JPH0862762A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PURPOSE: To obtain a silver halide photographic sensitive material superior in rapid processing aptitude and small in fluctuation of sensitivity during and after long time storage and that due to temperature at the time of exposure by incorporating a silver halide emulsion sensitized with a specified spectral sensitizing dye and regulating the total calcium content in photographic constituent layers to a specified value or lower. CONSTITUTION: At least one silver halide emulsion layer in the photographic constituent layers formed on a support in the photographic sensitive material contains the silver halide emulsion containing silver chloride in an amount of >=95mol% and sensitized with the spectral sensitizing dye represented by the formula, and the photographic constituent layers have the total calcium content of <=10mg/m<2> . In the formula, each of X1 and X2 is a nonmetallic atomic group necessary to form a 5-membered hetero ring or the like; (n) is an integer of 1-4; each of (p) and (q), is 0 or 1; each of L1 and L2 is a methine group; each of R1 and R2 is an aromatic group or the like; and W1 is a counter ion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a color image forming method, and more specifically, it has excellent suitability for rapid processing, sensitivity fluctuation before and after long-term storage, and sensitivity due to temperature during exposure. The present invention relates to a silver halide photographic light-sensitive material having little fluctuation and excellent stability, and a color image forming method.

[0002]

2. Description of the Related Art Color photography, which has become widespread today, is progressing more and more rapidly and easily everywhere due to the progress of the light-sensitive material itself and the processing technology. Especially in the color printing field, a centralized processing method called a color lab called a mass production high-speed printer or a large-scale processing equipment installed at a production site, or a distributed processing using a small printer processor called a minilab installed at a store Due to the development of methods,
Production is carried out for various purposes. In recent years, due to the practical application of the light-sensitive material using a high silver chloride emulsion and the processing method thereof disclosed in International Publication WO88 / 04534, the speeding up of processing has become more and more advanced.

At the same time as the pursuit of such speeding up of the processing, the stabilization of the obtained print quality has always been required to be improved in order to improve the production efficiency. For that purpose, first, the stability of the performance of the color photographic paper used for print production is important. Considering the market conditions described above, the demand for this performance stability is increasing.
That is, in a large-scale laboratory that is mass-producing, if the performance of the color printing paper is stable, it is possible to set the printing conditions of the high-speed printer to a fixed value and perform the production, so that the efficiency is dramatically increased. In addition, in production using a minilab installed in stores, it is often difficult to secure a skilled operator, and stabilizing the performance of color photographic paper is directly linked to improving print quality and yield. There is.

In stabilizing the performance of the above-mentioned light-sensitive material, it is important to suppress the fluctuation of sensitivity before and after the unexposed light-sensitive material is stored for a long period of time and to suppress the fluctuation of sensitivity due to the temperature at the time of exposure. It has become a challenge. As a technique for suppressing fluctuations in sensitivity before and after long-term storage of a light-sensitive material, JP-A-3-156.
No. 449, the coating pH of a light-sensitive material using a chlorotriazine type hardener is adjusted to 4.0 to 6.5.
No. 142536 discloses that a localized phase having a silver bromide content of at least 10 mol% is formed in the vicinity of the surface of a high silver chloride emulsion grain, and then the surface of the high silver chloride grain is chemically sensitized. ing. As a technique for suppressing the variation in sensitivity due to temperature during exposure, use of a red-sensitizing sensitizing dye having a reduction potential of -1.27 V (vs SCE) or a base value lower than that described in JP-A-3-123340, Japanese Patent Laid-Open No. 4-
335347 and the like are selenium sensitized.
No. 134343 discloses that tellurium is increased. Using these disclosed techniques, when it was examined to suppress the sensitivity fluctuation when the unexposed light-sensitive material was stored for a long period of time and the sensitivity fluctuation due to the temperature at the time of exposure, there was an improvement effect, but the above-mentioned production efficiency improvement It was still inadequate, given the growing demand for.

[0005]

As is apparent from what has been described above, the object of the present invention is to provide a halogen which is excellent in rapid processability and has little sensitivity fluctuation before and after long-term storage and sensitivity fluctuation due to temperature during exposure. It is intended to provide a silver halide photographic light-sensitive material and a color image forming method.

[0006]

The object of the present invention is to:
It was achieved by the silver halide photographic light-sensitive material and the color image forming method described below. That is, (1) in a silver halide photographic light-sensitive material having a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer is spectrally sensitized represented by the following general formula (I). A silver halide photograph comprising a silver halide emulsion sensitized by a dye, the silver chloride content of which is 95 mol% or more, and the total content of calcium in the photographic constituent layers is 10 mg / m ² or less. Photosensitive material.

[0007]

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In the formula, X ₁ and X ₂ each represent a nonmetallic atom group necessary for completing a 5-membered or 6-membered heterocycle, X ₁ is substituted with Z ₁ , and X ₁ and X ₂ may further have a substituent, n represents a positive integer of 1 to 4, and p and q are 0 or 1 respectively.
And L ₁ and L ₂ each represent a methine group which may have a substituent, and R ₁ and R ₂ each have an aromatic group or a substituent which may have a substituent. Optionally represents an aliphatic group, Z ₁ represents a group represented by Ar— (L ₃ ) _m — which is more hydrophilic than a phenyl group, and Ar represents
Represents an aromatic group which may have a substituent, L ₃ represents a linking group, m represents 0 or 1, and W ₁ represents a counter ion when a counter ion is required. (2) A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least three kinds of silver halide emulsion layers having different color sensitivities each containing a coupler which develops yellow, magenta or cyan on a support. At least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more, which is sensitized by the spectral sensitizing dye represented by the general formula (I), and the photographic composition A silver halide color photographic light-sensitive material having a total calcium content of 10 mg / m ² or less in a layer is exposed by a scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then color development processing is performed. And a color image forming method. (3) A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least three kinds of silver halide emulsion layers having different color sensitivities each containing a coupler which develops yellow, magenta or cyan on a support. At least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more, which is sensitized by the spectral sensitizing dye represented by the general formula (I), and the photographic composition A silver halide color photographic light-sensitive material having a total calcium content of 10 mg / m ² or less is processed in a color development time of 25 seconds or less and a total processing time of 120 seconds or less including color development processing to drying. A method for forming a color image, comprising:

