁻⁶ seconds or 0.5 seconds, an image with good character quality and reproducibility of each scene image can be obtained, and when the exposure time is 0.10 or less, the image does not blur. Is found to be obtained, and particularly preferably 0.07 or less.

  In the present invention, the effects of the present invention can be obtained by satisfying the requirements stipulated in the present invention. However, in order to clarify the effects of the present invention, the following evaluation methods can be preferably used. .

  That is, using a laser scanning exposure apparatus adjusted so that the overlap between the rasters of the light beam is within the range of 5 to 30%, the 1 cm square patch is exposed on the photosensitive material while changing the exposure amount, Using the following color developer (CDC-1), color development for 45 seconds at 37 ± 0.5 ° C. (after color development, normal bleach-fixing and washing or stabilization treatment are performed) The reflection density of the gray patch portion of the obtained sample is measured, and a characteristic curve composed of the horizontal axis: exposure amount (Log E) and the vertical axis: reflection density (D) is created. The point gamma can be obtained by calculating the differential value. In the present invention, the time from the end of exposure to the start of development is 1 hour.

[Color developer (CDC-1)]
800ml of pure water
Triethylenediamine 2g
Diethylene glycol 10g
Potassium bromide 0.02g
Potassium chloride 4.5g
Potassium sulfite 0.25g
N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-
Aminoaniline sulfate 4.0g
5.6 g of N, N-diethylhydroxylamine
Triethanolamine 10.0g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g
30g potassium carbonate
Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.1 with sulfuric acid or potassium hydroxide.

In the present invention, the diameter of the light beam (beam diameter) is defined as the raster width. The light beam diameter here is the diameter of the light beam when the light beam intensity is e ^−2, and can be obtained by, for example, a beam monitor combining a slit and a power meter.

  In the present invention, even when exposure is performed with various digital exposure apparatuses having different exposure light sources, exposure methods, and the like, it is possible to stably reproduce a print with reduced character image reproducibility and scene image scanning unevenness, Even when the processing time from exposure to development changes, the mechanism for obtaining a stable print with little change in density is not clear, but the following phenomenon is estimated as a factor. That is, in a silver halide color photographic light-sensitive material, a latent image is formed around the photosensitive nuclei of the photosensitive silver halide by exposure, and a printed image is obtained by development processing, but it is mainly formed by chemical sensitization. The photosensitive nuclei and the latent images formed by exposure are not uniform, and there exist photosensitive nuclei and latent images in various states with a certain distribution. This distribution state is considered to be basically reflected in the characteristic curve, and it is considered that many photosensitive materials having different characteristic curve shapes have different distribution states of photosensitive nuclei or latent images. In high-intensity short-time exposure, there are photosensitive nuclei that are easily affected by exposure intensity and exposure time interval among the photosensitive nuclei that are the center of latent image formation, and each parameter is designed to be within the scope of the present invention. In this case, it is estimated that one of the factors that improve the print reproduction stability with respect to different exposure light sources and exposure methods is to reduce the ratio of sensitive nuclei that are easily affected. In addition, among latent images formed in high-intensity short-time exposure, there are latent images whose states tend to fluctuate over time after exposure, and when designed so that each parameter falls within the scope of the present invention, It is estimated that one of the factors that improve the print reproduction stability with respect to a change in processing time from exposure to development is that the ratio of the latent image that is easy to perform becomes small.

In the silver halide color photographic light-sensitive material of the present invention, an image is formed by exposure with an exposure time such as 10 ⁻⁶ seconds per pixel based on digital information. When image information is digitized and handled, the original image In general, a method is used in which density information is digitized and handled for each square. The original image is divided into grids and handled, and the minimum unit of digitized exposure information is one pixel. The exposure time per pixel can be considered as the time during which the intensity of the light beam or the irradiation time is controlled based on the digital data for one pixel. The exposure time per pixel of the present invention is preferably 10 ⁻³ seconds or less and 10 ⁻¹⁰ seconds or more, and this is one of the exposure conditions within the range of the exposure time. By satisfying the above, the effect of the present invention is obtained.

  In the present invention, it is preferable that one color image is formed by an independent single exposure. In the present invention, image formation by independent single exposure is, in other words, an exposure method in which a plurality of exposures are not performed simultaneously when forming one color image, and data of one pixel is converted into a silver halide color. This is an exposure method in which the light beam to be exposed on the photographic light-sensitive material does not exist at a plurality of locations simultaneously. The exposure of the pixels of the entire image is performed by relatively changing the positions of the luminous flux and the silver halide color photographic material. In this case, the light beam may move, the silver halide color photographic light-sensitive material may move, or each of them may move simultaneously. A typical example of this method is scanning exposure using a laser beam. This laser beam scanning exposure method uses a light beam diameter, a light beam overlap ratio (beam multiplicity) between adjacent scanning exposures, and a direction (sub-scanning direction) perpendicular to the light beam scanning direction (main scanning direction). ) And the exposure light source wavelength distribution. In particular, the light beam diameter and the light beam overlap ratio (beam multiplicity) between adjacent scanning exposures are the parts where the characteristics of each exposure apparatus appear most frequently, and apparatuses having different two characteristic values have different characteristics. Have. Each of these characteristic values can be arbitrarily set, and there are an infinite number of types of exposure apparatuses composed of these combinations.

  The means for satisfying the requirements of the present invention is not particularly limited. For example, the characteristics of the photosensitive silver halide contained in the photosensitive material can be optimally controlled, It can be achieved by using, for example, a method of appropriately controlling the types and amounts of various photographic additives such as couplers and inhibitors, alone or in combination.

  The silver halide color photographic light-sensitive material of the present invention has ΔLogE (LogEd-LogEa) as defined above of 0.15 or less, contains a vinyl sulfone hardener, and the vinyl sulfone hardener contains And dissolved and added by the compound represented by the general formula (I).

  First, the vinyl sulfone hardener will be described.

  Examples of the vinyl sulfone hardener according to the present invention include aromatic compounds such as those described in German Patent 1,100,942 and US Pat. No. 3,490,911. Alkyl compounds bonded with hetero atoms as described in 29622, 47-25373, 47-24259, and the like, sulfonamides and ester compounds as described in JP-B 47-8736, etc. 1,3,5-tris [β- (vinylsulfonyl) -propionyl] -hexahydro-s-triazine as described in JP-A-49-24435 or JP-B-50-35807, JP-A-51- Also included are alkyl compounds such as those described in No. 44164 and compounds described in JP-A No. 59-18944.

  In the present invention, it is preferable that the vinyl sulfone hardener is a vinyl sulfone hardener represented by the general formula [HI] from the viewpoint that the object and effects of the present invention can be exhibited.

In the general formula [HI], R ¹ , R ⁴ and R ⁷ each represent an alkylene group or an arylene group. R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ represent —O—, —S—, — (C═O) —, —CH (OH) —, —NHCO— or —CONH—. m1 and m2 each represents 0 or 1; Furthermore, in the present invention, R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are each preferably a hydrogen atom, an alkyl group or a hydroxyl group.

Examples of the alkylene group represented by R ¹ , R ⁴ and R ⁷ include groups such as methylene, ethylene, propylene and methylethylene, and examples of the arylene group include groups such as phenylene and naphthalene.

  The following are typical examples of vinylsulfone hardeners represented by the general formula [HI] preferably used in the present invention, but are not limited thereto.

  Examples of the vinyl sulfone hardener according to the present invention include U.S. Pat. No. 4,029,542, Japanese Examined Patent Publication Nos. 44-29622, 47-24259, 47-25373, and Japanese Unexamined Patent Publication No. 49-24435. It can be obtained by synthesis according to the synthesis method described in JP 53-41221, 59-18944 and the like.

  In addition to the above exemplary compounds, the vinyl sulfone hardener according to the present invention reacts with a compound having at least three vinyl sulfone groups in the molecular structure, such as exemplary compounds H-5 to 23, with the vinyl sulfone group. And a compound having a water-soluble group, for example, a reaction product (vinylsulfone precursor) obtained by reacting diethanolamine, thioglycolic acid, sarcosine sodium salt, taurine sodium salt and the like.

  When used in a silver halide color photographic light-sensitive material, the vinyl sulfone hardener according to the present invention may be used alone, in combination of two or more, or with other known hardeners. You may use together.

