JP2005215412A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color image forming method and a silver halide color photographic sensitive material, in which the changes in the developed color density and in the gradation are small, even in a rapid transport system in a sheet shape and rapid transport processing system, and by which color prints in which the image quality will not change with time in raw storage can stably be produced. <P>SOLUTION: In the color image forming method, the silver halide color photographic sensitive material contains at least one each of dye forming couplers represented by Formula (M-I) and Formula (IA), the sensitive material is conveyed at a speed of 40.0-100 mm/s in a processing procedure, and a color developing step, a bleach-fixing step and a drying step are terminated within 18 s, 18 s and 26 s, respectively. The silver halide color photographic sensitive material is used for high-speed sheet transport. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material and a silver halide color photographic light-sensitive material, and more specifically, development unevenness in a color image forming method for obtaining a color image by conveying a developing process at a high speed sheet. The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material and a silver halide color photographic light-sensitive material capable of providing an improved high-quality image.

  In the photo processing service industry, color negatives, reversal light-sensitive materials, and in recent years, color print systems for obtaining color prints from digital cameras and the like have become widespread not only in laboratories specializing in print development processing, but also in photo shops. . The exposure method of this color print system is a digital camera that can obtain color prints from a digital camera from the so-called direct (analog) exposure method, in which the projection light of a film such as a color negative is incident on color paper and the photosensitive material is surface exposed. The mainstream is shifting to a printing apparatus using exposure. Even for images recorded on a film, a digital exposure method has been widely used in which information is photoelectrically read and the information is converted into digital signals and image processing is performed, and then scanning exposure is performed with recording light modulated in accordance with the image data to record an image. It is being done.

  In these color printing systems, the photosensitive material is loaded in a photosensitive material-containing light-shielding magazine while being wound in a roll shape, and is pulled out of the magazine and conveyed during exposure and development. Conventionally, the photosensitive material is exposed in a roll form without being cut in the middle and is subjected to development processing, and after development processing is cut into a desired length to obtain a print for each sheet, so-called roll conveyance for color paper However, it is necessary to form frame information for clearly indicating the boundary of each print, and there is a problem that the portion is wasted.

For this reason, recently, a color printing system has been put to practical use that employs a sheet conveying method in which a photosensitive material is preliminarily cut into a size corresponding to one printed sheet to form a sheet and then subjected to exposure and development processing. In this transport method, the photosensitive material cut into a sheet is transported and developed by a transport method using a pair of transport rollers and a belt conveyor. Here, the sheet-like photosensitive material is subjected to development processing after being exposed, but in the development processing step, the photosensitive material is conveyed as a sheet by a pair of conveyance rollers.
For this reason, this type of color print system is characterized by a higher number of print outputs per hour than conventional methods, but a system with higher productivity is desired, and in addition, it is relatively compact. It is desired that this can be realized with a simple device.

  In addition, the photosensitive material used in this system, that is, the color print material, is exposed at high illuminance corresponding to a digital exposure method in which a laser beam modulated by image data is scanned to record an image. It is necessary not to be accompanied by a decrease in sensitivity due to failure. In addition, color print materials are less likely to have uneven development that is likely to occur during rapid development processing under high-speed conveyance, and scratches due to contact with guides or blades installed in the conveyance path in the processing liquid. A stable finish is desired in that it is difficult to occur.

  On the other hand, in the production of color print materials, in order to obtain suitable film properties, a period of several days from application to shipment is stored in the factory. Mainly used in photo shops. Storage after shipment from the factory is preferably refrigerated, but the actual situation is often left in a place that is not refrigerated, and depending on the region, it is often exposed to a high temperature or high humidity environment. For example, Patent Document 1 discloses a method for imparting raw storage stability and rapid dura- bility after production of a color print material.

  As the color printing system is diversifying, including a quick type, a sheet-type high-speed conveyance type color printing system with improved productivity is required to have the same quality as before. However, at present, the quality required in terms of variations in color density, gradation, flaw occurrence frequency, etc. is not always fully met. In particular, it has been found that, when the storage history (temperature and humidity) after manufacture of the color print material is not appropriate, the variation in color development and the frequency of occurrence of scratches increase.

JP 2000-98527 A

  The present invention has been made from the above background, and is a sheet-like high-speed conveyance type silver halide color which can provide stable quality in exposure and development processing of photosensitive materials, particularly color print materials, and has high color print productivity. It is an object to provide a color image forming method of a photographic light-sensitive material and a silver halide color photographic light-sensitive material. In particular, the present invention provides a color image forming method in which color development is good regardless of the storage period from the production of the color print material to exposure, and the frequency of failures such as density unevenness and scratches is reduced, and a stable finish quality is obtained. And a silver halide color photographic light-sensitive material.

