JP2007017844A - Silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material having high sharpness (dot reproducibility) and excellent in fogging stability during long-term storage and in processing stability. <P>SOLUTION: The silver halide color photosensitive material has a photosensitive silver halide emulsion layer and a non-photosensitive layer on a reflective support, wherein at least one layer of the non-photosensitive layer is adjacent to at least one layer of the photosensitive silver halide emulsion layer and contains black colloidal silver. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silver halide color photosensitive material having improved sharpness and excellent storage stability and processing stability.

  Silver halide color light-sensitive materials (hereinafter also referred to as silver halide light-sensitive materials or simply light-sensitive materials) are prosperous today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. It is used. Because of these characteristics, the silver halide color photosensitive material is not only used in the general photographic field for photography, but also in the printing field, especially in the middle of printing, so-called proof field for checking the state of the final finished printed matter in advance. Is becoming widely used.

  In the proof field, an image edited on a computer is output to a printing film, and a developed film is appropriately exchanged and subjected to decomposition exposure, whereby yellow (Y), magenta (M), cyan (C ) And the image of the final printed matter is formed on color photographic paper, thereby determining the suitability of the layout and color of the final printed matter.

  Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread, and in such a case, a color image can be obtained directly from the data on the computer without using a film. It was desired.

  For this purpose, various methods such as a fusion thermal transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image has a drawback in that it is expensive and inferior in productivity. However, there is a drawback that the image quality is inferior in the method which is low in cost and excellent in productivity. High-quality image formation, such as the ability to form images with almost no noise (granular structure) in the system using silver halide color photosensitive materials and the ability to form accurate halftone images due to excellent sharpness On the other hand, it is possible to realize high productivity from the advantages that continuous development processing is possible and images can be simultaneously written in a plurality of color image forming units.

  In consideration of the above situation, as one of the methods for improving the sharpness of the silver halide color photographic material, in order to prevent the deterioration of the sharpness caused by the reflection of incident light at the support interface, A method of providing an antihalation layer at an adjacent position is widely adopted. In this antihalation layer, colloidal metallic silver particles are mainly used.

  However, conventionally used black colloidal silver dispersions cannot be completely dissolved during the development process, and particularly when used on a white support such as color photographic paper, Therefore, the usage is limited at present.

  When used for the purpose of proofing printed matter as disclosed in Japanese Patent Application Laid-Open No. 2000-221638, high sharpness that reproduces halftone dots with a resolution of about 2400 dpi (dpi represents the number of dots per 2.54 cm). Sex is required. In addition, it is difficult to change the solid density in the conventional proof system. The solid portion is reproduced with halftone dots by a CMS (color management system) or the like, and the halftone is adjusted by shifting from the halftone dot size of the printed matter. Therefore, as disclosed in Japanese Patent Application Laid-Open No. 2004-264800, it is desirable that the solid density can be set in accordance with printing.

  In silver halide photographic light-sensitive materials, it is possible to change the solid density by using the halftone density part of the characteristic curve. Cheap. In particular, the achromatic color tone has a high visual detection power.For example, in black nets, not only the density is stabilized, but also high stability against the subtle color tone of halftone dots is desired. In order to minimize the number of fringe portions that are easily received, development of a silver halide color photosensitive material having high sharpness has been desired. On the other hand, it is necessary to reproduce a white background with no stain similar to that of printing paper. However, the black colloidal silver dispersion that has been used in the past can achieve both the above-mentioned high level of sharpness and white background performance. The current situation is that it has not been achieved.

  As one of the solutions to the above problem, for example, an antihalation substance having a hydrophilic colloid layer and a silver halide photosensitive emulsion layer on a support coated with a polyolefin resin, from which the hydrophilic colloid layer can be removed, and about A photographic element containing 20 to 80% by mass of a white pigment and having improved sharpness is disclosed (for example, see Patent Document 1). Further, the support has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a colloidal silver-containing hydrophilic layer, and the average thickness of the colloidal silver is 5 to 5. There is disclosed a color photographic material having a range of 30 nm, wherein the colloidal silver-containing hydrophilic layer contains an absorptive compound such as azaindenes, and has improved sharpness and storage stability (for example, patent documents) 2). Furthermore, the support has a light-sensitive emulsion layer and a non-photosensitive layer containing colloidal silver, and the colloidal silver-containing layer contains hindered phenol and a chroman compound, and has excellent color reproducibility and storage stability. In addition, a silver halide color photographic light-sensitive material is disclosed (for example, see Patent Document 3).

  Further, an example in which a silver halide emulsion layer is provided on a reflective support via an antihalation layer and an intermediate layer, and the antihalation layer contains black colloidal silver, an antioxidant, an inhibitor, a polymer and the like is described. (For example, refer to Patent Documents 4 and 5).

  However, in each of the proposed patent documents, when the black colloidal silver-containing layer and the silver halide emulsion layer are formed via an intermediate layer, the productivity increases as the number of coating layers increases. And the effect of preventing halation due to the black colloidal silver-containing layer is reduced due to the presence of the intermediate layer. In addition, when the black colloidal silver-containing layer and the silver halide emulsion layer are adjacent to each other, the silver halide emulsion is affected by the physical development of the black colloidal silver and the reducing agent during the preparation of the black colloidal silver. The contact fogging of the layer occurs, and fogging becomes more remarkable particularly when stored for a long period of time.

As described above, in the sharpness improving technique using black colloidal silver, it is difficult to achieve both the sharpness improving effect and the storage stability, and the obtained halftone quality, halftone color stability and Regarding the characteristics of white background, it is hard to say that the quality is never satisfactory.
JP-A-6-175278 JP-A-6-347940 Japanese Patent Laid-Open No. 7-20608 JP 2002-122969 A Japanese Patent Laid-Open No. 2004-4687

  The present invention has been made in view of the above-mentioned problems, and its purpose is a halogenation having high sharpness (halftone dot reproducibility) and excellent fog stability and processing stability during storage over a long period of time. The object is to provide a silver color light-sensitive material.

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

(1)
In a silver halide color light-sensitive material having a light-sensitive silver halide emulsion layer and a light-insensitive layer on a reflective support, at least one of the light-insensitive layers is at least one layer of the light-sensitive silver halide emulsion layer. And a silver halide color light-sensitive material characterized by containing black colloidal silver.

(2)
The silver halide color photosensitive material as described in (1) above, wherein the non-photosensitive layer containing black colloidal silver contains a polyvinylpyrrolidone derivative.

(3)
The silver halide color photosensitive material as described in (1) or (2) above, wherein the non-photosensitive layer containing black colloidal silver contains a white pigment.

(4)
The black colloidal silver contained in the non-photosensitive layer is prepared by reducing a soluble silver salt in the presence of a compound represented by the following general formula (S) (1) The silver halide color light-sensitive material according to any one of (1) to (3).

[Wherein T represents an atomic group necessary to form a 5-membered heterocycle, J represents a hydrogen atom, a hydroxy group, —SO ₃ M ¹ , —COOM ¹ (where M ¹ represents a hydrogen atom, an alkali metal atom) Or a substituted or unsubstituted amino group, a substituted or unsubstituted ammonio group, a C1-C19 alkylthio group substituted by one or more of these, a carbon number of 2 Represents an alkylamide group having -18 carbon atoms, an alkylcarbamoyl group having 2-18 carbon atoms, an alkyl group having 1-19 carbon atoms, or an aromatic group having 6-31 carbon atoms. M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt). ]
(5)
The silver halide color according to any one of (1) to (4), wherein the non-photosensitive layer containing the black colloidal silver is coated in contact with the reflective support. Photosensitive material.

  Moreover, the following means are mentioned as a preferable aspect of this invention.

(6)
The photosensitive silver halide emulsion layer comprises at least a blue-sensitive silver halide layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the photosensitive silver halide emulsion is silver chloride. The silver halide color light-sensitive material as described in any one of (1) to (5) above, which contains silver halide grains having a content of 95 mol% or more.

(7)
The silver halide color described in any one of (1) to (6) above, wherein the amount of binder in the non-photosensitive layer containing the black colloidal silver is 1.0 g / m ² or less. Photosensitive material.

(8)
Any one of (1) to (7) above, wherein the hardener of the binder constituting the non-photosensitive layer or the photosensitive silver halide emulsion layer is a vinyl sulfone type hardener. The silver halide color photosensitive material described.

(9)
The image to be formed is an area gradation image in which pixels with variable density are formed and halftone dots are reproduced by the pixel aggregate, wherein the image is formed as described in any one of (1) to (8) above Silver halide color photosensitive material.

(10)
The silver halide color photosensitive material as described in (9) above, wherein the pixel array is an image formed by an FM screening method.

  According to the present invention, it is possible to provide a silver halide color light-sensitive material having high sharpness (halftone dot reproducibility) and excellent in fog stability and processing stability during long-term storage.

  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 in a silver halide color photosensitive material having a photosensitive silver halide emulsion layer and a non-photosensitive layer on a reflective support, at least the non-photosensitive layer. One layer is adjacent to at least one of the light-sensitive silver halide emulsion layers and contains black colloidal silver. The silver halide color light-sensitive material is characterized by high sharpness (halftone dot reproducibility). The present inventors have found that a silver halide color light-sensitive material having excellent fog stability and processing stability during storage for a long period of time can be realized.

  Details of the present invention will be described below.

  In the silver halide color light-sensitive material of the present invention, at least one of the non-light-sensitive layers is adjacent to at least one of the light-sensitive silver halide emulsion layers and contains black colloidal silver. However, in addition to the above-mentioned conditions defined in the present invention, as a more specific method, a non-photosensitive layer containing black colloidal silver may contain a polyvinylpyrrolidone derivative or a white pigment, By using a compound prepared by reducing a soluble silver salt in the presence of the compound represented by S), and providing a non-photosensitive layer containing black colloidal silver at a position in contact with the reflective support. The object effect of the invention can be achieved.