The use amount of the vinyl sulfone hardener according to the present invention in the silver halide color photographic light-sensitive material is preferably 1.0 to 1000 mg / m ² with respect to the photographic constituent layer of the silver halide color photographic light-sensitive material. More preferably, it is 10-500 mg / m < ² >, 0.1-100 mg is preferable when converted per 1.0 g of gelatin, More preferably, it is 1.0-50 mg.

  The vinyl sulfone hardener according to the present invention can be dissolved in water or an appropriate organic solvent, but such a vinyl sulfone hardener solution is likely to precipitate when stored for a long time. Has a problem.

  In the present invention, based on the above problems, when the vinyl sulfone hardener according to the present invention is dissolved, the compound represented by the general formula (I) is mixed and dissolved in the coexistence. By adopting this configuration, the storage stability of the vinyl sulfone hardener solution can be dramatically improved.

  The vinyl sulfone hardener solution containing the compound represented by the general formula (I) according to the present invention may be added to the silver halide color photographic material in advance in the coating solution. Alternatively, it may be mixed with a coating solution immediately before coating. Moreover, this vinyl sulfone type hardener solution may be added to all layers of the photographic composition layer coated on the support, and may be added to any layer (one layer or plural layers). It may be added.

Examples of the compound represented by the general formula (I) according to the present invention include pentaerythritol, trimethylolethane, trimethylolpropane, trimethylolbutane, and trimethylolpentane, but the present invention is not limited thereto. Not. The amount of these compounds used is preferably 0.01 to 10 times as much as the vinyl sulfone hardener when dissolved in the vinyl sulfone hardener. More preferably, it is double. Further, the addition amount of the silver halide color photographic light-sensitive material preferably amount to be the amount with the 0.1-100 mg / m ^2, the amount added to be the amount with the 3~80mg / m ² is more preferable.

  In this invention, it is preferable to contain surfactant represented by the said general formula (SI) or (S-II) further.

  When coating is performed using a coating solution containing the vinylsulfone hardener according to the present invention, a coating failure such as a cissing failure or a tailing failure (failure caused by precipitates) is likely to occur. have.

  By using the surfactant represented by the general formula (SI) or (S-II), the surface tension characteristics of the coating film are optimized and the coating stability is greatly improved. As a result, a silver halide color photographic light-sensitive material excellent in coating film homogeneity can be obtained.

In the general formula (SI), R ² represents an alkyl or alkenyl group having 8 to 21 carbon atoms, which may be unsubstituted or substituted, but preferably has a total carbon number. 10 to 18 alkyl groups or alkenyl groups. M represents a hydrogen atom or a metal cation such as Na ⁺ or K ⁺ . Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation such as Na ⁺ or K ⁺ , and may be the same as or different from M. n represents 1 or 2.

  Although the example of a compound of surfactant represented by the said general formula (SI) based on this invention is shown below, this invention is not limited to these.

  In the silver halide color photographic light-sensitive material of the present invention, the surfactant represented by the general formula (SI) according to the present invention is any layer of the hydrophilic colloid layer constituting the color photographic light-sensitive material of the present invention. However, it is preferably added to a layer adjacent to the support and a layer farthest from the support, for example, a protective layer.

The addition amount of the surfactant represented by the general formula (SI) according to the present invention is preferably 0.1 to 1000 mg, more preferably 1 to 100 mg per 1 m ^{2 of the} silver halide color photographic light-sensitive material of the present invention. In the method for producing a silver halide color photographic light-sensitive material in which a coating solution for forming a plurality of photographic constituent layers is coated on a support in a multilayer manner, a layer adjacent to the support and a layer farthest from the support For example, it is preferable to add to a protective layer, and the usage-amount at that time is the range of 0.005-50g per kg of coating liquid, Preferably it is 0.05-5g.

  Next, the surfactant represented by the general formula (S-II) according to the present invention will be described.

In the general formula (S-II), R ³ represents an alkyl group or alkenyl group having 8 to 21 carbon atoms, which may be unsubstituted or substituted, but preferably has a total carbon number. 9 to 18 alkyl or alkenyl groups. M represents a hydrogen atom or a metal cation such as Na ⁺ or K ⁺ . p represents 1 or 2.

  Although the example of a compound of surfactant represented by the said general formula (S-II) based on this invention is shown below, this invention is not limited to these.

  In the silver halide color photographic light-sensitive material of the present invention, the surfactant represented by formula (S-II) according to the present invention is a hydrophilic colloid layer constituting the silver halide color photographic light-sensitive material of the present invention. Although it can be added to any layer, it is preferably added to a layer adjacent to the support and a layer farthest from the support, for example, a protective layer.

The addition amount of the surfactant represented by formula (S-II) according to the present invention is preferably 0.1 to 1000 mg, more preferably 1 to 100 mg per 1 m ^{2 of the} silver halide color photographic light-sensitive material of the present invention. In the method for producing a silver halide color photographic light-sensitive material in which a coating solution for forming a plurality of photographic constituent layers is coated on a support in a multilayer manner, a layer adjacent to the support and a layer farthest from the support For example, it is preferable to add to the protective layer, and the amount used at that time is preferably in the range of 0.005 to 50 g, more preferably 0.05 to 5 g, per kg of the coating solution.

  Next, each component of the silver halide color photographic light-sensitive material of the present invention will be described.

  The silver halide grains in the silver halide emulsion according to the present invention preferably have a silver chloride content of 90 mol% or more, more preferably a silver chloride content of 93 mol% or more, and 95 mol%. It is still more preferable that it is above. The silver bromide content is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and still more preferably 2 to 8 mol%. The silver iodide content is preferably 0.05 to 2 mol%, more preferably 0.05 to 1 mol%.

  In the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used. In this case, the portion containing silver bromide at a high concentration is epitaxially bonded to the silver halide emulsion grains. Or a so-called core-shell emulsion, or a complete layer may not be formed and only regions having different compositions may exist. Further, although the composition may change continuously or discontinuously, it is preferable that the silver halide grains have a silver bromide localized phase in at least a part of the outermost shell, in the vicinity of the vertex. It is more preferable to have a silver bromide localized phase.

  In the present invention, the silver bromide localized phase is a silver halide phase containing silver bromide having a silver bromide content of at least twice the average silver bromide content of the silver halide grains according to the present invention, It preferably contains silver bromide having a silver bromide content of 3 times or more of the average silver bromide content of the silver halide grains, and preferably contains silver bromide having a silver bromide content of 5 times or more.

  The silver bromide localized phase preferably contains a group 8 metal compound described later. In this case, the Group 8 metal compound used is preferably an iridium complex.

  In the present invention, silver halide grains having at least one silver iodide localized phase inside the grains can also be preferably used. In the present invention, the term “grain interior” refers to a silver halide phase excluding the grain surface in silver halide grains. In the present invention, the silver iodide localized phase is a silver halide phase containing silver iodide having a silver iodide content of at least twice the average silver iodide content of the silver halide grains according to the present invention, It preferably contains silver iodide having a silver iodide content of at least 3 times the average silver iodide content of the silver halide grains, and preferably contains silver iodide having a silver iodide content of 5 times or more. In the present invention, the position of the silver iodide localized phase is preferably 60% or more outside the silver halide volume from the grain center, more preferably 70% or more, and more preferably 80% or more outside. Is most preferred.

  One of the preferred forms of the silver iodide localized phase is that the silver iodide localized phase is present in a layered form inside the silver halide grains (hereinafter also referred to as a silver iodide localized layer). It is also preferable to introduce two or more silver halide localized layers. In that case, at least one layer (hereinafter referred to as sublayer) having a main layer introduced under the above conditions and having a concentration lower than the maximum iodide concentration is more than the main layer. Further, it is preferably introduced near the particle surface. The I concentration of the main layer and sublayer can be arbitrarily selected according to the purpose. From the viewpoint of latent image stability, the main layer preferably has a high density as much as possible, and the sublayer preferably has a lower density than the main layer. In the present invention, another preferred form of the silver iodide localized phase is that the silver iodide localized phase is present in the vicinity of the apex or the ridge line of the silver halide grain, and is used in combination with the above-mentioned silver iodide localized layer. It is also preferable to do.

  When the silver halide emulsion in the present invention contains silver bromide and / or silver iodide, the silver bromide content of silver halide grains and / or the inter-grain variation coefficient of silver iodide content are respectively It is preferably less than 30%, more preferably less than 20%. The lower limit of the coefficient of variation between grains of the silver bromide content is 0.01%.