The present invention will be described in more detail below. First, the spectral sensitizing dye represented by formula (I) will be described. Examples of the heterocyclic residue completed by X ₁ or X ₂ in the general formula (I) are benzothiazole nucleus, benzoxazole nucleus, benzoselenazole nucleus, benzoterrazole nucleus, quinoline nucleus, benzimidazole nucleus, thiazoline. Examples include a nucleus, an indoline nucleus, an oxadiazole nucleus, a thiazole nucleus, and an imidazole nucleus, preferably a benzothiazole nucleus, a benzoxazole nucleus,
It is a benzimidazole nucleus, a benzoselenazole nucleus, or a quinoline nucleus, and particularly preferably a benzoxazole nucleus. As the substituent on X ₁ or X ₂ , in addition to Z ₁ , halogen (F, Cl, Br, I), cyano, alkoxy (methoxy, ethoxy, methoxyethoxy, etc.),
Aryloxy (phenoxy, etc.), alkyl (methyl,
Ethyl, cyclopropyl, cyclohexyl, trifluoromethyl, methoxyethyl, allyl, benzyl, etc.),
Examples thereof include alkylthio (methylthio, ethylthio, etc.), alkenyl (vinyl, 1-propenyl, etc.), aryl (phenyl, thienyl, toluyl, chlorophenyl, etc.).

The substituent of the methine group represented by L ₁ or L ₂ is alkyl (preferably having 1 to 7 carbon atoms, for example, methyl, ethyl, cyclopropyl, benzyl, etc.) and aryl (preferably Phenyl, toluyl, chlorophenyl, pyrazolyl) having 6 to 10 carbon atoms, amino (preferably having 1 to 12 carbon atoms, diphenylamino,
Methylphenylamino, 4-acetylpiperazine-1-
Ile etc.) and the like. The groups on these methine groups may be linked to each other to form a ring such as a cyclopentene ring or a cyclohexene ring. n is preferably 1 to 3
Is an integer, particularly preferably 2. When n is 2, each methine group is unsubstituted, or it is preferable that only the central methine group among the three methine groups has a substituent, and the central methine group has a methyl group as a substituent. , A lower alkyl group such as ethyl, methylthio, phenyl, benzyl and the like are preferable, and an ethyl group is particularly preferable. W
_The counterion represented by ₁ is the number of cations or anions necessary to keep the charge balance of the compound (to make the compound electrically neutral), such as sodium ion, potassium ion, and tertiary ammonium. Examples thereof include cations such as ions, quaternary ammonium ions, pyridinium ions, and phosphonium ions, and anions such as halide ions, carboxylate ions, sulfonate ions, phenolate ions, and imidate ions.

At least one of the aromatic group and the aliphatic group represented by R ₁ or R ₂ preferably contains an acid group or a group corresponding to a salt thereof. Examples of the acidic group include a sulfo group, a carboxyl group and -CO-NH-SO.
Examples thereof include groups capable of releasing a proton to generate an anion, such as imide groups such as _2- and -CO-NH-CO-. Examples of groups formed by substituting these are 2-sulfoethyl group,
3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 3-methyl-4-sulfobutyl group, -CH
₂ CONHSO ₂ CH _{3 and the} like. As the other substituent, a relatively hydrophilic group such as a hydroxyl group, a carbonamido group, a carbamoyl group, a sulfonamide group, a sulfamoyl group or an alkoxy group is preferable. The group represented by R ₁ or R ₂ may simultaneously have a plurality of groups such as a combination of a sulfo group and a hydroxyl group. The total number of carbon atoms of the aromatic group represented by R ₁ or R ₂ is preferably 6 to 16. The aliphatic group represented by R ₁ or R ₂ preferably has 1 to 6 total carbon atoms. As a standard for selecting a hydrophilic group rather than a phenyl group as Z ₁ , see, for example, A. Leo and C. Hans, Substituen.
t Constants for Correlation Analysis in Chemistry
It is effective to calculate the hydrophilicity / hydrophobicity of a substituent according to the method of and Biology, Wiley New York (1979). Alternatively, it can be determined by preparing an appropriate compound having a phenyl group and a compound in which the phenyl group is replaced with Z ₁ and measuring and comparing the oil / water partition coefficient or the retention time of high performance liquid chromatography. it can.