Furthermore, from the viewpoint of further exerting the effects of the present invention, the photosensitive silver halide emulsion layer is composed of at least a blue-sensitive silver halide layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. And the photosensitive silver halide emulsion contains silver halide grains having a silver chloride content of 95 mol% or more, and the binder amount of the non-photosensitive layer containing black colloidal silver is 1.0 g / m ^2. It is preferable to use a vinyl sulfone type hardener as a hardener for the binder constituting the non-photosensitive layer or the photosensitive silver halide emulsion layer.

  Further, as an image forming method using the silver halide color light-sensitive material of the present invention, the formed image is an area gradation image in which pixels with variable density are formed and halftone dots are reproduced by the pixel aggregate. Furthermore, a halftone image having excellent reproducibility by high sharpening can be obtained by making the pixel arrangement an image formed by the FM screening method.

  The silver halide color light-sensitive material of the present invention has a light-sensitive silver halide emulsion layer and a non-light-sensitive layer on a reflective support, and the light-sensitive silver halide emulsion layer is at least a blue light-sensitive silver halide layer. A green light-sensitive silver halide emulsion layer and a red light-sensitive silver halide emulsion layer are preferred. Examples of the non-photosensitive layer include a protective layer, an ultraviolet absorbing layer, an intermediate layer, and an antihalation layer. In the present invention, among these, a non-photosensitive layer containing black colloidal silver (hereinafter, An antihalation layer) is provided at a position adjacent to the photosensitive silver halide emulsion layer, and more preferably, as described above, the non-photosensitive layer containing black colloidal silver is in contact with the reflective support. It is preferable to provide it at a position. That is, a non-photosensitive layer containing the black colloidal silver according to the present invention is provided on at least one surface of the reflective support, and a silver halide emulsion layer is further formed thereon without any other layer such as an intermediate layer. Are preferably provided in direct contact with each other.

  First, the black colloidal silver according to the present invention and the non-photosensitive layer containing the same will be described.

[Black colloidal silver]
Examples of the method for producing black colloidal silver according to the present invention include, for example, U.S. Pat. Nos. 2,688,601, 2,921,914, German Patent 1,096,193, and JP-A-5-134358. In general, in the presence of a protective colloid typified by gelatin, a soluble silver salt such as an aqueous silver nitrate solution is reduced to a reducing sugar compound such as phenol, hydrazine, a hydroxylamine compound or salt thereof, and dextrin, Fine metal (colloidal) silver particles are prepared by reduction using a reducing agent such as an oxytetronic acid compound.

  The black colloidal silver according to the present invention is preferably black colloidal silver prepared by reducing a soluble silver salt in the presence of the compound represented by the general formula (S).

  By reducing the soluble silver salt in the presence of the compound represented by the general formula (S) according to the present invention, a stable black colloidal silver can be produced, and a black colloidal silver having desired spectral absorption characteristics is obtained. In addition, when the black colloidal silver is formed, the compound represented by the general formula (S) is allowed to coexist on the surface of the black colloidal silver particles by allowing the compound represented by the general formula (S) to coexist. The electric repulsive force effectively prevented the aggregation of black colloidal silver particles.

  The mercapto compound represented by the general formula (S) will be described.

In the general formula (S), T represents an atomic group necessary for forming a 5-membered heterocycle, and J represents a hydrogen atom, a hydroxy group, —SO ₃ M ¹ , —COOM ¹ , a substituted or unsubstituted amino group. A substituted or unsubstituted ammonio group, an alkylthio group having 1 to 19 carbon atoms (for example, a methylthio group, an ethylthio group, an n-butylthio group, etc.) substituted by one or more of these, an alkylamide having 2 to 18 carbon atoms Group, an alkylcarbamoyl group having 2 to 18 carbon atoms, an alkyl group having 1 to 19 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl , Heptadecyl group, octadecyl group, etc.), or an aromatic group having a carbon number of 6 to 31 (e.g., a phenyl group, represents a naphthyl group), particularly preferably a hydrogen atom.

M ¹ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion. M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt).

  Hereinafter, although the specific compound of the mercapto compound represented with general formula (S) is enumerated, in this invention, it is not limited only to these illustrated compounds.

In the black colloidal silver according to the present invention, the preferred addition amount of the mercapto compound represented by the general formula (S) according to the present invention is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol per mol of colloidal silver, More preferably, it is 1 × 10 ⁻³ to 1 × 10 ⁻² .

  When the black colloidal silver according to the present invention is prepared, the mercapto compound represented by the general formula (S) according to the present invention is added at any position as long as the colloidal silver is reduced. However, in the method in which yellow colloidal silver is formed once as a core particle, which is a method preferably used in the present invention, and this is isolated once and reduced and grown using this as a nucleus, the yellow colloidal silver nucleus is converted into soluble silver. It is preferable to add it before reducing growth with a salt from the viewpoint of production stability.

  Next, the spectral absorption characteristics of the black colloidal silver according to the present invention will be described.

  Conventionally, spectral absorption characteristics desirable as black colloidal silver have been desired to have flat absorption over a wide wavelength range. Further, as described in Japanese Patent Application Laid-Open No. 2000-155387, spectral characteristics having absorption in the infrared region are desired in order to make the infrared sensor wait for an appropriate sensitivity. However, when observing black colloidal silver particles having absorption in the flat or long wave, which has been conventionally proposed, it has been found that a large number of small particle aggregates exist.

  On the other hand, in the method for producing black colloidal silver according to the present invention, the presence of the compound represented by the general formula (S) according to the present invention controls the aggregation state of the colloidal silver, thereby reducing aggregates. As a result, it is possible to obtain a preferable spectral absorption characteristic with little absorption in the infrared region.

  In the black colloidal silver according to the present invention, from the viewpoint of sharpness and desilvering property, the ratio of the spectral absorption density D950 at 950 nm to the spectral absorption density D650 at 650 nm, that is, the value of D950 / D650 is 0.70. Is preferably less than 0.50, more preferably less than 0.50, particularly preferably 0 and less than 0.20.

  Moreover, it is preferable that the maximum wavelength of the spectral absorption in 400 nm-1000 nm of colloidal silver exists in the range of 500 nm or more and 700 nm or less, More preferably, it is the range of 550 nm or more and 650 nm or less.

  Furthermore, the maximum absorption wavelength in the reflection system at 400 nm to 700 nm when coated on a white support is preferably in the range of 550 nm to 700 nm, and more preferably in the range of 580 nm to 680 nm.

The spectral absorption concentration defined in the present invention was measured by diluting black colloidal silver with water so that the silver concentration was 1.5 × 10 ⁻⁴ mol / L, and then using an ultraviolet-visible near-infrared spectrophotometer. It can be determined by measuring in the range of ˜1200 nm. As for the spectral absorption density in the reflection system, a sample in which black colloidal silver is coated on RC base paper so as to be 0.1 g / m ² in terms of silver is prepared, and UV-visible near-infrared spectroscopy with an integrating sphere is applied. It can be determined by measuring in the range of 300 to 1200 nm with a photometer.

The coating amount of the black colloidal silver according to the present invention is preferably 0.01 g / m ² or more and 0.35 g / m ² or less, more preferably 0.03 g / m ² or more and 0.20 g / m as the silver amount. ² or less, particularly preferably 0.05 g / m ² or more and 0.15 g / m ² or less.

  The reflection density of black colloidal silver is preferably 0.3 or more and 2.0 or less, more preferably 0.5 or more and 1.2 or less at the maximum absorption wavelength of colloidal silver.

  Next, a method for producing black colloidal silver according to the present invention will be described.

  Conventionally known methods for preparing black colloidal silver are described in U.S. Pat. Nos. 2,688,601, 2,921,914, and German Patent 1,096,193 as described above. In general, there is a description of a chemical method for reducing a soluble silver salt or a hardly soluble silver salt in the presence of a protective colloid represented by gelatin. Yes.

  The gelatin that can be applied to the present invention is preferably one that has been subjected to a peroxidation treatment at the time of production as a whole, and is preferably one in which chlorine ions and calcium ions have been reduced by a deionization step. The chlorine ion concentration is preferably 500 ppm or less, more preferably 300 ppm or less, particularly preferably 100 ppm or less, and calcium ions are preferably 50 ppm or less.

  The gelatin used for producing the black colloidal silver according to the present invention preferably has a maximum value of weight average molecular weight (hereinafter simply referred to as average molecular weight) of 120,000 or less. At an average molecular weight higher than this, the value of D950 / D650 tends to be small, and it is difficult to obtain desired absorption characteristics. More preferably, it is 100,000 or less, More preferably, it is 10,000 or more and 80,000 or less. In order to measure the average molecular weight of gelatin, for example, it can be determined by the method described in The Macromolecular Chemistry of Geratin (ACADEMIC PRESS-NEWYORK AND LONDON).

  Further, it is preferable that 60% or more of gelatin is contained within a range of ± 20% of the maximum value of the average molecular weight. More preferably, it is 75% or more. If it is less than 60%, the molecular weight distribution is too wide, so that it is difficult to adjust the absorption characteristics of black colloidal silver, and it is difficult to obtain a preferable absorption shape.

  In the present invention, it is preferable to use 20% by mass or more of gelatin extracted after adding a primary or secondary amine having no dissociable group in the lime treatment step during the production process. As the corresponding amine compound, many compounds having a relatively small molecular weight are used, and those having 5 or less carbon atoms are particularly preferably used.

  Examples of the compound include methylamine, dimethylamine, ethylamine, n-propylamine, ethylmethylamine, n-butylamine, guanidine, ethylenediamine, hydrazine, hydroxylamine, or cyclic compounds such as piperidine and piperazine.