  The silver bromide content and silver iodide content of the silver halide grains can be determined by the EPMA method (Electron Probe Micro Analyzer method). Specifically, a sample in which silver halide grains are well dispersed so as not to contact each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensities of silver, bromine and iodine, the silver bromide content and silver iodide content of the individual silver halide grains can be determined.

  By the above method, the silver bromide content and silver iodide content of the silver halide grains determined for each silver halide grain were determined for 300 or more silver halide grains, and the averages were average silver bromide, respectively. The content ratio and the silver iodide content, and the grain-to-grain variation coefficient of the silver bromide content and the silver iodide content of the silver halide grains according to the present invention are determined by the following formula.

Coefficient of variation between grains of silver bromide content = (standard deviation of silver bromide content of silver halide grains) / (average silver bromide content) × 100 (%)
Coefficient of variation between grains of silver iodide content = (standard deviation of silver iodide content of silver halide grains) / (average silver iodide content) × 100 (%)
In the present invention, it is also preferable to use silver halide grains having dislocation lines inside the grains.

  In the present invention, various bromides or iodides can be used to contain silver bromide or silver iodide in the silver halide grains. For example, silver halide fine particles containing silver bromide or silver iodide disclosed in JP-A-2-68538, etc., a method using an aqueous solution of bromide salt or iodide salt such as potassium bromide aqueous solution or potassium iodide Alternatively, a method using a halide ion releasing agent can be arbitrarily used. In the present invention, the silver iodide content, silver bromide content, silver iodide localized phase, silver bromide localized layer, or dislocation line introduction in the silver halide grains, the concentration and amount of these additives, etc. Can be adjusted arbitrarily.

  In order to obtain a silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given.

  In the present invention, the silver halide grains preferably contain one or more group 8 metal complexes, and include one or more group 8 metal complex complexes having one or more water ligands and / or organic ligands. It is more preferable to contain.

  The group 8 metal complex used in the present invention is preferably a metal complex of iron, iridium, rhodium, osmium, ruthenium, cobalt and platinum. As the metal complex, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, a two-coordinate complex, and the like can be used, and a six-coordinate complex and a four-coordinate complex are preferable. The group 8 metal complex having one or more water ligands and / or organic ligands is more preferably an iridium metal complex.

  In the present invention, the ligand constituting the Group 8 metal complex is a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, or water coordination. Arbitrary, halogen ligands, ammonia, hydroxide, nitrous acid, sulfurous acid, peroxide ligands and organic ligands can be used, but nitrosyl ligands, thionitrosyls. It is preferable to contain one or more ligands selected from a ligand, a cyano ligand, a water ligand, a halogen ligand, and an organic ligand.

  In the present invention, an organic ligand refers to a compound that contains one or more H—C, C—C, or C—N—H bonds and can be coordinated to a metal ion. The organic ligand used in the present invention is selected from pyridine, pyrazine, pyrimidine, pyran, pyridazine, imidazole, thiazole, isothiazole, triazole, pyrazole, furan, furazane, oxazole, isoxazole, thiophene, phenanthroline, bipyridine, and ethylenediamine. It is preferable that the compound is a compound, an ion, or a compound obtained by introducing a substituent into these compounds.

  In the silver halide emulsion according to the present invention, a group 8 metal complex represented by the following general formula (A) can also be preferably used.

Formula (A)
R _n [MX _m Y _6-m ]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is iron, cobalt, ruthenium, iridium, rhodium, osmium, or platinum, and more preferably iron, ruthenium, rhodium, iridium, or osmium. R represents an alkali metal, preferably cesium, sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. X and Y represent ligands, such as a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, a halogen ligand, ammonia, water Represents oxide, nitrous acid, sulfurous acid, and peroxide ligands.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When metal ions form a complex, any counter cation such as potassium ions, calcium ions, sodium ions, ammonium ions, etc. can be used. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as a counter anion.

  In order to contain heavy metal ions in the silver halide emulsion according to the present invention, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, during physical ripening after the formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide salt and continuously added throughout the grain forming process or a part thereof.

The amount of the heavy metal ion added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide, and 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol. Mole is more preferred.

  Any shape can be used for the silver halide grains according to the present invention, but a preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, and JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) Volumes of 21, 39 (1973) etc. are used to make particles having shapes such as octahedron, tetrahedron, twenty-fourhedron, dodecahedron, etc. Can also be used. Further, grains having a twin plane other than normal crystals or tabular grains may be used.

  The silver halide grains according to the present invention are preferably grains having a single shape, but two or more monodispersed silver halide emulsions can be added to the same layer.

  The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.8, considering other photographic performance such as rapid processability and sensitivity. It is in the range of 2 to 3.0 μm. In particular, when cubic particles are used, it is preferably in the range of 0.1 to 1.2 μm, more preferably 0.15 to 1.0 μm.

  The grain size distribution of the silver halide grains of the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, more preferably 0.10 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. Represent.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion according to the present invention may be obtained by any of acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt solution and a water-soluble halide salt aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Published Patent No. 2921164 An apparatus for continuously adding a water-soluble silver salt solution and a water-soluble halide salt aqueous solution described in JP-A No. 56-501776, etc. An apparatus that forms grains while maintaining the distance between silver halide grains constant by concentration by a method may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

  The silver halide photographic emulsion according to the present invention is preferably desalted after grain formation. Desalting can be performed, for example, by the method of RD17643, Item II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a noodle water washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. An anionic polymer (eg, polystyrene sulfonic acid) can be used, but a precipitation method using gelatin derivatives and chemically modified gelatin (eg, acylated gelatin, carbamoylated gelatin) or ultrafiltration using membrane separation. Desalting is preferred.

  As the dispersion medium used in the production of the silver halide emulsion according to the present invention, a compound having a protective colloid property for silver halide grains can be arbitrarily used. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin and acid-treated gelatin having a molecular weight of about 100,000, or oxidized gelatin and enzyme-treated gelatin. Can be preferably used. The average molecular weight of gelatin at the time of nucleation of silver halide grains is preferably 10,000 to 70,000, and more preferably 10,000 to 50,000. It is also preferable to use gelatin having a low methionine content during nucleation, and the methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, more preferably 20 μmol or less. Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and various kinds such as copolymers such as polyvinyl pyrazole A synthetic hydrophilic polymer substance or the like can be used.

  The silver halide emulsion according to the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer and / or a selenium sensitizer are usable. Agents are preferred.

  Sulfur sensitizers include 1,3-diphenylthiourea, triethylthiourea, thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, thiosulfuric acid Salt, sulfur alone and the like are preferable. In addition, as sulfur simple substance, the alpha-sulfur which belongs to an orthorhombic system is preferable. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, No. 3,656,955, etc., West German Published Application (OLS) 1,422,869, JP-A-56-24937, 55-45016, etc. are used. be able to.

  As the selenium sensitizer, an unstable selenium compound capable of reacting with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, and 4-109240. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (such as N, N-dimethylselenourea, N, N, N'-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'- 4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamide (eg selenoacetamido, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.) Phosphates (eg, tri-p-triselenophosphate, etc.), selenides (eg, dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, trifurylphosphine selenide, Trypyridylphosphine selenide). Particularly preferred selenium sensitizers are selenourea, selenoamides, and selenides.

  In the present invention, noble metal salts such as gold, platinum, palladium, iridium and the like described in RD magazine 307, 307105 are preferably used, and in particular, a gold sensitizer is preferably used in combination. Useful gold sensitizers include U.S. Pat. Nos. 2,597,856, 5,049,485, and Japanese Patent Publication No. 44-15748 in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like. And organic gold compounds disclosed in JP-A-1-147537 and 4-70650, gold sulfide, and gold sulfide silver. Further, when performing a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, and thioether as an auxiliary agent, and in particular, it is preferable to use thiocyanate. .

  In the above-mentioned various chemical sensitizers, postscript inhibitors, oxidizing agents and the like according to the present invention, JP 2001-318443, JP 2003-29472, JP 2004-37554, 2004-4144, 2004-4446, 2004-4442, 2004-4456, 2004-4458, 2004-4656, 2004-4672, 2003-307803, 2003-287841, 2003 287842, 2003-233146, 2003-172990, 2003-172991, 2003-113193, 2003-113194, 2003-114489, 2002-372765, 2002-296721 No. 2002-278011, No. 2002 No. 268169, No. 2002-244241, No. 2002-259882, No. 2002-258427, No. 2002-268168, No. 2002-268170, No. 2000-193942, No. 2001-75214, No. 2001-75215 2001-75216, 2001-75217, 2001-75218, 2001-100352, 2004-70363, 2004-67695, 2002-131858, 2001-166612, etc. The compounds described in the gazette, European Patent Nos. 1094360, 13888752, U.S. Pat. Nos. 6,686,143 and 6,322,961, and the techniques for using them can also be preferably used.