The aromatic group represented by Ar in Z ₁ may be a hydrocarbon or a heterocycle. The definition of aromatic ring is, for example, published by John Wiley & Sons in 1988.
J. March, Advanced Organic Chemistry, Chapter 2
It is described in. Examples of the aromatic group represented by Ar include phenyl, thienyl, furyl and pyrrolyl. Examples of substituents on Ar include hydroxy,
Halogen, cyano, acyl having 2 to 8 carbon atoms, optionally substituted amino having 0 to 8 carbon atoms, carbamoyl having 1 to 8 carbon atoms, sulfamoyl having 0 to 8 carbon atoms, and 2 carbon atoms To 8 carbon amides, 0 to 8 carbon sulfonamides, 1 to 8 carbon alkyls, 1 to 8 carbon atoms
Alkoxy and the like can be mentioned, but it is preferable that it is not a group having a charge such as carboxy or sulfo. Substituents on Ar are preferably substituents that do not prevent the aromatic group Z ₁ including L ₃ and the heterocycle completed by X _{1 from} being arranged in the same plane. Z ₁
As a preferred example of, for example, European Patent 599381A
The group having an amide group and an aromatic ring described in 1 above, the hydroxyarylacyl group described in EP 599382A1, the furan ring and the pyrrole ring described in EP 599383A1, and the like can be mentioned. L ₃ is preferably a divalent linking group having a chain length of 1 to 4 atoms and may further have a substituent. As an example of L ₃ , —NH
_{CO -, - NHSO 2 -,} - CH 2 -, - CH 2 CH 2
-, -COO-, -CO- and the like can be mentioned. However, A
When r is a phenyl group, a linking group (L ₃ ; -NHCO
A hydrophilic group such as-is always bound.

Particularly preferred as Z ₁ is Ar is a phenyl group, a hydroxy-substituted phenyl group, or an acylamino-substituted phenyl group, and L ₃ is * -CONH- or * -NHCO- (where * represents Ar and Ar). M is 0 or 1 (provided that when m is 1, Ar represents an aromatic heterocyclic group such as furyl or pyrrolyl). The position of the substituent of the heterocyclic nucleus completed by X ₁ or X ₂ is 5th position when the heterocyclic nucleus is a benzazole, and 6 or 7 when the heterocyclic ring is a quinoline ring. The position is preferred. The compounds represented by the general formula (I) used in the present invention can be synthesized according to the methods described in European Patents 599381A1, 599382A1, 599383.
This can be easily performed by referring to the descriptions of A1, 599384A1 and the documents cited in these specifications. The amount of the compound represented by the formula (I) used in the present invention is generally 0.1 to 4 mmol, preferably 0.2 to 2.5 mmol, per mol of silver halide, and other sensitizing dyes. You may use together with. The compound represented by the general formula (I) of the present invention is allowed to exist in the silver halide emulsion layer, but it is preferable that the compound is present in a state of being adsorbed to the photosensitive silver halide grains, and further a so-called J aggregate is formed. It is particularly preferable that the compound is present in the state of being adsorbed on the photosensitive silver halide grains. Specific examples of the compound represented by formula (I) of the present invention are shown below, but the scope of the present invention is not limited to these.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

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[0020]

[Chemical 9]

[0021]

[Chemical 10]

In the present invention, the total content of calcium contained in the photographic constituent layers of the light-sensitive material is 10 mg / m ^2.
It must be: Here, the content of calcium is represented by the weight of calcium ions, atoms or compounds containing calcium contained in 1 m ^{2 of the} light-sensitive material excluding the support, converted into calcium atoms. A known analysis method is used as a method for quantifying the calcium content. For example, in the area of chemistry, special issue 127 (Nankodo 198
0 years) and VA Fassel, Anal. Chem., 46, 11
The ICP analysis method described in detail in 10A (1974) and the like can be used. Calcium contained in the light-sensitive material is brought in as an impurity in gelatin which is usually used as a binder. Gelatin contains thousands of ppm of calcium salts derived from raw materials and manufacturing processes in terms of calcium atoms. When a light-sensitive material is prepared using such gelatin, for example, a light-sensitive material for color photographic paper contains calcium in an amount close to 20 mg / m ² . If the calcium content exceeds 10 mg / m ² , the performance of the photosensitive material varies greatly depending on the temperature during exposure after long-term storage. By setting the amount to 10 mg / m ² or less, the above performance fluctuation can be suppressed. The calcium content is more preferably 8 mg / m ² or less, further preferably 5 mg / m ^2.
m ² or less, most preferably 2 mg / m ² or less (0 mg /
m ^{2 is} also included). JP-A-1-303438 and the like show that the reduction of the calcium content is effective in preventing the failure due to the precipitates in the treatment liquid, and the relationship between the calcium content and the above performance is shown. Is not disclosed at all.

In order to reduce the calcium content in the light-sensitive material, gelatin having a low calcium content is used as a binder, or a gelatin dispersion composition such as a silver halide emulsion or a coupler dispersion used in the production of the light-sensitive material, or a combination thereof. A method of removing calcium by treating the mixture with noodle washing, dialysis, ultrafiltration or the like can be used. In the present invention, it is preferable to use gelatin having a low calcium content. Further, a binder containing no calcium may be used instead of gelatin. Ion exchange treatment is generally preferably used to reduce the calcium content in gelatin. The ion exchange treatment can be carried out by contacting a gelatin solution with an ion exchange resin, particularly a cation exchange resin, during production or use of gelatin, as described in, for example, JP-A-63-296035. it can. In addition, as the gelatin having a low calcium content, acid-treated gelatin in which calcium is hardly mixed in at the time of production can be mentioned. In the present invention, it is preferable to use lime-processed gelatin which has been subjected to ion exchange treatment in the preparation of various compositions.

When the light-sensitive material of the present invention is used as a color light-sensitive material, a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer are provided on a reflective support. At least one layer can be applied and configured. In a general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler that forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. It may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

At least one layer (preferably all layers) of the silver halide emulsion layer used in the present invention is silver chlorobromide or silver chloride composed of 95 mol% or more of silver chloride. The content of silver chloride is preferably 98 mol% or more. In the present invention, it is preferable that substantially no silver iodide is contained in order to accelerate the development processing time. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing storage stability of a light-sensitive material, an emulsion surface of 0.01 to 3 as described in JP-A-3-84545 is used. In some cases, high silver chloride grains containing mol% of silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform.