The inventors of the present invention have made extensive studies and found that the above-mentioned problems can be achieved by the following configuration, and have achieved the above-mentioned object. That is, the present invention has been achieved by the following means.
(1) Blue-sensitive silver halide emulsion layer containing yellow dye-forming coupler, green-sensitive silver halide emulsion layer containing magenta dye-forming coupler, red-sensitive silver halide emulsion layer containing cyan dye-forming coupler, and non-photosensitive A silver halide color photographic light-sensitive material having a photographic composition layer composed of at least one each of a hydrophilic hydrophilic colloid layer, sheet-shaped cutting and image-wise exposure, and then a color color development step while being conveyed by a pair of conveying rollers, A color image forming method formed through a development process including a bleach-fixing step, a rinsing step, and a drying step, wherein the silver halide color photographic light-sensitive material is represented by the following general formula (M-I) And at least one dye-forming coupler represented by the following general formula (IA), and the development processing step is 40.0 A color material characterized in that the photosensitive material is conveyed at a speed of not less than 100 m / sec and the color color development process is completed within 18 seconds, the bleach-fixing process is completed within 18 seconds, and the drying process is completed within 26 seconds. Image forming method.

(In the general formula (MI), R ₁ , R ₂ , and R ₃ each independently represents a hydrogen atom or a substituent. Za and Zb are either a hydrogen atom or a carbon atom having a substituent, The other represents a nitrogen atom, and the substituent of Za or Zb may further have a substituent, and X is a hydrogen atom or a group capable of leaving in the reaction with an oxidized form of an aromatic primary amine color developing agent. Represents.)

(In the general formula (IA), R ′ and R ″ each independently represent a substituent, and Z is removable in a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group.)
(2) The tank used in the rinsing step is a tank having a multi-chamber structure partitioned by a blade-like member for allowing the photosensitive material cut into a sheet shape to pass in the horizontal direction in the liquid. The color image forming method according to (1).
(3) The color image forming method as described in (1) or (2), wherein the conveyance speed in the development processing is a speed of 45.0 mm / second or more and 95 mm / second or less.
(4) Any of (1) to (3), wherein the dye-forming coupler represented by the general formula (M-I) is a dye-forming coupler represented by the following general formula (M-III) A color image forming method according to claim 1.

(In the general formula (M-III), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. X represents a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group capable of leaving in the reaction.)
(5) The hydrophilic colloid layer of the silver halide color photographic light-sensitive material is made of gelatin substantially hardened with a hardener represented by the following general formula (I): (4) The color image forming method according to any one of (4).

(In the general formula (I), X ¹ and X ² each independently -CH = CH ₂ or, represents one of -CH ₂ CH ₂ Y, X ¹ and X ² are different even in the same Wherein Y represents a group that can be substituted by a nucleophilic group or can be eliminated in the form of HY by a base, L is a divalent linking group and may be substituted.)
(6) A color color development process of 18 seconds or less, a bleach-fixing process of 18 seconds or less, and a rinse while being conveyed in a sheet form after imagewise exposure by a conveyance roller at a conveyance speed of 40.0 mm / second to 100 mm / second. A silver halide color photographic light-sensitive material for high-speed sheet conveyance that forms a color image through a development process including a process and a drying process within 26 seconds, wherein the silver halide color photographic light-sensitive material is represented by the general formula (M- A silver halide color photographic light-sensitive material for high-speed sheet conveyance, comprising at least one dye-forming coupler represented by I) and a dye-forming coupler represented by the general formula (IA).
(7) The tank used in the rinsing step is a tank having a multi-chamber structure in which the chambers are partitioned by a blade-like member, and the tank passes through the tank in the horizontal direction in the liquid. The silver halide color photographic material for high-speed sheet conveyance as described.
(8) The silver halide color photographic material for high-speed sheet conveyance according to (6) or (7), wherein the conveyance speed is 45.0 mm / second or more and 95 mm / second or less.
(9) Any of (6) to (8), wherein the dye-forming coupler represented by the general formula (M-I) is a dye-forming coupler represented by the general formula (M-III) 2. A silver halide color photographic light-sensitive material for high-speed sheet conveyance according to item 1.
(10) The hydrophilic colloid layer of the silver halide color photographic light-sensitive material is made of gelatin substantially hardened with a hardener represented by the general formula (I) (6) to (9) The silver halide color photographic light-sensitive material for high-speed sheet conveyance according to any one of (9).
(11) The silver halide color photographic light-sensitive material does not substantially contain a chlorotriazine-based hardener and has a gelatin layer substantially hardened by the hardener represented by the general formula (I). (5) The color image forming method described in (5).
(12) The silver halide color photographic light-sensitive material does not substantially contain a chlorotriazine-based hardener and is made of gelatin substantially hardened by the hardener represented by the general formula (I). The silver halide color photographic light-sensitive material for high-speed sheet conveyance as described in (10), which is characterized in that

  The color image forming method and the silver halide color photographic light-sensitive material of the present invention provide good color development and reduced image quality due to gradation changes, scratches, etc., even in sheet-type transport systems, high-illuminance scanning exposure by laser, and rapid processing. Thus, a color print having excellent image quality can be stably produced even when the photosensitive material is stored in the raw storage time (after storage of the photosensitive material until exposure).