The addition amount of the chalcogen sensitizer and gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, and the ripening conditions, but usually 1 × 10 ⁻⁹ per mole of silver halide. It is preferably ˜1 × 10 ⁻⁵ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. Depending on the nature of the sensitizer used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by premixing with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

  In the present invention, reduction sensitization may be used, and reducing compounds described in RD magazine 307, 307105, JP-A-7-78685, and the like may also be used.

  The silver halide emulsion according to the present invention is known for the purpose of preventing fogging that occurs during the preparation process of a silver halide photographic light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs during development. Antifoggants, oxidizing agents, inhibitors, stabilizers and the like can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferred specific compounds. As the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercapto Preferred are compounds such as tetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole, general formula (S) compounds described in JP-A-8-6201, thiosulfonic acid compounds, disulfide compounds, polysulfide compounds and the like. The compounds described in Nos. 29472, 2003-10482, 2002-31557 and the like can be preferably used.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. A preferable addition amount of these compounds is 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol / mol Ag ×, more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide. For the addition of these compounds, methods commonly used in the art when additives are added to photographic emulsions, coating solutions, preparation solutions and the like can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties, such as esters and amides, and added as a solution.

  In the silver halide color photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-252840, page 30 and The dyes described in JP-A-6-37706 are preferably used, and the infrared absorbing dyes are represented by the general formulas (I), (II), and (III) described in JP-A-1-280750, page 2, lower left column. The compounds have preferred spectral properties and are preferred without affecting the photographic properties of the silver halide photographic emulsion and without contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column.

  For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the unprocessed sample of the photosensitive material is 0.7 to 3.0. More preferably 0.

  It is preferable to add a fluorescent brightening agent to the silver halide color photographic light-sensitive material of the present invention because the white background can be improved. Preferred examples of the compound include compounds represented by the general formula (II) described in JP-A-2-232652.

  The silver halide color photographic light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments IRS-1 to IRS11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17.

  These sensitizing dyes may be added at any time from silver halide grain formation to coating solution preparation.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As a coupler used in the silver halide color photographic light-sensitive material of the present invention, any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Although a compound can also be used, particularly representative couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. And those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

  As a cyan dye-forming coupler that can be preferably used in the silver halide color photographic light-sensitive material of the present invention, general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. The coupler represented by these can be mentioned. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

  As a magenta dye-forming coupler that can be preferably used in the silver halide color photographic light-sensitive material of the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, right upper column. The coupler represented by these can be mentioned. Specific examples of the compound include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta dye-forming couplers, a coupler represented by the general formula (M-I) described in the upper right column on page 4 of the same publication is preferred. Among them, the RM of the general formula (M-I) is used. A coupler in which is a tertiary alkyl group is particularly preferred because of excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they are excellent in color reproduction from blue to purple and red, and are excellent in detail descriptive power.

  Examples of preferred couplers represented by the above general formula (M-I) are exemplified compounds 1 to 64 described on pages 5 to 9 of JP-A No. 63-253934 and JP-A No. 2-100048. Exemplified compounds M-1 to M-29 described on pages 5 to 6, Exemplified compounds (1) to (36) described on pages 5 to 12 of JP-A-7-175186, JP-A-7-219170 Exemplified compounds M-1 to M-33 described on pages 14 to 22 of the publication, Exemplified compounds M-1 to M-16 described on pages 5 to 9 of JP-A-8-304972, and JP-A-10- Exemplified compounds M-1 to M-26 described on pages 5 to 10 of 207024, Exemplified compounds M-1 to M-36 described on pages 5 to 22 of JP-A-10-207025, US Patent Exemplified compounds described on pages 3 to 6 of No. 5,576,150 -1 to M-24, Exemplified compounds M-1 to M-48 described on pages 3 to 9 of US Pat. No. 5,609,996, 3 of US Pat. No. 5,667,952 Exemplified compounds M-1 to M-23 described on pages 5 to 5, Exemplified compounds M-1 to M-26 described on pages 3 to 6 of US Pat. No. 5,698,386, etc. Can do.

Examples of yellow dye-forming couplers that can be preferably used include couplers represented by general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY _{1 in the} general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce a yellow color having a preferable color tone. Among these, as particularly preferred compound examples, YC-8, YC-9 described in JP-A-4-114154, page 4, upper left column, and No. described in JP-A-6-67388, pages 13-14 The compound shown by 1)-(47) can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  When using an oil-in-water emulsion dispersion method to add a coupler or other organic compound used in the silver halide color photographic light-sensitive material of the present invention, it is usually a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. In addition, if necessary, it is dissolved in combination with a low boiling point or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted on the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time from addition to coating after coating is shorter. It is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas [I] and [II] described on page 3 of JP-A-2-66541, and a general formula [IIIB] described in JP-A-3-1741503. A phenol compound represented by formula (A), an amine compound represented by formula [A] described in JP-A No. 64-90445, a general formula [XII], [XIII], [XIV described in JP-A No. 62-182741 ] And [XV] are particularly preferable for magenta dyes. Further, the compound represented by the general formula [I] described in JP-A-1-196049 and the compound represented by the general formula [II] described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound (d-11) described in JP-A-4-114154, page 9, lower left column, compound (A'-1) described in page 10, lower left column, etc. Can be used. In addition, fluorescent dye releasing compounds described in US Pat. No. 4,774,187 can also be used.

  In the silver halide color photographic light-sensitive material of the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the photosensitive layer to prevent color turbidity, or it is added to the silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 and compound-1 described on page 17 Is mentioned.

  In the silver halide color photographic light-sensitive material of the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by [III], UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula [I] described in JP-A-4-16333, JP-A-5-165144 And compounds represented by the general formulas (I) and (II) described in Japanese Patent Publication.

  In the silver halide color photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but other gelatins, gelatin derivatives, graft polymers of gelatin and other polymers, and proteins other than gelatin as necessary. Also, hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can be used. The calcium content in gelatin is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Further, the content of heavy metals such as zinc, copper, manganese, and iron in gelatin is preferably 10 ppm or less, more preferably 5 ppm or less, and still more preferably 3 ppm or less.

In the silver halide color photographic light-sensitive material of the present invention, the total Coating amount of gelatin structure layer is 3 g / m ² or more, preferably 6 g / m ² or less, 3 g / m ² or more, 5 g / m ² More preferably, it is as follows. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability, and residual color, the total thickness of the constituent layers is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6.5 μm. It is preferable that The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. Coated silver amount in the present invention is ^{0.3g / m 2 ~0.6g / m 2} .

  Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer. The film pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

  The silver halide color photographic light-sensitive material of the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but a plurality of color image forming layers as necessary. The unit may be formed by.

  As the support used for the silver halide color photographic light-sensitive material of the present invention, any material may be used, paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet Polypropylene which may contain a white pigment, polyethylene terephthalate support, baryta paper or the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained. Also, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, a trace amount of ultramarine, oil-soluble dyes, etc. It is preferable to add a blue tinting agent or a red tinting agent.

  The silver halide color photographic light-sensitive material of the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and directly or undercoat layer (adhesiveness of the support surface, antistatic properties). , One or more subbing layers for improving dimensional stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties).

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful. As the coating device, a slide coater, a curtain coater, an extrusion coater, or the like can be used.

  In order to form a photographic image using the silver halide color photographic material of the present invention, an image recorded on the negative is optically imaged on the silver halide photographic material to be printed. The image may be printed, or once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is formed on a silver halide photographic material to be printed and printed. Alternatively, printing may be performed by changing the intensity of laser light based on digital information and scanning.

  The silver halide color photographic light-sensitive material of the present invention is preferably applied to a silver halide color photographic light-sensitive material that does not contain a developing agent, and in particular, a silver halide color photographic light-sensitive material that forms an image for direct viewing. It is preferable that Examples thereof include color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display, and photosensitive material for color proof, and among them, a silver halide color photographic photosensitive material having a reflective support. It is preferable to apply to.