Regarding the halogen composition distribution inside the silver halide emulsion grains, the grains having a so-called uniform structure having the same composition in any portion of the silver halide grains, and the core and the inside of the silver halide grains are used. Particles with a so-called laminated structure having different halogen compositions with the shell (single layer or multiple layers) that surrounds, or a structure having a non-layered portion with different halogen compositions inside or on the surface (if the particles are on the surface, the particles are Particles having a structure in which different composition portions are joined to the edges, corners or surfaces of the above) can be appropriately selected and used. For high sensitivity,
It is advantageous to use either of the latter two types of particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion of the present invention preferably has a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content,
More preferred is more than 100 mol% and more than 100 mol%.
The silver bromide content of the silver bromide localized phase can be determined by X-ray diffractometry (for example,
"Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis" Maruzen,
It is described in. ) Etc. can be used for analysis. And these localized phases can be inside the grain, on the edges of the grain surface, on the corners or on the faces,
As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, and more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver chlorobromide emulsion or silver chloride emulsion used in the present invention is a Chemieet Phisique Photog by P. Glafkides.
raphique (Paul Montel, 1967), GF Du
By ffin Photographic Emulsion Chemistry (Focal Pr
Published by ess, 1966), Ma by VL Zelikman et al.
king and Coating Photographic Emulsion (FocalPres
s company publication, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the periodic table, and lead ions and thallium ions. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
It is usually chemically sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272, page 18, lower right column to second column.
Those described in the upper right column on page 2 are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Further EP 0447647
5-Arylamino-1,2,3,4-
A thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.
In the present invention, the compound represented by formula (I) is appropriately selected and used for spectral sensitization in a predetermined visible region and infrared region.

In the light-sensitive material of the present invention, in combination with the sensitizing dye represented by the general formula (I) of the present invention, or in a multilayer light-sensitive material other than the layer containing the emulsion spectrally sensitized with the dye of the present invention. Blue, green of the photosensitive emulsion contained in the photosensitive layer,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include Heterocyclic Compounds-Cyanin by FM Hamer.
e dyes and related compounds (John Wiley & Sons [N
ew York, London] 1964). Specific examples of the compound and the spectral sensitization method are described in JP-A-62-215272, No. 2
Those described on page 2, upper right column to page 38 are preferably used. Further, as a dye which can be used as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable and has strong adsorption. It is very preferable from the viewpoint of temperature dependence of exposure.

In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, EP-0,420,011
No. 4, line 21 to page 6, line 54, EP-0, 420, 012
No. 4, page 12, line 10 to page 33, EP-0,443,46
The sensitizing dyes described in US Pat. No. 6, US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes, including the sensitizing dyes of the general formula (I) of the present invention, into a silver halide emulsion, they may be dispersed directly in the emulsion or water. , Methanol, ethanol, propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol and the like, or may be dissolved in a single solvent or a mixed solvent and added to the emulsion. In addition, Japanese Patent Publication No. 44-23389,
As described in JP-B-44-27555 and JP-B-57-22089, an acid or a base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135 and US Pat.
As described in No. 06,025, an aqueous solution or colloidal dispersion in which a surfactant coexists may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. As described in JP-A-53-102733 and JP-A-58-105141, they may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion.

The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but U.S. Pat. No. 3,628,969,
And that the spectral sensitization is performed simultaneously with the chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 4,225,666 and JP-A-58-113928. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, and the spectral sensitization can be started by adding before the completion of the silver halide grain precipitation. Furthermore, US Pat. No. 4,2
It is also possible to add the spectral sensitizing dyes separately, as taught in US Pat. No. 25,666, ie to add some prior to chemical sensitization and the rest after chemical sensitization. , US Pat. No. 4,183,756, at any time during the formation of the silver halide grains. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 * 10 < ^-6 > mol to 5.0 * 10.
^-3 mol range. In the present invention, particularly when using a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region,
The compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column are preferably used in combination. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (IV) in the same patent in combination. These compounds are contained in an amount of 0.5 × 10 ^-5 mol to 5 mol per mol of silver halide.
0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.
An amount of 0 × 10 ⁻³ mol is used, and 0.1 to 10000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous amount used in the range of 0 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus that is compact, inexpensive, has a long life, and has high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG obtained by combining a semiconductor laser and a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, at least two layers are 670 nm
As described above, the necessity of having the maximum spectral sensitivity is reduced.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Also, upon exposure, US Pat. No. 4,880,7
It is preferable to use the band stop filter described in No. 26. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to carry out a bleach-fixing process after the color development for the purpose of rapid processing. Especially when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fixing solution is about 6.
It is preferably 5 or less, more preferably about 6 or less.

The silver halide emulsion and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and the processing method applied to process the light-sensitive material. As the processing additives, those described in the following patent publications, particularly European Patent No. 0,355,660A2 and JP-A-2-139544 are preferably used.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

High boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are water-immiscible compounds having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, and are good couplers. Any solvent can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high boiling point organic solvents are described in JP-A No. 62-215272, page 137, lower right column to page 144, upper right column. Further, the cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high-boiling organic solvent, or is water-insoluble and organic. It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, US Pat. No. 4,857,449, column 7,
Column 15 and the homopolymers or copolymers described on pages 12 to 30 of International Publication WO88 / 00723 are used, and more preferably a methacrylate-based or acrylamide-based polymer, particularly an acrylamide-based polymer is used. It is preferable in terms of image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, the compound in the aforementioned patent specification which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing It is possible to use the compounds in the above-mentioned patent specification, which are chemically bonded to the oxidized product of the residual aromatic amine color developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, For example, it is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the coupler with the residual color developing agent in the film or the oxidant thereof during storage after processing.