  These compounds are added to the lime suspension to a concentration of 0.01% to 0.1%. An example of a preferred compound is piperazine. Gelatin treated with the addition of piperazine is preferred because it can improve the dispersion stability of black colloidal silver over time. The ratio of the piperazine-treated gelatin is preferably 40% by mass or more, more preferably 60% by mass or more.

  One characteristic of gelatin used in the present invention is the gold value. To measure the gold value of gelatin, see Journal of Photographic Science, Vol. 28, 1980 (111 to 118) and JP-A-2-111940. Black colloidal silver produced in the presence of gelatin having a low gold value is excellent in stability over time, and the gold value of gelatin in the present invention is 20 (μmol / g gelatin) or less, preferably 15 ( [mu] mol / g gelatin) or less, more preferably 10 ([mu] mol / g gelatin) or less. The ratio used is preferably 40% by mass or more, more preferably 60% by mass or more.

One of the gelatins used in the present invention is a modified gelatin in which 50% or more of the amino groups of the gelatin molecule are substituted. Examples of substituents for the amino group of gelatin are described in US Pat. Nos. 2,691,582, 2,614,928, and 2,525,753. Useful substituents for obtaining modified gelatin by substituting amino groups include (1) acyl groups such as alkylacyl, arylacyl, acetyl and substituted, unsubstituted benzoyl, and (2) alkylcarbamoyl, arylcarbamoyl, etc. (3) sulfonyl groups such as alkylsulfonyl and arylsulfonyl, (4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) linear and branched alkyl groups having 1 to 18 carbon atoms, (6) Aromatic groups such as substituted and unsubstituted phenyl, naphthyl, pyridyl and furyl, and aryl groups such as heterocycles. Among them, preferred modified gelatin is an acyl group (—COR ₁₁ ) or a carbamoyl group (—CONR ₁₁ R ₁₂ ). Here, R ₁₁ is a substituted or unsubstituted aliphatic group (for example, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group or an aralkyl group (for example, a phenethyl group), and R ₁₂ is a hydrogen atom. An aliphatic group, an aryl group or an aralkyl group. Particularly preferred is the case where R ₁₁ is an aryl group and R ₁₂ is a hydrogen atom.

  Hereinafter, useful amino group substituents for obtaining a modified gelatin by substituting amino groups in the present invention will be exemplified, but the present invention is not limited thereto.

  In the case of using modified gelatin for removal of dissolved matter (desalting), the amount of addition is not particularly limited, but it is 0.1 to 5 times the amount (preferably gelatin) contained as a protective colloid at the time of removal ( (Mass) is generally suitable, particularly preferably 0.3 to 2 times (mass). As a particularly preferred gelatin, there is gelatin in which an amino group is phenylcarbamoylated.

  As the gelatin characteristic, a part or all of amino groups contributing to the hardening reaction are substituted. Therefore, when black colloidal silver containing this gelatin is coated on a support, for example, a typical hardening is performed. When a vinyl sulfone type or triazine type hardener, which is an agent, is used, the hardening property is inhibited. Accordingly, the amount used is naturally limited, but is preferably 50% by mass or less, and more preferably 40% by mass or less.

  Black colloidal silver is generally prepared by reducing silver ions in an aqueous gelatin solution. In the present invention, the gelatin aqueous solution temperature during the reaction is preferably 20 to 45 ° C., more preferably It is 25-45 degreeC, Most preferably, it is 30-40 degreeC. At temperatures outside this range, it is difficult to adjust the absorption characteristics of black colloidal silver to desirable characteristics. In addition, the pH of the gelatin aqueous solution during the reaction is preferably in the range of 8 to 10, more preferably 8.5 to 10. Similarly, if the pH is too low outside this range, the reduction reaction of the aqueous silver nitrate solution cannot be promoted sufficiently. On the other hand, if the pH is too high, the reduction reaction proceeds rapidly and the absorption characteristics of the black colloidal silver are adjusted to the desired characteristics. It becomes difficult. At least one of the temperature and pH of the gelatin aqueous solution during the reduction reaction of the silver nitrate aqueous solution needs to be in the above range, but both values are preferably in the above range.

  In the process of reducing the silver nitrate aqueous solution, which is a method for producing black colloidal silver, to prepare fine colloidal silver, a method of obtaining black colloidal silver as a final product by a one-step reaction is common. Is preferably prepared in two stages as the formation of black colloidal silver for the purpose of improving (stabilizing) the reproducibility of the absorption characteristics of black colloidal silver or adjusting to the desired absorption characteristics. Specifically, it comprises a nucleation step for forming yellow colloidal silver nuclei, and a growth step for growing the colloidal silver nuclei into black colloidal silver.

  According to this two-step method for producing a black colloidal silver dispersion, the colloidal silver nucleation can be controlled by controlling the conditions such as temperature and pH in the black colloidal silver nucleation step and the growth step, and by selecting the type of gelatin. The silver molar extinction coefficient can be increased, preferable spectral absorption characteristics as a black colloidal silver dispersion can be obtained, and black colloidal silver having high storage stability can be obtained.

  The black colloidal silver nucleation step is a step of forming black colloidal silver nuclei (yellow colloidal silver) with a small amount of silver ions and a small amount of reducing agent, and the black colloidal silver growth step is a large amount of remaining silver ions and a large amount of In this step, a reducing agent is added to the black colloidal silver nuclei by a double jet method or the like to grow new black colloidal silver nuclei while minimizing the generation of new nuclei.

  In the step of treating the prepared black colloidal silver, a desalting step is generally provided in order to remove excess water-soluble salts. The desalting method involves adding a flocculant such as salts such as magnesium sulfate or gelatin that is chemically modified with some or all of the amino groups in gelatin, and removing the supernatant after one or more flocculations. There is a so-called decantation method, a so-called ultrafiltration method that excludes dissolved salts out of the system using a semipermeable membrane having a fine network structure, and any method can be used for the black colloidal silver of the present invention. It can be applied as a desalting method.

  In the present invention, after the desalting step, the black colloidal silver dispersion is cooled to 30 ° C. or lower and gelled. The cooling gelation temperature is preferably 0 to 25 ° C, particularly preferably 4 to 15 ° C. It has been found that the stability of the black colloidal silver dispersion is increased by the cooling gelation step. That is, it is important that the black colloidal silver dispersion formed in the aqueous gelatin sol is subjected to practical use after being once cooled and gelled after the desalting step, and without being subjected to the cooling gelation step. When a coating solution is prepared and applied, the storage stability as a silver halide color photographic material may be slightly lowered, which is not preferable.

  A significant proportion of aggregated black colloidal silver is present in the desalted black colloidal silver gelatin sol. Aggregates are undesirable because they cause clogging of the filter in the subsequent manufacturing process and cause tailing failure on the coating film in the coating process, and can be reduced by mechanically dispersing them. However, in general, when the aggregate is reduced and the monodispersion is advanced, the absorption characteristics become sharper, and the absorption becomes clearer in a specific wavelength range. In general, the absorption characteristics required for black colloidal silver for the purpose are to have broad absorption characteristics over a wide wavelength range from the ultraviolet to the near-infrared region, which is contrary to the above-described properties. Therefore, it is necessary to appropriately set the dispersion strength in the mechanical dispersion step and adjust the particle size distribution of the black colloidal silver including the aggregated state. As a dispersion method, a method capable of obtaining a high collision pressure is preferable. In the present invention, a dispersion method using a Manton-Gorin disperser which is a pressure shear type dispersion method is preferable. The pressure during dispersion is 0.10 to 5.0 MPa, and the first stage pressure is preferably set to 0.02 to 0.80 MPa, and the second stage pressure is preferably set to 2.0 to 4.5 MPa. Moreover, in order to further improve dispersibility, the above cycle may be performed a plurality of times.

As the gelatin used in the non-photosensitive layer containing black colloidal silver according to the present invention, it is preferable to use gelatin as in the preparation of colloidal silver, and gelatin which is a binder in the non-photosensitive layer containing black colloidal silver The coating amount depends on the content of the black colloidal silver in the non-photosensitive layer, and thus cannot be generally determined, but is preferably 1.0 g / m ² or less, more preferably 0. .1g / m ² or more and 1.0 g / m ² or less.

[Polyvinylpyrrolidone derivatives]
In the present invention, the non-photosensitive layer containing black colloidal silver according to the present invention preferably contains a polyvinylpyrrolidone derivative. By using a polyvinylpyrrolidone derivative together with black colloidal silver, dissolution physical development of the black colloidal silver can be suppressed, and as a result, fogging of adjacent silver halide emulsion layers can be suppressed.

  The polyvinylpyrrolidone derivative used in the present invention refers to a polymer or copolymer having a pyrrolidone nucleus in the molecular structure. The polymer having a pyrrolidone nucleus in the molecular structure (hereinafter also referred to as vinylpyrrolidone polymer) may be a homopolymer of vinylpyrrolidone alone or a copolymer with other monomers.

  Other monomers that can be copolymerized with vinylpyrrolidone include vinyl esters (vinyl acetate, vinyl propionate, vinyl butyrate, etc.), acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid-2). -Ethylhexyl, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-2-ethylhexyl, etc.), acrylic acid, methacrylic acid, styrene, etc. It is preferable to use it at 5 to 100 mol%.

  The weight average molecular weight (Mw) of the vinylpyrrolidone polymer is usually 500 to 800,000, preferably 2,000 to 400,000. A polymer substance such as a polymer or copolymer having a pyrrolidone nucleus according to the present invention is generally composed of a mixture of homologs having different molecular weights, and thus has a molecular weight distribution. Accordingly, the molecular weight value gives different average molecular weights depending on the measurement method, and the value varies. As a method for measuring the average molecular weight, for example, it can be measured by the method described in the Polymer Materials Handbook published by Corona Co., Ltd. (1973).