  In the processing method of the silver halide color photographic light-sensitive material of the present invention, the exposed silver halide color photographic light-sensitive material is subjected to a bleaching step (bleaching solution), a fixing step (following the color developing step (color developing solution)). Fixing solution), bleach-fixing step (bleaching fixing solution), and stabilizing step (stabilizing solution), followed by drying. Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like. The color developer, bleaching solution, bleach-fixing solution, fixing solution, stabilizing solution, and rinsing solution used in the present invention will be described below.

  Preferred examples of the color developing agent used in the color developing solution according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. It is not something.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 mmol to 200 mmol, more preferably 6 mmol to 100 mmol, and particularly preferably 10 mmol to 40 mmol per liter of the developing solution.

  The color developer used in the present invention preferably contains a preservative to reduce the disappearance of the color developing agent due to oxidation. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Although the hydroxylamine derivative described in 1-187557 etc. can be used, the hydroxylamine derivative represented with the following general formula [A] is especially preferable.

  In the above general formula [A], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. Represents an ammonio group which may be substituted, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′; , R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

  In the above general formula [A], L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, and an ammonio group that may be alkyl-substituted. Preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted. Preferred examples include a carbamoyl group which may be substituted with a group or an alkyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, -O- (B -O) n-R 'and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Particularly preferred examples include a group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula [A], this invention is not limited to these compounds.

  Further, it is also preferable to use sulfite as a preservative, and the concentration thereof is preferably 0.005 to 1.0 mol / L in the color developer for color negative film, and in the color developer for color paper, 0 to 0.1 mol / L is preferable. Examples of sulfites that can be used in the present invention include sodium sulfite, potassium sulfite, and ammonium sulfite.

  In the color developer, in addition to the preservative according to the present invention described above, use of the preservative shown below is not limited. Hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably 9.0 or more and 13.5 or less, more preferably 9.5 or more and 12.0 or less, and an alkaline agent and a buffer so that the pH value can be maintained. Agents and optionally acids can be included.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, it is preferable to use the buffer shown below. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, and the like can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  These buffers are preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as required. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  As other bis (triazinylamino) stilbene sulfonic acid compounds, compounds I-1 to I-48 and JP-A-2001-2001 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 are disclosed. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter of color developer.

When bromine ions are contained in the color developing solution for color paper, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution for color paper preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually used as a by-product in development. Since it is released into the developer, it may not be necessary to add it to the replenisher.

In the present invention, the processing temperature of color development that can be applied by the processing method is preferably 30 to 55 ° C., more preferably 35 to 35 ° C., when the silver halide color photographic light-sensitive material to be developed is color paper. It is 55 degreeC, More preferably, it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

  In the present invention, any bleaching agent may be used as the bleaching agent used in the bleaching solution or the bleach-fixing solution. Particularly, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid). Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates Hydrogen peroxide is preferred.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  In the bleaching solution or the bleach-fixing solution, various compounds can be used as a bleaching accelerator. For example, a compound having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power. .

  In addition, the bleaching solution or the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide), chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution or the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid Water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas can be used singly or in combination of two or more. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably from 0.1 to 5.0 mol, more preferably from 0.3 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9.

  In addition, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain various other kinds of fluorescent whitening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

  Bleaching solutions, fixing solutions and bleach-fixing solutions are used as preservatives, such as sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed. The ammonium cation concentration in the bleaching solution, the fixing solution, and the bleach-fixing solution is preferably 50 mol% or less with respect to the total cations from the viewpoint of workability, but from the viewpoint of processability, the ammonium cation concentration is 50 mol% or more. It is preferable that there is.

The time required for the bleach-fixing step that can be applied to the method for processing a silver halide color photographic light-sensitive material of the present invention is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent rinsing or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, and more preferably ^{20ml / m 2 ~100ml / m 2} .

The replenishment rate of the bleaching treatment solution is preferably 200 ml / m ² or less, and more preferably ^{50ml / m 2 ~200ml / m 2} . The total processing time of the bleaching step is preferably 15 seconds to 90 seconds. The time required for the bleaching step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC. The replenishment rate of the fixing treatment solution is preferably 600 ml / m ² or less, and more preferably ^{20ml / m 2 ~500ml / m 2} . The total processing time of the fixing process is preferably 15 seconds to 90 seconds. The time required for the fixing process here refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC.

  Next, the rinsing or stabilizing process and the treatment liquid used therein will be described.

  Rinsing or stabilizing solution used in the stabilization step includes chelating agents (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (potassium carbonate, borate, acetate, Phosphates, etc.), antifungal agents (Dearside 702 (manufactured by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent brighteners (triazinyl stilbene compounds, etc.) ), Antioxidants (ascorbate, etc.), water-soluble metal salts (zinc salt, magnesium salt, etc.), and the like, which are usually contained in a stable solution, can be used as appropriate.

Furthermore, the rinse or stabilizing solution may contain arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid from the viewpoint of liquid storage stability, and may contain sulfite, bisulfite or metabisulfite. It is also preferable to contain a sulfite. Any organic or inorganic substance may be used as long as it releases sulfite ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more, more preferably 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L in the stabilizing solution. It is added to become L.

  4-10 are preferable and, as for the preferable pH of a stabilization process, More preferably, it is 5-8.

  The temperature of the stabilization step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute. However, when the silver halide color photographic light-sensitive material is color paper, the time required for the stabilization processing step is 8 to 26 seconds. In addition, when the silver halide color photographic light-sensitive material is a color negative film, the time required for the stabilization process is preferably 10 to 40 seconds.

  A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of silver halide color photographic light-sensitive material, which is brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method according to the present invention, the structure of the stabilization process using the stabilizing liquid may be composed of one tank or may be composed of two or more layers, preferably two or more tanks. It is preferable to use a multistage countercurrent system constituted by:

  Multi-stage counter-current system is a method of conveying silver halide photographic light-sensitive materials in a stabilizing tank divided into a plurality of stages, while the stabilizing solution overflows into each multi-stage divided stabilizing tank from the downstream to the upstream in the conveying direction of the photosensitive material. It is a system that flows along the road and performs a stabilization process.

The development processing apparatus used for processing the silver halide color photographic light-sensitive material of the present invention fixes the light-sensitive material to the belt even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank. It may be an endless belt system that conveys
From the viewpoint of exhibiting the objective effects of the present invention, it is preferable to use a roller transport type in which the silver halide color photographic light-sensitive material cut into a sheet is conveyed by being sandwiched between rollers.

  Further, as the processing tank, the processing tank is formed in a slit shape, and the processing liquid is supplied to the processing tank and the photosensitive material is conveyed, the spraying method for spraying the processing liquid, and the processing liquid is impregnated. A web system using contact with a carrier, a system using a viscous treatment liquid, or the like can also be used. In the case of processing in large quantities, it is normal that the running processing is performed using an automatic processor. In this case, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technique 94-16935 is most preferable.

The silver halide color photographic light-sensitive material of the present invention is particularly preferable since the image quality improvement by the light-sensitive material of the present invention is particularly large when an image is formed by exposure through a negative film having an area per screen of 3 to 7 cm ² . The negative film may have information recording ability.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

<< Preparation of silver halide emulsion >>
[Preparation of silver halide emulsion (B-1)]
While stirring vigorously using a mixing and stirring apparatus described in JP-A-62-160128, a double ion exchange treated ossein gelatin (calcium content 10 ppm) 2% gelatin aqueous solution kept at 40 ° C. Using the jet method, the following (A1 liquid) and (B1 liquid) were simultaneously added over 17 minutes while controlling pAg = 7.3 and pH = 3.0. Subsequently, the following (A2 solution) and (B2 solution) were simultaneously added over 90 minutes while controlling pAg = 8.0 and pH = 5.5. Furthermore, the following (A3 liquid) and (B3 liquid) were simultaneously added over 15 minutes, controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled and adjusted using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution)
Sodium chloride 3.42g
Potassium bromide 0.021g
Water was added to make up to 200 ml.

(A2 liquid)
Sodium chloride 72.0g
K ₂ IrCl ₆ 1.8 × 10 ⁻⁸ mol / mol AgX
K ₂ IrBr ₆ 5.0 × 10 ⁻⁹ mol / mol AgX
K ₄ Fe (CN) ₆ 4.5 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.44g
Water was added to make 420 ml.

(A3 liquid)
Sodium chloride 30.7g
Potassium bromide 0.63g
Water was added to make 180 ml.

(B1 solution)
Silver nitrate 10g
Water was added to make up to 200 ml.

(B2 liquid)
210g silver nitrate
Water was added to make 420 ml.