Further, as a cyan coupler, JP-A-2-
No. 33144, a diphenylimidazole type cyan coupler, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0,333,185A2, and a cyclic active methylene type cyanine described in JP-A-64-32260. Coupler, European Patent EP 0,45
6,226A1 specification, pyrrolopyrazole-type cyan coupler, European Patent EP 0,484,909, pyrroloimidazole-type cyan coupler, European Patent E
P0,488,248 and EP0,491,1
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

As the yellow coupler, in addition to the compounds described in the above table, European Patent EP 0,447,9
69A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, and a malondianilide type yellow coupler having a cyclic structure described in EP 0,482,552A1.
The acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler as described in the known documents in the above table is used, and among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6 position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A. As the method for processing the color light-sensitive material of the present invention, in addition to the methods described in the above table, JP-A-2
-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20 The treatment method is preferred.

[0054]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 Sodium chloride 6.6 in a 3% aqueous solution of lime-processed gelatin
g, and 3.2 ml of N, N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. After adjusting the pH of this solution to 3.5, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.196 mol of sodium chloride and 0.004 mol of potassium bromide are stirred vigorously. Added and mixed at 0 ° C. continue,
Aqueous solution containing 0.8 mol of silver nitrate and sodium chloride 0.78
An aqueous solution containing 4 mol and 0.016 mol of potassium bromide was added and mixed at 72 ° C. with vigorous stirring. From the time when 7/8 of the addition amount of the reaction liquid added for the second time was added to the end of the addition, 2 × 10 ⁻⁸ mol of potassium hexachloroiridium (IV) and hexacyanoiron (II) were added. 6 × 10 ⁻⁶ of potassium acid was introduced into the reaction vessel. After maintaining at 72 ° C. for 5 minutes, desalting and water washing were performed, and 90.0 g of lime-processed gelatin was added. The pH of the obtained emulsion was adjusted to 6.5, the spectral sensitizing dye C-4 was added at 58 ° C., sodium thiosulfate and chloroauric acid were further added to perform spectral sensitization, sulfur sensitization and gold sensitization. gave. At the end of chemical sensitization, 80 mg of 1- (3-methylureidophenyl) -5-mercaptotetrazole was added for the purpose of stabilization and prevention of fog. The thus obtained silver chlorobromide emulsion (cubic having an average grain size of 0.79 μm and a variation coefficient of grain size distribution of 8%, silver bromide 2 mol%) was designated as emulsion B1.

Then, grain formation was carried out in the same manner except that sodium bromide contained in the alkali halide solution to be reacted with emulsion B1 was replaced with equimolar sodium chloride. Further, an emulsion was prepared in the same manner as Emulsion B1 except that the amounts of the sulfur sensitizer and the gold sensitizer were adjusted so that the chemical sensitization was optimized after the addition of 0.05 μm silver bromide fine grain emulsion. B2 (average particle size 0.78 μm,
Cubic with 7% variation coefficient of grain size distribution, silver bromide 1.5
Mol%). Electron micrographs of emulsion B2 containing fine silver bromide particles are compared with those of emulsion B1 containing no fine silver bromide particles and emulsions sampled immediately before the addition of fine silver bromide particles when preparing emulsion B2. The corners of the cube had a more pointed shape. In addition, the X-ray diffraction of Emulsion B2 showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol% to 60 mol%. From the above, it can be said that Emulsion B2 is obtained by epitaxially growing a localized phase having a silver bromide content of 10 mol% to 60 mol% at the corners of cubic silver chloride grains. Next, Emulsion B3 and Emulsion B4 were prepared in the same manner except that I-63 was used in an equimolar amount instead of the spectral sensitizing dye C-4 used in Emulsion B1 and Emulsion B2.

Samples were prepared using the emulsions B1 to B4 by the following method. A cellulose triacetate film support was used as the support. The support side first layer coating solution was prepared by adding an aqueous gelatin solution to Emulsion B1 and heating and dissolving. The second coating liquid was prepared by adding an acrylic modified copolymer of polyvinyl alcohol (modification degree: 17%) and liquid paraffin to an aqueous gelatin solution and emulsifying and dispersing the mixture in advance, further adding an aqueous gelatin solution and heating and dissolving. The coating amount of the first layer was 1.4 g / m ² , the amount of gelatin was 3.2 g / m ² , and the amount of gelatin in the second layer was 1.0 g / m 2.
^2, acrylic modified copolymer is 0.04 g / m ² of polyvinyl A recall, liquid paraffin 0.02 g / m ²
It was set so that As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was mixed with the coating solution immediately before coating and used. The obtained coated sample was designated as sample (101). The calcium content of Sample 101 was 18 mg / m ² .

The gelatin used in the first layer of the sample (101) was replaced by a calcium-reduced one, and the calcium content was 9 mg / m ² (10).
2) and 2 mg / m ² of sample (103) was prepared.
Emulsion B1 used in Samples (101) to (103) was B2,
Samples (104) to (112) were prepared in the same manner except that B3 or B4 was used instead. The prepared sample was stored at room temperature and normal humidity for 1 week, and the photographic characteristics were examined by the following methods. For each sample, a photometer (FWH type manufactured by Fuji Photo Film Co., color temperature of light source 3
200 C) and 250 CMS for 1/10 second for sensitometric exposure, and then 2 with a developing solution having the following composition.
It was developed at 0 ° C. for 5 minutes, stopped, fixed and washed with water.