  The polymer or copolymer having a pyrrolidone nucleus according to the present invention may be used alone or in combination of two or more.

In the present invention, the addition amount of polyvinyl pyrrolidone derivatives, preferably ^{0.01~1g / m 2, 0.05~0.5g / m} 2 is more preferable.

  Specific examples of the polyvinyl pyrrolidone and vinyl pyrrolidone polymer used in the present invention include the following.

P-1: Polyvinylpyrrolidone (Mw about 40,000)
P-2: Polyvinylpyrrolidone (Mw about 9,000)
P-3: Polyvinylpyrrolidone (Mw about 16,000)
P-4: Vinylpyrrolidone-vinyl acetate copolymer (copolymerization molar ratio = 7: 3, Mw about 4,000)
P-5: Vinylpyrrolidone-methyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 1,000)
P-6: Vinylpyrrolidone-ethyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 25,000)
P-7: Vinylpyrrolidone-butyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 7,000)
P-8: Vinylpyrrolidone-2-ethylhexyl acrylate copolymer (copolymerization molar ratio = 7: 3, Mw about 18,000)
P-9: Vinylpyrrolidone-styrene copolymer (copolymerization molar ratio = 1: 3, Mw about 20,000)
[White pigment]
In the present invention, the non-photosensitive layer containing black colloidal silver according to the present invention preferably contains a white pigment.

  As the white pigment, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used. Rutile titanium dioxide is preferred. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The content of the white pigment is preferably 40% by mass or more, and more preferably 60% by mass or more. However, when the content is more than this, troubles occur in terms of brittleness and applicability. The white pigment may contain a coloring substance.

The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / m 2} .

[Other additives for non-photosensitive layer]
In the non-photosensitive layer containing black colloidal silver and other non-photosensitive layers according to the present invention, various additives can be used as necessary in addition to the above-mentioned additives. Agents, stain inhibitors, stabilizers, ultraviolet absorbers, antifading agents, high-boiling organic solvents, surfactants, antistatic agents, matting agents, dyes, fluorescent whitening agents, hardeners, and the like can be used.

  In the non-photosensitive layer containing black colloidal silver according to the present invention, it is desirable to avoid the addition of a compound having a reducing ability, for example, a hydroquinone derivative. When a hydroquinone derivative is added to a non-photosensitive layer containing black colloidal silver, it is adjacent to the reflective support and becomes the bottom layer when multi-layer coating is applied. It becomes easy to wake up, and tends to cause a decrease in color developability of the silver halide emulsion layer directly coated thereon.

  Next, the constitution of the silver halide color light-sensitive material of the present invention will be described sequentially.

  The silver halide emulsion used in the silver halide emulsion layer according to the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride. Silver chloride, silver chlorobromide, silver chloroiodobromide, salt Those having an arbitrary halogen composition such as silver iodide are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. Of the silver halide emulsion having a silver bromide-rich portion, the silver bromide-containing portion may be a so-called core-shell emulsion, or simply forming a complete layer without forming a complete layer. A so-called epitaxy-bonded region in which only a region having a partially different composition exists may be formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

It is advantageous that the negative silver halide emulsion used in the present invention contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening on the shadow side. 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, and cobalt, and group 12 metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, water, pyridine, Pyrrol, pyrazole, imidazole, thiazole, 1,2,4-triazole, 2,2′-biimidazole, 2,2′-bipyridine or 2,2 ′: 6 ′, 2 ″ -terpyridine compound is preferably used. Cyanide ion, chloride ion, bromide ion, water, nitrosyl, 5-methylthiazole, 1,2,4-triazole, etc. In order to contain a heavy metal ion in a silver halide emulsion, the heavy metal compound is added. Before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains In order to obtain a silver halide emulsion satisfying the above-described conditions, the heavy metal compound is dissolved together with the halide salt to completely or partly form the grain. In addition, it is also possible to prepare silver halide fine particles containing these heavy metal compounds in advance and then add the heavy metal ions to the silver halide. The amount added to the emulsion is preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and more preferably 1 × 10 ⁻⁸ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide. preferable.

  Any particle shape can be used in the present invention. One preferable 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, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) No. 21, page 39 (1973), etc., can be used to produce particles having a shape such as octahedron, tetrahedron, dodecahedron, etc. . Furthermore, particles having twin planes may be used.

  The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred that two or more monodispersed silver halide emulsions are added to the same layer.

  The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 when considering other photographic performances such as rapid processability and sensitivity. It is the range of -1.0 micrometer.

  This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains used in 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, and particularly preferably a coefficient of variation of 0.1. Two or more monodispersed emulsions of 15 or less are added to the same layer. 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.)
As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The emulsion used in the present invention may be obtained by any of the 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 negative silver halide emulsion used in 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 the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer, it is preferred to vary the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^- A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide. Mole is preferred. More preferably, it is 1 * 10 <^-5> mol-1 * 10 <^-8> mol.

  As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.

  The silver halide emulsion used in the present invention is known for the purpose of preventing fogging that occurs during the preparation process of the silver halide color light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs during development. Antifoggants and stabilizers can be used. Examples of preferable 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 preferable specific compounds. Are the compounds of (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, as well as JP 2000-267,235 page 8, right column 32. To the compound described in line 36, a mercaptopyrimidine compound represented by the general formula (I) in JP-A-9-152675, an adsorption promoting group and a substitution with silver halide represented by the general formula (II), Compounds having a substituted hydroxyl group or amino group, specifically, (I-1), (I-2), (I-7), (I-9), (II-1), (II-3) ) Can be mentioned. Further, compounds having sulfides and polysulfide groups shown in (A) to (D) of JP-A-10-31279 can be mentioned, and specifically, (C-1), (C-9), (C-14), (C-15), (C-16), (D-1), (D-6), α-sulfur, JP-A 2000-122204 (I-4), (I- 6).

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. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 1 × 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

  In the silver halide color photographic material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing 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-3-251840, page 308 and JP-A-6 A dye described in No. 3770 is preferably used.

  In the silver halide color light-sensitive material of the present invention, it is preferable that a whitening property can be further improved by adding a fluorescent brightening agent. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  The silver halide color 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. 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, the BS described in JP-A-3-251840, page 28, can be used. -1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. how mechanically pulverized and dispersed to 1μm or less of the fine particles in the water-based under the conditions of ^{8,60~80 ℃, 3.8 × 10 -2 N} / m or less surface tension described in JP-B-60-6496 A method of dispersing in the presence of a surfactant that suppresses to a minimum, dissolved in an acid that does not substantially contain water and that does not exceed pKa as described in JP-A-50-80826, and adds the solution to an aqueous solution A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include a high speed stirring type disperser described in FIG. 1 of JP-A-4-125561, a ball mill, a sand mill, an ultrasonic disperser, and the like. be able to.

  Further, when using these dispersing apparatuses, as described in JP-A-4-125632, a pre-treatment such as dry pulverization is performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

  As the coupler used in the silver halide color photographic material of the present invention, any compound 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. However, as typical examples, yellow dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, magenta dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical cyan dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm is representative.

  As the magenta coupler used in the silver halide color light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of its good spectral absorption characteristics. Specific examples of the preferred compound include compounds M-1 to M-19 described on pages 8 to 11 of the same. As other specific examples, compounds M-1 to M-61 described in European Patent No. 0273712, pages 6 to 21 and compounds 1 to 223 described in JP 0235913, pages 36 to 92 are described above. There are other than the typical examples.

The magenta coupler can also be used in combination with other types of magenta couplers and is usually 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol, per mol of silver halide. Can be used in a range.

  The λmax of spectral absorption of the magenta image formed in the silver halide color photographic material of the present invention is preferably 530 to 560 nm, and λL0.2 is preferably 580 to 635 nm. λL0.2 is a wavelength on the spectral absorbance curve of the magenta image that is longer than the wavelength at which the maximum absorbance is 1.0 and the absorbance is 0.2.

  The magenta image forming layer of the silver halide color light-sensitive material of the present invention preferably contains a yellow coupler in addition to a magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. A preferred yellow coupler to be contained in the magenta image forming layer of the present invention is a coupler represented by the general description [Y-Ia] described in JP-A-6-95283, page 12, right column. Of the couplers represented by the general formula [Y-1] of the same publication, a coupler represented by [M-1] is preferable when combined with a magenta coupler represented by the general formula [M-1]. The coupler has a pKa value not lower than 3 or lower than the pKa value not lower than 3 pKa.

  Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283 and compounds described on pages 13 to 17 of JP-A-2-139542 ( Y-1) to (Y-58) can be preferably used, but of course not limited thereto.

  As a cyan coupler which can be preferably used for the cyan image forming layer of the silver halide color light-sensitive material of the present invention, a pyrrolotriazole coupler is preferably used, and a general formula (I) or (II) described in JP-A-5-313324 is used. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Examples of cyan couplers other than those described above include pyrroloazole type cyan couplers described in European Patent Nos. 488,248 and 491,197 A1, and 2,5 described in US Pat. No. 5,888,716. -Diacylaminophenol coupler, pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in US Pat. Nos. 4,873,183 and 4,916,051 In particular, pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-31360, and JP-A-8-339060 are also preferable.

  In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent No. 333,185A2 (particularly couplers listed as specific examples ( 42) 4-equivalent couplers having a chlorine-eliminating group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyanides described in JP-A No. 64-32260. Couplers (among others, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 456,226A1, and EP 484,909. A pyrroloimidazole type cyan coupler can also be used.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. Paragraph Nos. [0012] to [0059] of the patent. The above description includes the exemplary cyan couplers (1) to (47) and is applied to the present application as it is.

The cyan coupler can usually be used in the silver halide emulsion layer in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  As the yellow coupler contained in the yellow image forming layer in the silver halide color light-sensitive material of the present invention, known acylacetanilide couplers can be preferably used.