(B3 liquid)
90g silver nitrate
Water was added to make 180 ml.

  After completion of the addition, a 15% aqueous solution containing 30 g of chemically modified gelatin (modified ratio 95%) in which the amino group is phenylcarbamoylated was added using the method described in JP-A-5-72658, and then desalted. By mixing with an aqueous solution, a silver halide emulsion (B-1) having an average particle size of 0.68 μm was prepared.

[Preparation of silver halide emulsion (B-2)]
A silver halide emulsion (B-2) was prepared in the same manner as in the preparation of the silver halide emulsion (B-1) except that (A2a solution) having the following composition was used instead of (A2 solution). Prepared.

(A2a solution)
Sodium chloride 72.0g
K ₂ [IrCl ₆ ] 3.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 2.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 1.8 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 1.0 × 10 ⁻⁸ mol / mol AgX
K ₄ Fe (CN) ₆ 5.0 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.44g
Water was added to make 420 ml.

[Preparation of silver halide emulsions (BB-1) and (BB-2)]
In the preparation of the silver halide emulsions (B-1) and (B-2), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl _{5 in} (A2 solution) and (A2a solution) are used. The amounts of (H ₂ O)], K ₂ [IrCl ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 1.6 times, and (A1 solution), (A2 solution), (A2a Solution), (A3 solution), (B1 solution), (B2 solution), and (B3 solution), except that the addition time was changed appropriately. Similarly, a silver halide emulsion (BB-) having an average grain size of 0.60 μm 1) and (BB-2) were prepared.

[Preparation of silver halide emulsions (G-1) and (G-2)]
In the preparation of the silver halide emulsions (B-1) and (B-2), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl _{5 in} (A2 solution) and (A2a solution) are used. The amounts of (H ₂ O)], K ₂ [IrCl ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 2.0 times, and (A1 solution), (A2 solution), (A2a Solution), (A3 solution), (B1 solution), (B2 solution), and (B3 solution), except that the addition time was changed appropriately. Similarly, a silver halide emulsion having an average grain size of 0.55 μm (G- 1) and (G-2) were prepared.

[Preparation of silver halide emulsions (GG-1) and (GG-6)]
In the preparation of the silver halide emulsions (B-1) and (B-2), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl _{5 in} (A2 solution) and (A2a solution) are used. The amounts of (H ₂ O)], K ₂ [IrCl ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 3.8 times, and (A1 solution), (A2 solution), (A2a Solution), (A3 solution), (B1 solution), (B2 solution), and (B3 solution), except that the addition time was changed appropriately. Similarly, a silver halide emulsion (GG-) having an average grain size of 0.45 μm 1) and (GG-2) were prepared.

[Preparation of silver halide emulsions (R-1) and (R-2)]
In the preparation of the silver halide emulsions (B-1) and (B-2), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl _{5 in} (A2 solution) and (A2a solution) are used. The amounts of (H ₂ O)], K ₂ [IrCl ₅ (thiazole)] and K ₄ Fe (CN) ₆ were changed to 4.5 times each, and (A1 solution), (A2 solution), (A2a Solution), (A3 solution), (B1 solution), (B2 solution), and (B3 solution), except that the addition time was changed appropriately. Similarly, a silver halide emulsion (R- 1) and (R-2) were prepared.

[Preparation of silver halide emulsion (RR-1), (RR-2)]
In the preparation of the silver halide emulsions (B-1) and (B-2), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl _{5 in} (A2 solution) and (A2a solution) are used. The amounts of (H ₂ O)], K ₂ [IrCl ₅ (thiazole)] and K ₄ Fe (CN) ₆ were each changed to 8.0 times, and (A1 solution), (A2 solution), (A2a) Solution), (A3 solution), (B1 solution), (B2 solution), and (B3 solution), except that the addition time was changed appropriately. Similarly, a silver halide emulsion (RR-) having an average grain size of 0.35 μm 1) and (RR-2) were prepared.

  In each silver halide emulsion prepared as described above, cubic silver halide grains accounted for 99% or more of the number of silver halide grains.

<Preparation of blue-sensitive silver halide emulsion>
[Preparation of blue-sensitive silver halide emulsion (B-1a)]
To the silver halide emulsion (B-1) prepared above, the following sensitizing dyes BS-1 and BS-2 were added at 60 ° C., pH 5.8, and pAg 7.5, followed by sodium thiosulfate and chloroauric acid. Were sequentially added to give spectral and chemical sensitization. After the chemical sensitizer is added and optimally ripened, the compounds (S-1), (S-2), and (S-3) are sequentially added to stop the ripening, and the blue-sensitive silver halide emulsion (B -1a) was obtained.

Sodium thiosulfate 6.5 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-2) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-3) 2.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
[Preparation of blue-sensitive silver halide emulsion (B-1b)]
In the preparation of the blue-sensitive silver halide emulsion (B-1a), the silver halide emulsion (B-2) prepared above was used instead of the silver halide emulsion (B-1). The addition amount was changed to 3.9 × 10 ⁻⁶ mol / mol AgX, and after addition of sodium thiosulfate, trifurylphosphine selenide was added to 2.6 × 10 ⁻⁶ mol / mol AgX, and then gold chloride was added. A blue-sensitive silver halide emulsion (B-1b) was obtained in the same manner except that acid sensitization was performed to add an acid.

[Preparation of blue-sensitive silver halide emulsions (BB-1a) and (BB-1b)]
In the preparation of the blue-sensitive silver halide emulsions (B-1a) and (B-1b), the silver halide emulsions (B-1) and (B-2) were each prepared as described above. 1) and (BB-2), respectively, and addition amounts of sodium thiosulfate, trifurylphosphine selenide, chloroauric acid, sensitizing dye (BS-1) and sensitizing dye (BS-2) In consideration of the increase in the surface area of the silver halide grains accompanying the change in the average grain size of the silver halide grains from 0.68 μm to 0.60 μm, the addition amount per unit surface area is changed to be the same. Blue sensitive silver halide emulsions (BB-1a) and (BB-1b) were prepared in the same manner as described above.

<< Preparation of green sensitive silver halide emulsion >>
[Preparation of green-sensitive silver halide emulsion (G-1a)]
To the silver halide emulsion (G-1), the following sensitizing dye (GS-1) was added at 60 ° C., pH 5.8, pAg 7.5, and then sodium thiosulfate and chloroauric acid were added successively. Spectral sensitization and chemical sensitization were performed. After the chemical sensitizer was added and optimally ripened, the compound (S-1) was added to stop the ripening to obtain a green sensitive silver halide emulsion (G-1a).

Sensitizing dye: GS-1 5.3 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 5.5 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.5 × 10 ⁻⁴ mol / mol AgX
[Preparation of green sensitive silver halide emulsion (G-1b)]
In the preparation of the green-sensitive silver halide emulsion (G-1a), the silver halide emulsion (G-2) prepared above was used instead of the silver halide emulsion (G-1), and the amount of sodium thiosulfate added Was changed to 3.3 × 10 ⁻⁶ mol / mol AgX, and after addition of sodium thiosulfate, 2.2 × 10 ⁻⁶ mol / mol AgX of trifurylphosphine selenide was added, and then chloroauric acid was added. Green-sensitive silver halide emulsions (G-1b) were prepared in the same manner except that they were added and chemically sensitized.

[Preparation of green-sensitive silver halide emulsions (GG-1a) and (GG-1b)]
In the preparation of the green-sensitive silver halide emulsions (G-1a) and (G-1b), instead of the silver halide emulsions (G-1) and (G-2), the prepared silver halide emulsion (GG) -1) and (GG-2), and the addition amount of sodium thiosulfate, trifurylphosphine selenide, chloroauric acid, and sensitizing dye (GS-1) is changed to the average grain size of silver halide grains. In consideration of the increase in the surface area of the silver halide grains accompanying the change of the diameter from 0.55 μm to 0.45 μm, the green color is changed in the same manner except for changing each so that the addition amount per unit surface area becomes the same. Sensitive silver halide emulsions (GG-1a) and (GG-1b) were prepared.

<< Preparation of red-sensitive silver halide emulsion >>
[Preparation of red-sensitive silver halide emulsion (R-1a)]
The following sensitizing dyes (RS-1) and (RS-2) are added to the silver halide emulsion (R-1) at 60 ° C., pH 5.0, and pAg 7.1, followed by sodium thiosulfate and chloride. Gold acid was sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, compound (S-1) was added to stop ripening, and a red-sensitive silver halide emulsion (R-1a) was prepared.