Composition of Developer Metol 2.7 g L-Ascorbic Acid 10.0 g Sodium Chloride 1.0 g Nabox 35.0 g Water was added to 1000 ml pH (20 ° C.) 9.6 The resulting processed sample silver The characteristic curve was obtained by measuring the image density. From the obtained characteristic curve, the exposure amount that gives a density 0.5 higher than the fog density was read, and the reciprocal thereof was taken as the sensitivity (S). Samples (101) to (11
Regarding 2), it was expressed as a relative value with the sensitivity of the sample (101) being 100. In order to examine the change in photographic characteristics due to the temperature during exposure, the same exposure as above was performed under the conditions of 40 ° C. 60% RH and 10 ° C. 60% RH. The same treatment as described above was performed below to obtain sensitivity. Sensitivity when exposed at 40 ° C (S ₄₀
^. Sensitivity when exposed at 10 ° C. and _C) (S _{^10. C)} of the ratio of the logarithm ^{_{(ΔS = log (S 40.}} C / S 10. C)) takes a photo identification by temperature when exposed to light It was set as the value showing the stability of. The closer ΔS is to 0, the more the stability is improved. Further, in order to examine the photographic characteristics after long-term storage, the photographic characteristics after the unexposed sample was aged for 1 month under the condition of 30 ° C. and 70% RH (corresponding to the forced deterioration test) were similarly evaluated. Table 6 shows the presence / absence of a silver bromide localized phase in the emulsion contained in each sample, the sensitizing dye species used and the calcium content, and summarizes the evaluation results of photographic characteristics.

[0059]

[Table 6]

Samples (101) to (106) and (107)
From the comparison of (112) to (112), it is understood that the presence of the silver bromide localized phase in the emulsion contained in the sample reduces the sensitivity fluctuation before and after the long-term storage of the sample. However, the sample (10
From the comparison of (1) to (103) and (107) to (112), it can be seen that the sample having the sensitizing dye C-4 of the present invention was stored after long-term storage regardless of the presence or absence of the silver bromide localized phase in the emulsion. It can be seen that the sensitivity variation due to the temperature during exposure becomes large. The sensitivity variation due to temperature during exposure after long-term storage is improved by the samples containing the sensitizing dye I-63 of the present invention and having a calcium content of 10 mg / m ² or less (105, 106, 111, 112).

Example 2 The spectral sensitizing dyes C-4 to I were added to the blue photosensitive emulsion B2.
A blue-sensitive silver chlorobromide emulsion B5 was obtained in the same manner except that the molar ratio was changed to -65 and the amounts of the sulfur sensitizer and the gold sensitizer were adjusted to optimize the chemical sensitization. To the emulsion B2, the grain size was changed by changing the temperature at the time of grain formation, and the spectral sensitizing dye C-1 was added, and the amounts of the fine bromide fine particles, sulfur sensitizer and gold sensitizer added were chemically sensitized. Green light-sensitive silver chlorobromide emulsion G in the same manner except that the feeling is optimized.
Got 1. Sensitizing dyes C-1 to C- for emulsion G1
2, I-21 and 1-43 are replaced by equimolar amounts, and the amount of the sulfur sensitizer and the amount of the gold sensitizer are adjusted to optimize the chemical sensitization, and the green-sensitive silver chlorobromide emulsion G2, G3 and G4 were obtained (emulsions G1 to G4 had an average grain size of 0.4
5 μ, coefficient of variation of particle size distribution 8%, cubic, 1.8 mol% of silver bromide localized on the surface of the silver chloride substrate). Emulsion B2
On the other hand, the temperature at the time of grain growth is changed, the sensitizing dye C-3 and the following compound S are added, and chemical sensitization is optimal for the amounts of silver bromide fine particles, sulfur sensitizer and gold sensitizer to be added. A red-sensitive silver chlorobromide emulsion R1 was obtained in the same manner except that the above adjustments were made. Sensitizing dyes from C-3 to I-61 for Emulsion R1
And I-57 were replaced by equimolar amounts, and red-sensitive silver chlorobromide emulsions R2 and R3 were obtained in the same manner except that the amounts of the sulfur sensitizer and the gold sensitizer were adjusted to optimize the chemical sensitization. (Emulsions R1 to R3 had an average grain size of 0.50 μm, a variation coefficient of grain size distribution of 8%, and cubic and 1.7 mol% of silver bromide were locally contained on the surface of the silver chloride substrate). However, in the preparation of these emulsions, the amounts of potassium hexachloroiridium (IV) and potassium hexacyanoferrate (II) added at the time of grain formation were changed in inverse proportion to the grain volume of each silver halide grain. The comparative spectral sensitizing dyes used in the preparation of these emulsions, the compound S and the addition amounts thereof are shown below.

[0062]

[Chemical 11]

[0063]

[Chemical 12]

Using these silver halide emulsions, a multilayer color photographic paper was prepared by the following method. The support was a polyethylene double-sided laminated paper support prepared by the method shown in Example 1 of JP-A-3-156439, and 14% by weight of dioxide was added to the polyethylene on which the silver halide emulsion layer was coated. Contains titanium. After the corona discharge treatment was applied to the surface of the paper support, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and the photographic constituent layers shown below were applied to form a multilayer color photographic paper, Sample (201) to (201). 212) was prepared. The coating liquid for each layer was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
25 g of solvent (Solv-1), solvent (Solv-2) 2 of 7.5 g and color image stabilizer (Cpd-3) 16.0 g
It was dissolved in 5 g and 180 cc of ethyl acetate, and this solution was added with a 10% aqueous solution of sodium dodecylbenzenesulfonate 6%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 0 cc and 10 g of citric acid. On the other hand, the silver chlorobromide emulsion prepared by the above-mentioned method and this emulsified dispersion A were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-13 and Cpd are added to each layer.
-14, Cpd-15 and Cpd-16 the entire amount respectively ^{15.0mg / m 2, 60.0mg / m} 2, 5.0
It was added as a mg / m ² and 10.0 mg / m ^2. Further, 1- (5-methylureidophenyl) -5-mercaptoterazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer at 6 × 10 ⁻⁵ per mol of silver halide. Mole, 7.8 × 10 ^-4
Mol and 2.2 x 10 ^-4 mol. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layers.