  Specific examples of the yellow coupler include compounds described in pages 5 to 9 of JP-A-3-241345, compounds represented by YI-1 to Y-I-55, or JP-A-3-209466. The compounds described on pages 11 to 14 and the compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283, compounds of general formulas (I) and (II) described in JP-A-2002-352023, and the like can also be mentioned. .

  The λmax of the spectral absorption of the yellow image formed by the silver halide color photographic material of the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

  The spectral absorption λL0.2 of the yellow color image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24, and is a long wave in the spectral absorption characteristics of the yellow dye image. Indicates the size of unnecessary absorption on the side.

The yellow coupler can usually be used in the silver halide emulsion layer in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, a phosphoric acid ester compound represented by the general formula [HBS-I] described in JP-A-6-95283, page 22 and a phosphine oxide compound represented by [HBS-II] are more preferable. A compound represented by the general formula [HBS-II] described on page 22 of the same number is preferred. Further, higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A-4-265975 can be raised.

  In the silver halide color light-sensitive material of the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, Particularly preferred for magenta dyes are amine compounds represented by the general formula A described in No. 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A No. 62-182741. Further, a compound represented by the general formula I ′ described in JP-A-1-196049 and a compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  When using an oil-in-water emulsion dispersion method to add a stain inhibitor or other organic compound used in the silver halide color light-sensitive material of the present invention, it is usually a water-insoluble high-boiling organic material having a boiling point of 150 ° C. or higher. If necessary, the solvent is dissolved in combination with a low boiling point and / 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 organic solvent after the dispersion or simultaneously with the dispersion may be added. As high-boiling organic solvents that can be used to dissolve and disperse stain inhibitors, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  As a preferable compound as a surfactant used for dispersing a photographic additive used for the silver halide color light-sensitive material of the present invention or adjusting the surface tension at the time of coating, a hydrophobic compound having 8 to 30 carbon atoms in one molecule. And those containing a group and a sulfonic acid group or a salt thereof. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time until the coating after addition to the coating solution should be short, and 10 hours each. Is preferably within 3 hours, and more preferably within 20 minutes.

  In the silver halide color light-sensitive material of the present invention, a compound that reacts with oxidized developing agent is added to the layer between the light-sensitive layer to prevent color turbidity or added to the silver halide emulsion layer. The fog and the like can be improved. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Examples thereof include compounds represented by general formula II described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 of the same, and compound 1 described on page 17.

  In the silver halide color light-sensitive material of the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and compounds represented by general formula III described in JP-A 64-66646. Compounds represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, general formula I described in JP-A No. 4-1633, general formula (I) described in JP-A No. 5-165144, The compound shown by (II) is mentioned.

  The silver halide color light-sensitive material of the present invention preferably contains an oil-soluble dye or pigment because the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  In the silver halide color light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As these hardeners for binders, known hardeners can be used, and among them, vinylsulfone type hardeners are preferably used. Examples of the vinyl sulfone type hardener include compounds described in JP-A-61-249054, page 25, upper right column, line 13 to page 27, upper right column, line 2. In addition, a chlorotriazine type hardener can be used in combination as long as the effect of the vinyl sulfone type hardener is not impaired. As the chlorotriazine type hardener, JP-A 61-245153, page 3, lower left column 1 Examples include the compounds described in the 4th line from the lower right column of the 3rd line to the 3rd page and the 4th line to the lower 5th page of the lower right from the 3rd page.

  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 mold and bacteria which adversely affect the photographic performance and image storage stability. In order to improve the physical properties of the surface of the silver halide color light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer. Of these, silica fine particles are preferable from the viewpoint of achieving the object effect of the present invention, and examples thereof include Silicia 350 and 445 manufactured by Fuji Silysia Chemical Ltd.

  As the support used for the silver halide color photosensitive 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 and 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 support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is preferably used further 70~120g / m ² base paper.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  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 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.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, it is more preferable that the average surface roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect that the gloss is good is obtained.

  The photographic light-sensitive material used in the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic properties, dimensions). One or more subbing layers for improving the degree of stability, rub resistance, hardness, antihalation, 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 width of the photosensitive material, a material having an arbitrary width can be used according to the use, but a width of 400 mm or more is preferably used for the proof use. A photosensitive material having a width of 800 mm or more is also preferably used.

  Next, an image forming method using the silver halide color photographic material of the present invention will be described.

  In the present invention, the image is preferably formed by an area gradation image forming method in which pixels with variable density are formed and halftone dots are reproduced by the pixel aggregate.

  The area gradation image referred to in the present invention is not represented by the shade of the color of each pixel, but is represented by the size of the area of the color developed to a specific density, It may be considered synonymous with. The halftone dots used for normal printing are arranged at equal intervals according to the number of screen lines, and the shade of the image is expressed by the size of the arranged halftone dots.

  In the image forming method according to the present invention, the pixel array is preferably formed by the FM screening method.

  Normally, halftone dots used for printing are AM (Amplitude Modulation = amplitude modulation) in which halftone dots are arranged at equal intervals according to the number of screen lines and the density of the image is expressed by the size of the arranged halftone dots. There is a method called “screen” and a method called “FM (Frequency Modulation) = frequency modulation (Frequency Modulation) screen” that expresses the density of the image by the density of small dots of a certain size arranged in a pseudo-random arrangement. The FM screen method, which is a halftone dot conversion method, is becoming mainstream.

  The features of the FM screen method include the following.

  1) Moire is not visible (AM only adjusts the screen angle of each color plate to minimize output moire).

  2) Rosette pattern does not occur (AM produces a tortoiseshell pattern from the highlight to the intermediate mesh).

  3) Density jump does not occur (in AM, a density step occurs at a halftone dot near 50%).

  4) Vivid color expression.

  5) If the output data amount is the same, the resolution is higher than that of the AM (FM generated from the same input data amount requires relatively small image data).

  6) Generally, since the dot gain increases remarkably from the midpoint to the shadow portion, the ink amount can be reduced accordingly.

  In the original plate making and plate making process, when making a plate making film, when making a printing plate, when printing, the halftone dots that occur when printing, etc., can not be reproduced sufficiently, the quality is not stable, In addition, there is a problem that the roughness of the highlight portion is remarkable. However, in recent years, with the spread of the Computer To Plate (CTP) system, a plate is created directly from image data, and the halftone dot can be stably reproduced by the FM screen method. In addition, new FM screen technology has been developed and sold by various printing related manufacturers. Examples include Staccato from Creo Co., Ltd., RandotX from Dainippon Screen Mfg. Co., Ltd., and Fairdot from Dainippon Screen Mfg. Co., Ltd., which incorporates the advantages of both AM and FM screens. .

  In order to obtain DDCP corresponding to not only image formation by the FM screen method but also high-definition printing, it is necessary to improve the sharpness of the silver halide color photosensitive material. The silver halide color light-sensitive material is the most effective.

  In the present invention, any known exposure light source of the exposure apparatus used in the image forming method can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use. An edge-emitting diode that is a kind of a small area light-emitting diode as described in JP-A-2002-72367 can be preferably used.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of direct modulation, the amount of emitted light may be changed by adjusting the current value, or a pulse width modulation method in which light is emitted in pulses and the width of the pulse (light emission time) is changed may be used. A pulse number modulation method in which the number is changed may be adopted. In the case of LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, a device such as AOM or EOM (electro-optic modulator) is generally used.

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used if the amount of light is weak.

  The light emission wavelength of the light source can be preferably used as long as the photosensitive material has a sufficient sensitivity, but a wavelength region having a sufficient sensitivity difference from other photosensitive layers in order to prevent color turbidity. It is preferable to use it. Although it depends on the contrast of the photosensitive material, it is preferable that the common logarithm of the exposure amount has a sensitivity difference of 0.6 or more, preferably 1.0 or more. In addition, when the emission wavelength varies depending on the environmental conditions and operating conditions in which the light source is placed, it is theoretically preferable to match the peak wavelength of the spectral sensitivity. It is preferable to select the wavelength in consideration of the relationship. Examples thereof include JP-A-6-75342 and JP-A-2001-83663. Further, when not only the emission wavelength but also the emission intensity varies, it is preferable to select the emission wavelength in relation to the spectral sensitivity. Examples thereof include Japanese Patent Application Laid-Open No. 2002-72367 and Nikkei New Material September 1987. It is described on page 54 of the 14th of the month.

  As an apparatus used for the image forming method, a method in which a plurality of photosensitive materials are set in advance and the photosensitive materials are appropriately selected and used can be preferably used. In this case, the two types of photosensitive materials can be, for example, photosensitive materials having different widths or photosensitive materials having different surface properties (unevenness of the support). The selection of the photosensitive material may be a method of setting using a switch of the image forming apparatus or the like, or setting information may be transmitted together with image data and selected based on the setting information. It is also advantageous to automatically select the optimum photosensitive material size according to the size of the image data. In special cases, the same type of photosensitive material can be loaded, and when one photosensitive material is used up, the other photosensitive material can be automatically used. This is advantageous because continuous unattended operation is possible. Can be used.

  In general, in the case of area gradation exposure, the purpose can be achieved by developing colors of Y, M, C, and black. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the light flux on the silver halide color photosensitive material, but the photosensitive material is wound around a cylindrical drum and rotated in a direction perpendicular to the rotation direction while rotating at high speed. Alternatively, a cylindrical outer surface scanning method for moving the light beam may be employed, and a cylindrical inner surface scanning method in which a silver halide color photosensitive material is brought into close contact with a cylindrical depression for exposure can also be preferably used. A plane scanning method may be employed in which the polyhedral mirror is rotated at a high speed to expose the silver halide color photosensitive material conveyed by moving the light beam at right angles to the conveying direction. In order to obtain a high image quality and a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide color photosensitive material must be brought into close contact with the cylindrical drum accurately. For this to be done accurately, it needs to be accurately aligned and transported. The silver halide color light-sensitive material used in the present invention can be preferably used because the surface on the side to be exposed is wound outwards can be more accurately aligned. From the same point of view, the support used for the silver halide color photographic material used in the present invention has an appropriate rigidity, and the Taber rigidity is preferably 0.8 to 4.0.