Sodium thiosulfate 1.2 × 10 ⁻⁵ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Preparation of red-sensitive silver halide emulsion (R-1b)]
In the preparation of the red-sensitive silver halide emulsion (R-1a), the silver halide emulsion (R-2) prepared above was used instead of the silver halide emulsion (R-1), and the addition amount of sodium thiosulfate Was changed to 7.2 × 10 ⁻⁶ mol / mol AgX, and after addition of sodium thiosulfate, 4.8 × 10 ⁻⁶ mol / mol AgX of trifurylphosphine selenide was added, and then chloroauric acid was added. A red-sensitive silver halide emulsion (R-1b) was prepared in the same manner except that it was added and chemically sensitized.

[Preparation of red-sensitive silver halide emulsions (RR-1a) and (RR-1b)]
In the preparation of the red-sensitive silver halide emulsions (R-1a) and (R-1b), instead of the silver halide emulsions (R-1) and (R-2), the prepared silver halide emulsion (RR) -1) and (RR-2), and the addition amount of sodium thiosulfate, trifurylphosphine selenide, chloroauric acid, sensitizing dye (RS-1) and sensitizing dye (RS-2) is halogenated Considering the increase in the surface area of the silver halide grains accompanying the change of the average grain size of the silver halide grains from 0.42 μm to 0.35 μm, the respective addition amounts are set so that the addition amount per unit surface area is the same. Red-sensitive silver halide emulsions (RR-1a) and (RR-1b) were prepared in the same manner except that the changes were made.

In the preparation of each red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

  In the preparation of each photosensitive silver halide emulsion, when the addition interval of the sensitizing dye, the chemical sensitizer, and the chemical sensitization time are used in the silver halide color photographic light-sensitive material, Table 4 described later is used. As appropriate, the ΔLogE value described in (1) was adjusted.

<< Preparation of silver halide color photographic material >>
[Preparation of Sample 101]
High-density molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass is laminated on the photosensitive layer coated surface of paper pulp having a basis weight of 180 g / m ² , and the back surface has a high density. A silver halide color photographic light-sensitive material is formed by subjecting a reflective support laminated with polyethylene to corona discharge treatment, and then providing a gelatin subbing layer and further coating each photographic constituent layer having the constitution shown in Tables 1 and 2. Sample 101 was prepared.

  The coating solution was prepared as follows.

  The details of the silver halide emulsion used in each photosensitive layer are as follows.

Blue-sensitive silver halide emulsion of the first layer (blue-sensitive layer): Blue-sensitive silver halide emulsion (B-1b): Blue-sensitive silver halide emulsion (BB-1b) = 90: 10
Green sensitive silver halide emulsion of the third layer (green sensitive layer): green sensitive silver halide emulsion (G-1b): green sensitive silver halide emulsion (GG-1b) = 5: 95
5th layer (red-sensitive layer) red-sensitive silver halide emulsion: red-sensitive silver halide emulsion (R-1b): red-sensitive silver halide emulsion (RR-1b) = 33: 67
In the preparation of the sample 101, an (HS-1) aqueous solution was added as a hardener, and an amount of 0.02 g / m ² as a hardener was divided and added to the second layer, the fourth layer, and the seventh layer. did.

In addition, surfactant (SU-2) is used for the preparation of the coupler dispersion of each layer, and surfactants (SU-1) and (SU-3) are used as coating aids for adjusting the surface tension of each constituent layer. ) Was added. Moreover, the antifungal agent (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.

  Details of each additive used for preparation of the sample 101 are as follows.

Sol-1: tricresyl phosphate Matting agent 1: SiO ₂ (average particle size: 3.0 μm)

[Production of Sample 102]
In the preparation of Sample 101, Sample 102 was prepared in the same manner except that the same molar amount of Exemplary Compound H-46 aqueous solution was used instead of the hardener (HS-1).

[Production of Sample 103]
Sample 103 was prepared in the same manner as in the preparation of Sample 101 except that the same molar amount of the exemplary compound H-25 aqueous solution was used instead of the hardener (HS-1).

[Production of Sample 104]
Sample 104 was prepared in the same manner as Sample 101 except that the following hardener solution 1 was used instead of the hardener (HS-1). The amount of Example Compound H-25 added was the same mol as the hardener of Sample 101.

(Hardener solution 1)
Exemplified Compound H-25 4g
Trimethylolpropane (abbreviated as TMP in Table 3) 1 g
95g of water
The above-mentioned additives were mixed and dissolved to prepare a hardener solution 1.

[Preparation of Sample 105]
In the preparation of Sample 104, the blue-sensitive silver halide emulsion of the first layer was changed to blue-sensitive silver halide emulsions (B-1a) and (BB-1a), and the green-sensitive silver halide emulsion of the third layer was changed to green-sensitive halide. Except that the silver emulsions (G-1a) and (GG-1a) and the red-sensitive silver halide emulsion of the fifth layer were changed to red-sensitive silver halide emulsions (R-1a) and (RR-1a) Sample 104 was manufactured.

[Production of Sample 106]
A sample 106 was prepared in the same manner as in the preparation of the sample 104 except that the following hardener solution 2 was used instead of the hardener solution 1. The amount of Example Compound H-46 added was the same mole as the hardener of Sample 101.

(Hardener solution 2)
Exemplified Compound H-46 4g
1 g of trimethylolpropane (TMP)
95g of water
The above-mentioned additives were mixed and dissolved to prepare a hardener solution 2.

[Preparation of Sample 107]
A sample 107 was prepared in the same manner as in the preparation of the sample 104 except that the following hardener solution 3 was used instead of the hardener solution 1. The amount of Example Compound H-42 added was the same mole as the hardener of Sample 101.

(Hardener solution 3)
Illustrative compound H-42 4 g
1 g of trimethylolpropane (TMP)
95g of water
[Preparation of Sample 108]
A sample 108 was prepared in the same manner as in the preparation of the sample 104 except that the following hardener solution 4 was used instead of the hardener solution 1. The amount of Example Compound H-25 added was the same mol as the hardener of Sample 101.

(Hardener solution 4)
Exemplified Compound H-25 4g
Trimethylolpentane (abbreviated as TMPE in Table 3) 1 g
95g of water
[Production of Sample 109]
Sample 109 was prepared in the same manner as in the preparation of Sample 104, except that the same amount of Exemplary Compound (S-II-5) was used instead of the surfactant (SU-4) in the seventh layer.

[Preparation of Sample 110]
In the production of the sample 104, a sample 110 was produced in the same manner except that the same amount of the exemplified compound (SI-3) was used instead of the surfactant (SU-4) in the seventh layer.

<< Evaluation of each characteristic >>
[Evaluation of precipitation resistance of hardening liquid]
After putting the hardener aqueous solution and the hardener solution used for the preparation of the samples 101 to 110 into a glass container so that the filling rate is 80%, the container is stirred in a constant temperature bath at 40 ° C. Stored for 24 hours. After storage, the state of the hardener aqueous solution or hardener solution in the container was visually observed, and the precipitation resistance of the hardener was evaluated according to the following criteria.

A: The dura solution is completely clear and no generation of precipitates is observed. B: Slight turbidity is observed in the dura solution, but no generation of visual precipitates is observed. Δ: In dura solution. Weak turbidity is observed, but is practically acceptable. ×: Strong turbidity occurs in the dura mater, and a small amount of sediment is observed at the bottom. Precipitation occurs over time, and hard turbidity and precipitate formation are observed in the dura mater. [Evaluation of coatability]
About 1 m < ² > of each sample produced by the said method, the presence or absence of application | coating failure was observed using the loupe, and also the visual observation was performed about the presence or absence of application | coating nonuniformity, and applicability | paintability was evaluated according to the following reference | standard.

A: There is no occurrence of coating failure or coating unevenness, and coating film uniformity is excellent. ○: Very weak coating unevenness is observed, but there is no coating failure, and the coating film quality is good. unevenness was observed, generation of minute coating defects below 0.5mm per 1 m ² is 2 or less, practically is the coating quality of the acceptable range ×: coating unevenness was observed, 1 m ² Occurrence of minute coating failure of 0.5 mm or less per 3 to 3 is a coating quality which is a practical problem. XX: Generation of strong coating unevenness is observed, and 1.0 mm or more per 1 m ² There are 5 or more occurrences of coating failure, and this is a coating quality that is a practical problem. [Measurement of maximum point gamma difference ΔLogE]
(Evaluation A)
Each of the prepared samples was cut into a L-size sheet, and then subjected to wedge exposure in 0.5 seconds using a light source of 5400 ° K, and development processing was performed according to the following development processing 1. Each step of the gray step image thus obtained was measured for each reflection density using a densitometer PDA-65 (manufactured by Konica Minolta Photo Imaging), and the horizontal axis—exposure amount (Log E), A characteristic curve composed of reflection density (D) was prepared. Next, with respect to the magenta image, the differential value of the density with respect to the exposure amount was calculated for each step to obtain the maximum point γ (γma).