[0067]

[Chemical 13]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion B2 0.25 Gelatin 1.60 Yellow coupler (ExY) 0.61 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv -1) 0.22 Solvent (Solv-2) 0.22

Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.11 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.19 Solvent (Solv-7) 0.09 Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion G1 0.11 Gelatin 1.19 Magenta Coupler (ExM) 0.12 Ultraviolet Absorber (UV- 1) 0.12 color image stabilizer (Cpd-2) 0.01 color image stabilizer (Cpd-5) 0.01 color image stabilizer (Cpd-6) 0.01 color image stabilizer (Cpd-8) 0.01 Solvent (Solv-4) 0.30 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.79 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.14 Solvent (Solv-7) 0.06

Fifth layer (red sensitive emulsion layer) Silver chlorobromide emulsion R1 0.19 Gelatin 0.95 Cyan coupler (ExC) 0.28 Ultraviolet absorber (UV-3) 0.19 Color image stabilizer (Cpd-1) 0.24 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd -10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.21

Sixth Layer (UV Absorbing Layer) Gelatin 0.60 UV Absorber (UV-2) 0.39 Solvent (Solv-8) 0.05 Seventh Layer (Protective Layer) Gelatin 1.01 Acrylic of Polyvinyl Alcohol Modified copolymer (Modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

[0073]

Embedded image

[0074]

[Chemical 15]

[0075]

Embedded image

[0076]

[Chemical 17]

[0077]

[Chemical 18]

[0078]

[Chemical 19]

[0079]

Embedded image

[0080]

[Chemical 21]

The total content of calcium contained in the photographic constituent layers of these samples was 18 mg. Sample (2
The sample used in each emulsion layer of (01) was replaced with one whose calcium was reduced by ion exchange to prepare a sample (202) having a calcium content of 9 mg and a sample (203) having a calcium content of 2 mg. Sample (201)
To (203), the emulsion B2 for the blue-sensitive layer is changed to B4 and B5 and / or the emulsion G1 for the green-sensitive layer.
To G2 to G4 and / or by changing the emulsion R1 for the red photosensitive layer to R2 and R3.
~ (212) were created. Obtained sample (201)-
For (212), the same evaluation as in Example 1 was carried out in order to examine the change in photographic characteristics due to temperature during exposure before and after long-term storage. However, the filter used during exposure was changed to a three-color separation filter of blue, green and red, and the treatment process and treatment liquid composition were changed to the following.

Treatment Process Temperature Treatment Time Replenishment Amount ^* Tank Capacity Color Development 38 ° C. 45 sec 90 ml 1 liter Bleach-fix 30-36 ° C. 45 sec 161 ml 2 liter Rinse 1 30-35 ° C. 30 sec −2 liter Rinse 2 30-35 ° C. 30 seconds - 2 liters rinse 3 30 to 35 ° C. 30 seconds 200 ml 2 liters drying 70 to 80 ° C. 60 seconds * photosensitive material 1 m ² per replenishment rate color developer tank solution replenisher water 800 ml 800 ml ethylenediamine -N, N, N, N-tetramethylenephosphonic acid 3.0 g 6.0 g potassium bromide 0.015 g-triethanolamine 10.0 g 10.0 g sodium chloride 4.2 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 11.0 g N, N-bis (carboxymethyl) hydrazine 4.4 g 10.4 g N, N-di (sulfoethyl) hydroxyamine.1Na 4.0 g 8.0 g Fluorescent brightener (WHITEX 4B, Sumitomo Chemical) 2.0 g 4.0 g Water was added 1000 ml 1000 ml pH 10.20 10.85

Bleach-fixing solution (same composition as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Ice Acetic acid 9 g Water was added to 1000 ml pH 5.40 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively)

A characteristic curve was obtained by measuring the yellow, magenta and cyan color densities of the treated sample, and the exposure amount giving a density 1.0 higher than the fog was read from the obtained characteristic curve and the reciprocal thereof was used to determine the sensitivity. Photographic properties were evaluated in the same manner as in Example 1 except that the above was used. Table 7 shows the evaluation results of the emulsion used in each emulsion layer, the sensitizing dye contained therein, the calcium content of the sample, and the photographic characteristics.

[0085]

[Table 7]

As is apparent from Table 7, the present invention is effective also in the multilayer color light-sensitive material. That is, in Samples (201) to (209), it is possible to suppress the sensitivity variation due to the temperature at the time of exposure after long-term storage that the spectral sensitizing dye within the scope of the present invention is contained and the calcium content of the sample is It is clear that the amount is 10 mg / m ² or less. In addition, samples (209) to (21
From 2), the spectral sensitizing dyes I-63, I within the scope of the present invention
It is apparent that the samples using other spectral sensitizing dyes I-65, I-43, and I-57 within the scope of the present invention instead of -21 and I-61 also have similar effects.