  The drum diameter can be arbitrarily set according to the size of the silver halide color photosensitive material to be exposed. The number of revolutions of the drum can also be set arbitrarily, but an appropriate number of revolutions can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern and the sensitivity of the photosensitive material. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide color photosensitive material can be fixed to the drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material. Can be sucked into close contact. In order to prevent troubles such as image unevenness, it is important to make the photosensitive material as close as possible to the drum.

  Next, the processing method of the silver halide color photographic material of the present invention will be explained.

  In the method for processing a silver halide color photographic material of the present invention, it is preferable to employ a stabilization treatment with a stabilizing solution or a water washing treatment with ion-exchanged water following the color development processing step and the bleach-fixing processing step.

  First, the color development process will be described.

  A known aromatic primary amine developing agent can be used in the color developer according to the present invention. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N , N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N Ethyl-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the color developer used in the present invention, a color developing agent is used. In order to reduce disappearance due to oxidation, it is preferable to contain a preservative. 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, Hydroxylamine derivatives described in, for example, 1-1875557 can be used.

  Other preservatives include hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, 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, US Pat. Nos. 3,615,503, 2,494,903, JP-A-52. -1433020, Japanese Patent Publication No. 4830696 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, the following buffering agent is preferably used. 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-propandiol 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 or 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 thioether 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 represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182 and 4,230,796. 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.

  In the present invention, the color developer can be used in any pH range, but is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing. It is done.

  The temperature of the color developer used in the color development step according to the present invention is preferably high in terms of simply increasing the image density obtained, but there is also a problem with the stability of the color developer itself, and the temperature is excessively high. If set, it may be a factor that degrades image stability. Accordingly, the temperature of the color developer is preferably 40 ° C. or lower, more preferably 38 ° C. or lower.

  Next, details of the bleach-fixing step according to the present invention will be described.

  In the present invention, any bleaching agent can be used as a bleaching agent used in the bleach-fixing solution, and in particular, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediamine). Aminopolycarboxylic acids such as tetraacetic 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 and the like are preferable.

  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. A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. 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.

  Various compounds can be used as a bleaching accelerator in the bleach-fixing solution. 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 bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide) or 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 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; ethylenebisthioglycolic acid, 3, These are water-soluble silver halide solubilizers such as thioether compounds such as 6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. 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.

  Bleach fixers may contain sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite as preservatives. In general, ascorbic acid, a carbonyl bisulfite adduct, or a carbonyl compound 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.

  In the present invention, in order to increase the activity of the bleach-fixing solution, air or oxygen may be optionally blown in the processing bath and in the processing replenisher storage tank, or a suitable oxidizing agent such as peroxidation may be used. Hydrogen, bromate, persulfate, or the like may be added as appropriate.

  The pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 5.5 to 8.0. The pH of the bleach-fixing solution is the pH of the processing tank at the time of processing the photosensitive material, and not the pH of the replenishing solution.

The time required for the bleach-fixing step applied to the processing method 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 washing solution 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 amount of the bleaching solution is preferably 200 ml / m ² or less, more preferably 150 ml / m ² or less from the viewpoint of further achieving the object effect of the present invention, and particularly 50 ml / m ^{2 to} 150 ml / m ^2. It is preferable that

  Further, the temperature of the bleach-fixing solution used in the bleach-fixing step is preferably high in terms of simply improving the bleach-fixing ability and improving the white background, but like the color developer, the bleach-fixing solution itself has a preserving property. From the problem, it is preferably 43 ° C. or lower, more preferably 40 ° C. or lower.

  Next, the stabilizing solution will be described.

  It is particularly preferred for the purposes of the present invention that the stabilizer contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is L.I. G. Sillen, A.M. E. "Stability Constants of Metal-ion Complexes" by Martell, The Chemical Society, London (1964), S.M. Chaberek, A .; E. This means a constant generally known by Martell's “Organic Sequencing Agents” Wiley (1959).

Examples of the chelating agent having a chelate stability constant for iron ions of 8 or more include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

  Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, Examples include techol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1. -Diphosphonic acid, etc. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

  The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, more preferably 0.05 to 20 g.

  Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilizer. These are supplied by various inorganic and organic ammonium salts, specifically ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluoride. Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, laurin Ammonium tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, malic acid water Ammonium, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetic acid ammonium, ethylenediaminetetraacetic acid ferric ammonium, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, Ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium and the like. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably in the range of 0.001 mol to 1.0 mol, and more preferably in the range of 0.002 to 0.8 mol, per liter of the stabilizer.

Furthermore, it is preferable that the stabilizer contains sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. The sulfite is preferably added in an amount of at least 1 × 10 ⁻³ mol / liter, more preferably 5 × 10 ⁻³ mol / liter to 10 ⁻¹ mol / liter, in the stabilizer. Such an amount is added, and has an effect of preventing stains in particular. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stable replenishing solution.

  Other compounds that can be added to generally known stabilizers include polyvinylpyrrolidone (PVP K-15, K-30, K-90), organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid). Acid), pH adjusters (phosphate, borate, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, siabendazole derivatives, organic halogen compounds, other papers) Antifungal agents known as pulp industry slime control agents) or optical brighteners, surfactants, preservatives, metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc. is there. One or more of these compounds can be selected and used as long as the effects of the present invention are not impaired.

  After the stabilization treatment, no water washing treatment is required, but rinsing by a small amount of water washing in a very short time, surface washing, etc. can be optionally performed.

The presence of a soluble iron salt in the stabilizing solution is preferable for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizing solution at a concentration of at least 5 × 10 ⁻³ mol / liter, more preferably in the range of 8 × 10 ⁻³ to 15 × 10 ⁻² mol / liter, and still more preferably The range is 12 × 10 ⁻³ to 10 × 10 ⁻² mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenisher, or they may be added to the stabilizing solution (tank solution) by elution from the photosensitive material in the stabilizing solution. It may be added to the stabilizer (tank solution) by adhering it to the photosensitive material to be processed from the pre-bath and bringing it in.

  Further, in the present invention, a stabilizing solution in which calcium ion and magnesium ion are reduced to 5 ppm or less by performing an ion exchange resin treatment may be used, and a method of further containing the above-mentioned antibacterial agent or halogen ion releasing compound. It may be used.

  In the present invention, the pH of the stabilizing solution is preferably in the range of 5.5 to 10.0. The pH adjuster that can be contained in the stabilizing solution may be any of commonly known alkali agents or acid agents.

  One of the characteristics of the present invention is that the treatment temperature during the stabilization treatment or the water washing treatment is 40 ° C. or more in the first tank, but other than that, 15 ° C. to 70 ° C. is preferable, and more preferably 20 ° C. to It is in the range of 55 ° C. In particular, the temperature of the liquid in the total stabilization treatment tank or the washing tank is preferably 40 ° C. or higher. The treatment time for the stabilization treatment or the water washing treatment is preferably 120 seconds or less.

  The replenishment amount of the stabilizing solution is preferably 0.1 to 50 times, especially 0.5 to 30 times the amount of the pre-bath (bleach fixing solution) brought in per unit area of the light-sensitive material from the viewpoint of quick processing and dye image storage. Is preferred.

  In the present invention, the washing or stabilizing solution is also characterized in that it contains only additives such as scale inhibitor, antifungal agent, or preservative in addition to the sulfite. Examples of compounds having these effects include orthophenylphenol, benzoisothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-propanediol, and 8-hydroxy. Examples include quinoline, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2,4-dichloro-S-hydroxytriazine sodium. Particularly preferred are orthophenylphenol, 2-bromo-2-nitro-1,3-propanediol, 2,4-dichloro-S-hydroxytriazine sodium and the like.

  In the treatment process of the stabilization tank, it is preferable to replenish each tank individually to become waste liquid, but it is not effective in reducing the replenishment amount. Therefore, it is preferable to use a so-called counter current method in which the replenisher enters the last tank, sequentially overflows to the previous tank, and overflows from the front tank as waste liquid.

  The development processing apparatus used for the development processing of the silver halide photosensitive material of the present invention fixes the photosensitive material to the belt even if it is a roller transport type that conveys the photosensitive material between rollers arranged in a processing tank. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank, and the photosensitive material is transported and the processing liquid is sprayed. Also, a web system by contact with a carrier impregnated with a treatment liquid, a system by a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, a running process is usually performed using an automatic processor. At this time, the replenishment 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 replenishment method. And the method described in the published technical report 94-16935 is most preferable.

  In addition, a semicircular guide made of a material such as plastic or Teflon (registered trademark) with a low surface slip resistance is arranged at the transition portion provided between the treatment tanks, thereby efficiently on the liquid surface. A method of carrying a U-turn to convey a photosensitive material is also generally used.

  Further, in the drying process, particularly in the case of an automatic developing machine for a photosensitive material having a large size of A3 or larger, the photosensitive material is conveyed by driven opposed rollers provided at the entrance and exit portions of the photosensitive material. In the case of the air drying method, generally, a plurality of elongated bars such as piano wires are arranged on the upper and lower surfaces or the lower surface of the photosensitive material inside the unit, and the photosensitive material is designed to slide there. All of these guides are arranged in parallel to the conveyance direction of the photosensitive material. However, it is preferable to arrange the guides at a slight angle in the conveyance direction so that the photosensitive material can be conveyed more smoothly. A preferred angle is 3 ° or more and 20 ° or less. More preferably, it is 3 ° or more and 10 ° or less. As the direction in which the angle is given, an arrangement is preferred in which each of them faces outward from the center in the transport direction.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of silver halide color photosensitive material >>
[Preparation of Sample 101]
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having a layer structure shown in the following Table 1 is coated on the polyethylene layer side containing titanium oxide, and gelatin is 7.20 g / m on the back side. ² and 0.65 g / m ² of silica matting agent (average particle size: 4.0 μm) were applied. At this time, H-2 was added to the back side as a hardener so as to be 0.05 g / m ² .