(Evaluation B)
Change the exposure device to a xenon flash high intensity exposure sensitometer (Yamashita Denso Co., Ltd. SX-20 type) and combine the latten filter to adjust the exposure appropriately so that a gray step image can be obtained. Then, after performing exposure with an exposure wedge of 10 ⁻⁶ seconds through an optical wedge for sensitometry, the same development processing 1 and reflection density measurement as in the above evaluation A are performed. The maximum value γ (γmd) was obtained by calculating the differential value of the concentration with respect to.

(Calculation of ΔLogE)
In each of the characteristic curves obtained in the evaluations A and B, the position difference of the exposure amount (LogEd, LogEa) showing the maximum point gamma, that is, the characteristic curve is such that the point of D = 0.8 overlaps. When the two characteristic curves are slid and the two characteristic curves are superimposed, an exposure point (LogEa) that gives the maximum point γ on the characteristic curve in evaluation A and a maximum point γ on the characteristic curve in evaluation B are given. The difference ΔLogE value (LogEd−LogEa) from the exposure point (LogEd) was determined.

(Development process 1)
Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml
Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120ml
Stabilization 30-34 ° C 60 seconds 150ml
Drying 60-80 ° C. 30 seconds <Color developer tank solution and replenisher>
Tank liquid Replenisher Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g
N, N-diethylhydroxylamine 6.8 g 6.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Water was added to adjust the total volume to 1 liter, the tank liquid was adjusted to pH 10.10, and the replenisher was adjusted to pH 10.60.

<Bleach fixer tank solution and replenisher>
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing liquid tank liquid and replenisher liquid>
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Bismuth chloride (45% aqueous solution) 0.65 g
Magnesium sulfate-7 hydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5 g
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[Evaluation of pressure resistance]
Each sample was subjected to wedge exposure with blue light through a green filter using a xenon flash high illuminance exposure photometer (SX-20 model, manufactured by Yamashita Denso Co., Ltd.) exposed at 10 ⁻⁶ seconds. Each sample after exposure was immersed in pure water at 38 ° C. for 45 seconds, then pressure was applied to the sample according to the following pressurization method, and then development processing was performed according to the development processing 1 described above.

<Pressurizing method>
The sample was fixed on a horizontal base, and a pressure was applied to the sample by moving the loaded needle at a constant speed in a direction perpendicular to the step of the exposure wedge. At this time, a sapphire needle having a contact portion with a sample of 0.3 mm was used as the needle, the scanning speed of the needle was 1 cm / second, and the load was changed sequentially from 10 g to 100 g.

  Each sample subjected to the development processing as described above was visually observed, and the pressure resistance of the sample was evaluated from the viewpoint of the correlation between the density change in the unexposed area and the exposed area due to pressurization and the load. In addition, the evaluation of the superiority or inferiority of the sample is made into 5 stages of A to E, the concentration change due to pressurization is not observed, A is the most excellent sample, the change in concentration due to pressurization occurs from a low load, and the sample with the lowest pressure resistance Was expressed as E, and the levels between A and E were equally divided into ranks B to D.

[Evaluation of processing stability]
The samples 101 to 116 were exposed and developed 1 in accordance with the evaluation B described above. Next, after the samples 101 to 116 were exposed according to the above evaluation B, development processing 2 was performed according to the following method.

(Development process 2)
<Processing process>
Processing step Processing temperature Time Replenishment amount Color development 42.0 ± 0.3 ℃ 20 seconds 80ml
Bleach fixing 40.0 ± 0.5 ℃ 20 seconds 120ml
Stabilization 30-34 ° C 20 seconds 150ml
Drying 60 to 80 ° C. 30 seconds The processing solution used in each step of the development processing 2 was the same as the processing solution composition described in the development processing 1.

  Next, a characteristic curve is prepared by the same method as described above for the samples processed in the development process 1 and the development process 2, and the density of the minimum density +1.0 is obtained for the magenta image density of the third layer (green sensitive layer). The exposure amount required to obtain the value is obtained, the reciprocal of this exposure amount is defined as the sensitivity, the relative sensitivity obtained in the development processing 2 when the sensitivity obtained in the development processing 1 is defined as 100, and this is processed stably. A measure of gender. The closer the relative sensitivity in the development process 2 is to 100, the better the processing stability when the rapid processing is performed.

[Evaluation of image quality: Analog / digital suitability]
A portrait image of a person and an outdoor daylight scene were photographed using Centuria 400, a color negative film manufactured by Konica Minolta Photomerging, and developed in accordance with a designated development process to produce a negative image sample.

Using this negative image sample, an analog image is created as an image A using an analog-type Konica minilab system NPS-858JType II (exposure time: 0.5 seconds average, manufactured by Konica Minolta Photomerging), and an image B Digital minilab R1 SUPER (exposure time: average 1 × 10 ⁻⁵ seconds, manufactured by Konica Minolta Photomerging Co., Ltd.) was used to create digital images, and each image was evaluated for image quality according to the following criteria: .

○: There is no difference between the analog image and the digital image, and both are good reproducibility. △: There is almost no difference between the analog image and the digital image, and the reproducibility is almost good. Differences in gradation reproducibility and color reproducibility are recognized among the results. Table 3 shows the results obtained as described above.

  As is clear from the results shown in Table 3, it can be seen that the sample having the configuration defined in the present invention is superior in pressure resistance, processing stability, and analog / digital suitability to the comparative example.

  Moreover, it turns out that the hardening solution used for sample preparation of this invention is excellent in the precipitation tolerance of a hardening agent solution with respect to the hardening solution used by the comparative example.

  Furthermore, in addition to the constitution of the present invention, by using the surfactant represented by the general formula (SI) or (S-II) according to the present invention as the surfactant of the protective layer, the coatability is further improved. It was confirmed that it could be further improved. Moreover, according to the said method, as a result of having similarly evaluated about the blue sensitive layer (yellow image) and the red sensitive layer (cyan image), it can confirm the effect similar to the result of Table 3 of a green sensitive layer. did it.

Claims (4)

In a silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer and cyan image forming layer each containing a photosensitive silver halide on a support, 10 ⁻ per pixel. After exposure with an exposure time of ⁶ seconds, development processing was performed, and exposure was performed with an exposure amount (LogEd) giving the maximum point γ (γmd) of each obtained color image and an exposure time of 0.5 seconds per pixel. Thereafter, the difference ΔLogE (LogEd-LogEa) from the exposure amount (LogEa) giving the maximum point γ (γma) of each color image obtained after development processing is 0.15 or less, and the vinylsulfone-based dura A silver halide color photographic light-sensitive material containing an agent, wherein the vinyl sulfone hardener is dissolved and added by a compound represented by the following general formula (I).

[Wherein, X represents a substituted or unsubstituted alkylene, and Y represents a hydroxyl group or a hydrogen atom. However, at least three of Y are hydroxyl groups at the same time. ] 2. The silver halide color photographic material according to claim 1, wherein the vinyl sulfone hardener is a compound represented by the following general formula [HI].

[In formula, R < ¹ >, R < ⁴ > and R < ⁷ > represent an alkylene group and an arylene group, respectively. R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, a hydroxyl group or a vinylsulfonyl group. J ₁ and J ₂ represent —O—, —S—, — (C═O) —, —CH (OH) —, —NHCO— or —CONH—. m1 and m2 each represents 0 or 1; ] The R ² , R ³ , R ⁵ , R ⁶ , R ⁸ and R ^{9 in the} general formula [HI] are each a hydrogen atom, an alkyl group or a hydroxyl group. Silver halide color photographic light-sensitive material. The silver halide color photographic material according to any one of claims 1 to 3, further comprising a surfactant represented by the following general formula (SI) or (S-II).

[Wherein, R ² represents an alkyl group or alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation, and may be the same as or different from M. n represents 1 or 2. ]

[Wherein R ³ represents an alkyl or alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. p represents 1 or 2. ]