Example 3 The photosensitive material produced in Example 2 was evaluated in the same manner as in Example 2 except that the following exposure was carried out. The results obtained were similar to those of Example 2. (Exposure) YAG solid-state laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source is KNbO ₃ SHG
A YVO ₄ fixed laser (oscillation wavelength: 106 nm) with a wavelength of 473 nm obtained by wavelength conversion by a crystal and a semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm) as an excitation light source
4 nm) was wavelength-converted by a KTP SHG crystal and extracted 532 nm, AlGaInP (oscillation wavelength, about 6 nm).
70 nm: Toshiba type No. TOLD9211) was used. The laser light is an apparatus capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this apparatus, the amount of light was changed to obtain the relationship D-1 ogE between the density (D) of the photosensitive material and the amount of light (E), and gradation exposure was performed based on this relationship. At this time, of the laser lights of three wavelengths, the light amount of 473 nm and 532 nm was modulated with an external modulator to control the exposure amount. Also, 670 nm
Laser light was controlled by changing both the light emission amount and the light emission time of the semiconductor laser. This scanning exposure is 400
The average exposure time per pixel at this time is about 5
× 10 ⁻⁸ seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature.

Example 4 The light-sensitive material prepared in Example 2 was exposed to light as in Example 2 except that a color developing solution and a processing step were used in the following processing steps using a paper processor. Example 2
Evaluation was performed by performing the same process as in. The obtained results are the same as in Example 2, and in the constitution of the present invention, it was possible to suppress the sensitivity fluctuation due to the temperature at the time of exposure after long-term storage.

Processing Step Temperature Time Tank Capacity Color Development 40 ° C. 15 seconds 2 liters Bleaching Fixing 40 ° C. 15 seconds 2 liters Rinse 40 ° C. 3 seconds 1 liter Rinse 40 ° C. 3 seconds 1 liter Rinse 40 ° C. 3 seconds 1 liter rinse 40 ℃ 3 seconds 1 liter Rinse 40 ℃ 6 seconds 1 liter Dry 70-80 ℃ 15 seconds

The rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not permeate the reverse osmosis membrane was returned to the rinse for use. In addition, in order to shorten the crossover time between the rinses, a blade was installed between the tanks and the blades were passed between them. The composition of each treatment liquid is as follows.

Color developer tank liquid replenisher water 700 ml 700 ml ethylenediaminetetraacetic acid 1.5 g 3.75 g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.25 g 0.7 g triethanolamine 5. 8g 14.5g potassium chloride 10.0g-potassium bromide 0.03g-potassium carbonate 18.0g 24.0g optical brightener (UVX) 1.5g 4.5g sodium sulfite 0.1g 0.1g disodium-N , N-bis (sulfonate ethyl) hydroxylamine 14.8 g 29.6 g 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline.2-p-toluenesulfonic acid 9.8 g 29. 3 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.05 11. 60

Bleach-fixing solution (replenishing solution was prepared by separating components into two solutions) [First replenishing solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite monohydrate 190 g Ethylenediaminetetraacetic acid 7.5 g Bromide Ammonium 30g Ammonium thiosulfate (700g / l) 340ml Acetic acid (50%) 250ml Water is added 1000ml pH (25 ° C) 4.8 [Second replenisher] Water 140ml Ethylenediaminetetraacetic acid (11.0g) Ethylenediaminetetraacetic acid (III) Ammonium 715 g Tetraacetic acid (50%) 100 ml Water was added to 1000 ml pH (25 ° C) 2.0

Tank solution of bleach-fixing solution First replenishing solution 300 ml Second replenishing solution 200 ml Water is added 1000 ml pH (25 ° C.) 5.0 Replenishing amount of bleach-fixing solution (35 m per 1 m ^{2 in the following} amount)
l) First replenisher 21 ml Second replenisher 14 ml Rinse (same as tank and replenisher) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

[0094]

According to the present invention, there can be obtained a silver halide color photographic light-sensitive material which is excellent in rapid processability and has improved performance variation due to temperature during exposure even after the photographic material is stored for a long period of time.

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Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support, said emulsion layer being spectrally sensitized represented by the following general formula (I). A silver halide photograph comprising a silver halide emulsion sensitized by a dye, the silver chloride content of which is 95 mol% or more, and the total content of calcium in the photographic constituent layers is 10 mg / m ² or less. Photosensitive material. Embedded image In the formula, X ₁ and X ₂ each represent a nonmetallic atom group necessary for completing a 5-membered or 6-membered heterocycle,
₁ is substituted with Z ₁ , and X ₁ and X ₂ may further have a substituent, n represents a positive integer of 1 to 4, and p and q independently represent 0 or 1. Represent, L ₁
And L ₂ each represent a methine group which may have a substituent, and R ₁ and R ₂ each represent an aromatic group which may have a substituent or an aliphatic which may have a substituent. Represents a group, Z ₁ is Ar- (L which is more hydrophilic than a phenyl group.
₃ ) represents a group represented by _m −, Ar represents an aromatic group which may have a substituent, L ₃ represents a linking group, m represents 0 or 1, and a counter ion is required. In which W ₁ represents a counterion. 2. A silver halide color having a photographic constituent layer comprising on a support at least three silver halide emulsion layers having different color sensitivities each containing one of a coupler which develops yellow, magenta and cyan. A photographic light-sensitive material, wherein at least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more sensitized with a spectral sensitizing dye represented by the general formula (I).
And the total content of calcium in the photographic constituent layers is 10 mg
/ M ² or less silver halide color photographic light-sensitive material,
A color image forming method comprising exposing by a scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then performing color development processing. 3. A silver halide color having a photographic constituent layer comprising at least three kinds of silver halide emulsion layers having different color sensitivities each containing a coupler capable of coloring yellow, magenta or cyan on a support. A photographic light-sensitive material, wherein at least one of the emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more sensitized with a spectral sensitizing dye represented by the general formula (I).
And the total content of calcium in the photographic constituent layers is 10 mg
/ M ² or less silver halide color photographic light-sensitive material,
A color image forming method, wherein a color development time is 25 seconds or less, and a total processing time including color development processing to drying is 120 seconds or less.