The coupler and the stain reducing agent were dissolved in a high boiling point solvent and ultrasonically dispersed and added as a dispersion. At this time, (SU-1) was used as a surfactant. Further, the ultraviolet absorber was also ultrasonically dispersed and added as a dispersion. Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

  In this way, Sample 101, which is a silver halide color photosensitive material consisting of 8 layers, was produced.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- A mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2. Q-4: 2,5-di-t-butylhydroquinone Silica matting agent: Silica fine particles, manufactured by Fuji Silysia Chemical Co., Ltd., Silicia 350 (average particle size: 4.0 μm * average particle size is SALD-2000 type manufactured by Shimadzu Corporation) (This is a value measured with a laser diffraction scattering method particle size distribution analyzer.)

[Preparation of photosensitive silver halide emulsion]
The silver halide emulsion used for the preparation of Sample 101 was prepared according to the following method.

(Preparation of blue-sensitive silver halide emulsion)
The following (A solution) and (B solution) were simultaneously added to 1 liter of 2% gelatin aqueous solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) and (D liquid) was simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

<Liquid A>
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
<Liquid B>
Silver nitrate 10g
200ml with water
<C liquid>
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
600ml with water
<D liquid>
300 g of silver nitrate
600ml with water
After completion of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm and a coefficient of variation in particle size distribution. An emulsion (EMP-101) which was a monodispersed cubic emulsion having a silver chloride content of 0.07 and a silver chloride content of 99.5 mol% was obtained.

  The emulsion (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B101).

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Subsequently, in the preparation of the emulsion (EMP-101), the average particle size was similarly changed except that the addition times of (A solution) and (B solution) and (C solution) and (D solution) were changed appropriately. An emulsion (EMP-102) was obtained which was a monodisperse cubic emulsion having 0.64 μm, a coefficient of variation of grain size distribution of 0.07 and a silver chloride content of 99.5 mol%.

  The blue-sensitive silver halide emulsion (Em-B101) was prepared in the same manner as in the preparation of the blue-sensitive silver halide emulsion (EMP-101), except that the emulsion (EMP-102) was used instead of the emulsion (EMP-101). Em-B102), and a 1: 1 mixture of blue-sensitive silver halide emulsion (Em-B101) and blue-sensitive silver halide emulsion (Em-B102) was added to the seventh layer of blue-sensitive halogenated halide. Used as a silver emulsion.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole

(Preparation of green photosensitive silver halide emulsion)
In the preparation of the emulsion (EMP-101), the average particle size was 0.40 μm, except that the addition times of (A liquid) and (B liquid), (C liquid) and (D liquid) were appropriately changed. An emulsion (EMP-103), which is a monodispersed cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%, was prepared.

  The emulsion (EMP-103) was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green photosensitive silver halide emulsion (Em-G101).

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-2 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Subsequently, in the preparation of the emulsion (EMP-103), the average grain size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were appropriately changed. An emulsion (EMP-104) which was a monodispersed cubic emulsion having a diameter of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was prepared.

  The green-sensitive silver halide emulsion (Em-G101) was prepared in the same manner as in the preparation of the above-mentioned emulsion (EMP-104) instead of the emulsion (EMP-103). An emulsion (Em-G102) was prepared, and a 1: 1 mixture of the green-sensitive silver halide emulsion (Em-G101) and the green-sensitive silver halide emulsion (Em-G102) was added to the green sensitivity of the fifth layer. Used as a silver halide emulsion.

(Preparation of red-sensitive silver halide emulsion)
The prepared emulsion (EMP-103) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R101).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
Next, the prepared emulsion (EMP-103) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R102).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
A 1: 1 mixture of the red-sensitive silver halide emulsion (Em-R101) and the red-sensitive silver halide emulsion (Em-R102) prepared above was used as the red-sensitive silver halide emulsion for the third layer. .

  STAB-4: p-toluenethiosulfonic acid

[Preparation of black colloidal silver 1]
The black colloidal silver 1 used in the first layer (colored layer) was prepared according to the following method.

(Nucleation process of black nuclear colloidal silver)
In a 2 liter kettle equipped with a stirrer and temperature-controllable, 820 ml of pure water was added at room temperature and stirred at about 1500 rpm. When the water temperature was raised to 33 ° C., 30.0 g of dextrin was added and dissolved. About 5 minutes later, after confirming that the dextrin was dissolved, a solution in which 5.2 g of sodium hydroxide was dissolved in 30 ml of pure water was added to adjust the pH to 9.9, and the temperature in the kettle was adjusted to 37 ° C. When the temperature reached 37 ° C., the stirring intensity was changed to about 2,000 rpm, and a silver nitrate solution in which 15.0 g of silver nitrate was dissolved in 150 ml of pure water was added. Subsequently, stirring was continued for 10 minutes at pH 9.9, and after cooling and the temperature in the kettle being 23 ° C., pure water was added to finish the total amount to 1030 ml to prepare a yellow colloidal silver core dispersion.

  When the absorption characteristics of the yellow colloidal silver core dispersion prepared as described above were measured, it had a relatively sharp absorption maximum at 395 nm.

(Growth process of black colloidal silver)
[Additive formulation]
<1> Liquid: 125 ml of pure water
<2> Solution: Gelatin solution (40 ° C.) in which 6.0 g of gelatin is dissolved in 40 ml of pure water
<3> Liquid: 44 ml of nuclear colloidal silver dispersion
<4> Solution: A solution (3.2 ° C.) obtained by dissolving 3.2 g of hydrazine sulfate in 125 ml of pure water.
<5> Liquid: Silver nitrate solution in which 14.4 g of silver nitrate is dissolved in 70 ml of pure water <6> Liquid: 19.5 ml of 15% by mass ammonia water
<7> Solution: A solution in which 28.2 mg of 2-mercapto-benzthiazole and 0.30 mg of sodium hydroxide are dissolved in 35 ml of pure water <8> Solution: 430 ml of pure water (40 ° C.)
<9> Liquid: 40.5 ml of 5% by weight demole (manufactured by Kao Atlas) solution
<10> Liquid: 48.6 ml of 20% by weight magnesium sulfate solution
<11> Liquid: 900 ml of pure water (40 ° C.)
<12> Liquid: 21.8 ml of 20% by mass magnesium sulfate solution
<13> Liquid: Gelatin solution (55 ° C.) in which 20.4 g of gelatin is dissolved in 150 ml of pure water
In a 2.5-liter kettle equipped with a stirrer and temperature-controllable, the <1> solution was placed at room temperature and stirred at about 1000 rpm. <2> Solution was added to this solution at 23 ° C., <3> Solution was added after 1 minute, <4> Solution was added after 1 minute, and <5> Solution was added after 1 minute.

  After 20 minutes, the <6> solution was slowly added over 5 minutes. At this time, the pH in the kettle was 9.2, and the temperature was 32 ° C. After an additional 20 minutes, solution <7> was added.

  After that, when the stirring intensity is changed to about 1100 rpm and the temperature is adjusted to 40 ° C., the <8> solution is added, the <9> solution is added after 2 minutes, and the <10> solution is further added after 2 minutes. Stir for minutes. After leaving still for 40 minutes, the supernatant was drained. The stirring intensity was returned to 1000 rpm, the <11> solution was added, the <12> solution was added after 5 minutes, and the stirring was continued for another 5 minutes. Finally, the <13> solution was added and stirred at 50 ° C. for 20 minutes. Then, using a Menton-Gorin disperser, the collision pressure was changed to 1.0 MPa at the first stage and 1.5 MPa at the second stage, and then the whole was finished to 285 g with pure water to obtain a black colloid. Silver 1 was prepared. The pH of this dispersion containing black colloidal silver 1 was 6.10. Further, the conductivity was 2.09 mS / cm and the specific gravity was 1.056.

[Preparation of Sample 102]
Sample 102 was prepared in the same manner as in the preparation of Sample 101 except that the gelatin coating amount of the second layer was changed from 0.50 g / m ² to 1.2 g / m ² .

[Preparation of Sample 201]
Sample 201 was prepared in the same manner as in the preparation of Sample 101 except that the layer configuration shown in Table 2 and the addition amount of each additive were changed.

[Production of Samples 301 to 306]
In the preparation of the sample 201, polyvinyl pyrrolidone K-90 (molecular weight 630,000, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polyvinyl pyrrolidone derivative is added to the first layer (colored layer containing black colloidal silver 1) as shown in Table 3. Samples 301 to 306 were prepared in the same manner except that was added.

<Evaluation of silver halide color photosensitive material>
[Pretreatment of sample]
After preparing each sample, pretreatment sample A, pretreatment sample B, and pretreatment were stored for 4 weeks under conditions of a refrigerator (5 ° C.), 40 ° C./55% RH, and 40 ° C./80% RH, respectively. Sample C was prepared.

〔exposure〕
The pretreatment samples A to C subjected to the pretreatment and the reference sample S not subjected to the pretreatment were exposed according to the following method.

  Ten blue (B) LEDs were arranged as a light source in the main scanning direction, and the exposure timing was gradually delayed so that the same place could be exposed with ten LEDs. Further, an exposure head was prepared in which 10 LEDs were arranged in the sub-scanning direction and exposure for 10 adjacent pixels could be performed at once. Similarly, green (G) and red (R) were combined with LEDs to prepare exposure heads. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 100 μm. The exposure time per pixel was about 100 nanoseconds.

  As the image data, test charts with halftone dots of 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, and 100% for each color of Y, M, C, and K were used. . A square pattern of 5 cm square was used for each halftone dot%. The size of the photosensitive material used was 670 mm (width) × 970 mm (length). The halftone dots were halftone dots generated by the FM screen method.

<Development processing>
After the exposure, the following development processing was performed.

Processing step Processing temperature Time Replenishment amount Color development 40.0 ± 0.3 ° C 120 seconds 200ml / m ²
Bleach fixing 40.0 ± 0.5 ° C 90 seconds 100ml / m ²
Stabilization 40.0 ± 0.5 ° C 60 sec 150ml / m ²
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-hydroxyethyl) -4-aminoaniline sulfate
2.9g 4.8g
N, N-disulfoethylhydroxylamine 20.4 g 18.0 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
Add water to bring the total volume to 1 liter, adjust the tank solution to pH = 10.0, and the replenisher to pH = 10.6.

[Bleaching fixer tank solution and replenisher solution]
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
Potassium bromide 25.0g
Imidazole 20.0g
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]
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Ammonium sulfite 2.0 g
Ethylenediaminetetraacetic acid disodium salt 2.0g
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.1 with potassium hydroxide.

<Evaluation of formed image>
[Evaluation of storage stability: variability on white background]
The magenta density of the white background part (unexposed part) of each sample subjected to the development treatment was measured using a reflection densitometer manufactured by X-rite.

  Subsequently, the magenta concentration increase width ΔDminA (pretreatment sample A−reference sample S) and ΔDminB (pretreatment sample B−reference) of each of the pretreatment samples A to C subjected to the pretreatment with respect to the magenta concentration of the reference sample S. Sample S) and ΔDminC (pretreatment sample C-reference sample S) were determined and used as a measure of storage stability.

[Evaluation of sharpness: small dot reproducibility]
The 3% dot image of the prepared reference sample S was visually evaluated, and small dot reproducibility was evaluated according to the following criteria.

◎: 3% halftone dot image can be clearly recognized ○: 3% halftone dot image is almost recognizable △: 3% halftone dot image is observed blurry, and there is some practical concern ×: No halftone dot Table 3 shows the results obtained as described above.

  As apparent from the results shown in Table 3, the sample of the present invention containing black colloidal silver in the colored layer as the first layer and adjacent to the red-sensitive silver halide emulsion layer is a comparative example. On the other hand, it can be seen that it has excellent sharpness without impairing storage stability.

  Furthermore, in this invention, it turns out that the fog density | concentration fluctuation | variation at the time of storage on various conditions is restrained low by adding a polyvinylpyrrolidone derivative to the 1st layer containing black colloidal silver.

Example 2
<< Preparation of silver halide color photosensitive material >>
In the preparation of Samples 301 to 306 described in Example 1, as a polyvinyl pyrrolidone derivative added to the first layer (colored layer containing black colloidal silver 1), polyvinyl pyrrolidone K-90 (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 630,000) ), Samples 401 to 406 were prepared in the same manner except that polyvinylpyrrolidone K-15 (molecular weight 10,000, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<< Exposure, development and evaluation of silver halide color photographic materials >>
About the produced samples 401-406 and the samples 101, 102, and 201 produced in Example 1, exposure, development processing and evaluation (storage stability and sharpness) were performed in the same manner as in the method described in Example 1. The results obtained are shown in Table 4.

  As is apparent from the results shown in Table 4, fogging when stored under various conditions was obtained by using polyvinylpyrrolidone K-15 having a lower molecular weight instead of polyvinylpyrrolidone K-90 as the polyvinylpyrrolidone derivative. It can be seen that the concentration suppressing effect is larger.

Example 3
<< Preparation of silver halide color photosensitive material >>
In the preparation of Samples 102, 201, 401 to 406 described in Table 4 of Example 2, titanium dioxide (TiO ₂ , average primary particle size: 0.00) was added to the first layer (colored layer containing black colloidal silver 1). Samples 112, 211, and 411 to 416 were prepared in the same manner except that 1.14 g / m ^{2 was} added.

<< Exposure, development and evaluation of silver halide color photographic materials >>
About each sample produced above and the samples 102, 201, 401 to 406 produced in Examples 1 and 2, exposure, development processing and evaluation (sharpness: small dot reproduction) were performed in the same manner as the method described in Example 1. Table 5 shows the results obtained.

  As is clear from the results shown in Table 5, the addition of titanium dioxide to the colored layer containing the black colloidal silver specified in the present invention further improves the small dot reproducibility. I understand.

Example 4
<< Preparation of silver halide color photosensitive material >>
In the preparation of Samples 211, 402 to 404, 412 to 414 described in Table 5 of Example 3, the stain inhibitor (HQ-2, HQ-3) in the first layer (colored layer containing black colloidal silver 1) Samples 213, 422 to 424, and 432 to 434 were prepared in the same manner except that the high-boiling organic solvent (SO-2) was removed.

<< Exposure, development and evaluation of silver halide color photographic materials >>
Samples 211, 402 to 404 and 412 to 414 containing the above-prepared samples and the first layer containing a stain inhibitor and a high-boiling organic solvent are stored for 4 weeks in an environment of 40 ° C. and 55% RH, respectively. Then, exposure is performed in the same manner as described in Example 1, and then, in the development processing described in Example 1, the color developer is processed at three levels of 38 ° C., 40 ° C., and 42 ° C. As a result of confirming the change width of the maximum magenta concentration (Dmax) of each developed sample obtained, the sample containing no stain inhibitor and the high-boiling organic solvent changed the processing conditions with respect to the sample containing them. It was confirmed that the fluctuation range of the maximum density with respect to was small, and the processing stability after the storage treatment was good.

Example 5
<< Preparation of silver halide color photosensitive material >>
In preparation of Samples 101, 201, 404, and 414 described in Examples 1, 2, and 3, black colloidal silver 2 prepared according to the following method was used instead of black colloidal silver 1 used in the first layer (colored layer). Samples 101B, 201B, 404B, and 414B were prepared in the same manner except that was used.

[Preparation of black colloidal silver 2]
In the preparation of the black colloidal silver 1 described in Example 1, 10 to 10 were exemplified compounds S-4 as compounds represented by the general formula (S) in the additive liquid <2> used in the growth process of the black colloidal silver. Black colloidal silver 2 was prepared in the same manner except that 0.0 mg was added.

<< Exposure, development and evaluation of silver halide color photographic materials >>
The sample 101B, 201B, 404B, and 414B (black colloidal silver 2) produced above and the sample 101, 201, 404, and 414 (black colloidal silver 1) produced in Examples 1, 2, and 3 are described in Example 1. The same processing except that the replenishing amount of the bleach-fixing replenisher in the bleach-fixing step was changed to 50 ml / m ² (1/2 of the replenishing amount described in Example 1) after exposure in the same manner as in the above method. Under the conditions, continuous processing was performed until the total replenishment amount of the color developer replenisher became twice the volume of the color developer tank.

[Evaluation of desilvering properties]
Using a spectrophotometer CM-2022 manufactured by Konica Minolta Sensing Co., Ltd. for each sample immediately after the start of continuous processing and a sample at the end of continuous processing, a geometric condition d-0 for illumination and light reception, xenon Measure light using a pulsed light source, measure 10 values of L ^* , a ^* , b ^* with 2 ° field of view, auxiliary standard light D50, determine the average value, and immediately after starting continuous processing of each sample The L ^* difference at the end (ΔL ^* ) and the b ^* difference (Δb ^* ) immediately after the start of the continuous treatment and at the end of the continuous treatment for each sample were obtained, and this was used as a measure of desilvering properties. Table 6 shows.

  As is apparent from the results shown in Table 6, the silver halide color light-sensitive material of the present invention is a comparative example in which the colloidal silver is removed even after continuous processing with a bleach-fixing solution having reduced bleaching ability. It turns out that it is excellent in silver property. Among them, a high desilvering effect is obtained at the level using the black colloidal silver 2 prepared using the compound represented by the general formula (S), and further at the level using the polyvinylpyrrolidone derivative of the first layer. I understand that.

Claims (5)

In a silver halide color light-sensitive material having a light-sensitive silver halide emulsion layer and a light-insensitive layer on a reflective support, at least one of the light-insensitive layers is at least one layer of the light-sensitive silver halide emulsion layer. And a silver halide color light-sensitive material characterized by containing black colloidal silver. 2. The silver halide color photosensitive material according to claim 1, wherein the non-photosensitive layer containing black colloidal silver contains a polyvinylpyrrolidone derivative. 3. The silver halide color photosensitive material according to claim 1, wherein the non-photosensitive layer containing black colloidal silver contains a white pigment. The black colloidal silver contained in the non-photosensitive layer is prepared by reducing a soluble silver salt in the presence of a compound represented by the following general formula (S). The silver halide color photosensitive material of any one of -3.

[Wherein T represents an atomic group necessary to form a 5-membered heterocycle, J represents a hydrogen atom, a hydroxy group, —SO ₃ M ¹ , —COOM ¹ (where M ¹ represents a hydrogen atom, an alkali metal atom) Or a substituted or unsubstituted amino group, a substituted or unsubstituted ammonio group, a C1-C19 alkylthio group substituted by one or more of these, a carbon number of 2 Represents an alkylamide group having -18 carbon atoms, an alkylcarbamoyl group having 2-18 carbon atoms, an alkyl group having 1-19 carbon atoms, or an aromatic group having 6-31 carbon atoms. M represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt). ] The silver halide color photosensitive material according to any one of claims 1 to 4, wherein the non-photosensitive layer containing the black colloidal silver is coated in contact with the reflective support.