The present invention is described in detail below.
The image forming method and the color photographic light-sensitive material of the present invention include a silver halide color photographic light-sensitive material cut into a sheet shape, subjected to imagewise exposure, and then conveyed by a pair of conveyance rollers. An image is formed by performing a development process.
The exposure step may be before or after the cutting step, or may be cut while being exposed. Preferably, after the cutting step.

  The silver halide color photographic light-sensitive material is suitable for a scanning exposure method using a cathode ray tube (CRT) or a laser beam, in addition to being used in a printing system using a normal negative printer. In the latter case, imagewise exposure is performed on the basis of image information. As an exposure method, 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 optical crystal are used. A digital scanning exposure method using monochromatic high-density light such as a combined second harmonic light source (SHG) is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, 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 photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time per pixel in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻³ seconds or less, more preferably 1 × 10 6. ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds or less. The effect of the present invention is more likely to be exhibited under conditions where reciprocity failure occurs during high-illuminance exposure and silver development in the shadow portion is unlikely to occur, but the same effect can be obtained even in low-illuminance exposure.

Specifically, as a semiconductor laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength: about 940 nm) ) a waveguide-like inverted domain structure about 470nm blue laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having a semiconductor laser (oscillation wavelength: LiNbO ₃ having about 1060 nm) a waveguide-like inverted domain structure A green laser with a wavelength of about 530 nm, a red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), etc., are preferably used. .
In particular, imagewise exposure is preferably performed using coherent light of a blue laser having an oscillation wavelength of 430 to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.

The imagewise exposure may be performed a plurality of times on the same photosensitive layer (emulsion layer) of the silver halide photosensitive material, and in that case, it is preferably performed at least twice. Particularly preferably, the exposure time is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ seconds, and when the exposure time is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ seconds, it is preferable to perform exposure at least 8 times. The light source may be any of the gas laser, the solid laser (LD), the LED (inorganic or organic) described above, and the Xe light source with a narrow spot, but a solid laser or LED is particularly preferable. The light source needs to be spectrally divided into the color-sensitive wavelength of each dye-forming layer. For this purpose, an appropriate color filter (containing dye or vapor deposition) or the oscillation wavelength of LD or LED is selected and used. May be. Furthermore, you may use combining both. The spot diameter of the light source is not particularly limited, but is preferably from 5 to 250 μm, particularly preferably from 10 to 100 μm, in terms of the half value width of the light intensity. The spot shape may be circular, elliptical, or rectangular. The light amount distribution of one spot may be a Gaussian distribution. In particular, one light source may be used, but an array in which a plurality of light sources are arranged may be used.

The imagewise exposure is preferably performed by scanning exposure, and the light source may be scanned or the photosensitive material may be scanned. Both of them may be scanned.
Here, one exposure time is defined by the following equation.

  Exposure time = spot diameter / light source moving speed (or photosensitive material moving speed)

The spot diameter is the spot diameter in the direction in which the light source used for scanning exposure moves during exposure (in the case of a Gaussian beam, the width at which the intensity is 13.5% or more with respect to the peak intensity, unit: μm) Say. The moving speed of the light source refers to the speed (unit: μm / second) at which the light source used for scanning exposure moves per unit time.
In general, the spot diameter need not be the same as the pixel diameter, and may be larger or smaller. The number of exposures referred to in the present invention is the number of times of irradiation of light perceived by the same color-sensitive layer with respect to one point (pixel) on the photosensitive material. On the other hand, the number of times of exposure with an intensity of 1/5 or more. Therefore, exposure less than 1/5, stray light, and overlap between spots are not included in the number of times.

  In addition to the scanning exposure method using these light sources, the exposure method used in a printing system using a normal negative printer or the scanning exposure method using a cathode ray (CRT) can be used. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used.

  Further, when the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a cathode ray tube. Alternatively, a plurality of color image signals may be input to emit light from the tube surface. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

Next, the color development processing step will be described.
The color development processing applied to the light-sensitive material and image forming method of the present invention is a development processing step including at least a color color development step, a bleach-fixing step, a rinsing step, and a drying step, and is usually processed in this order. . In the present invention, the rinsing step is used in the sense of including a water washing step or stabilization step, and further includes a water washing substitute stabilization step and an image stabilization stabilization step (these are also simply referred to as stabilization steps).
In the color development processing step, auxiliary steps such as a rinsing step, an intermediate water washing step, and a neutralization step can be inserted between the respective steps. The bleach-fixing solution is for desilvering, and in the present invention, the desilvering step is performed by a one-step process using the bleach-fixing solution. In addition to a water washing alternative stabilizing bath instead of the water washing step, an image stabilizing bath for the purpose of image stabilization can be provided between the water washing or stabilizing bath step and the drying step.

  Here, in the present invention, the color development time (that is, the time during which the color color development process is performed) is 18 seconds or less, preferably 18 seconds or less and 6 seconds or more, and most preferably 18 seconds or less and 12 seconds or more. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is 18 seconds or less, preferably 18 seconds or less and 6 seconds or more, and most preferably 18 seconds or less and 12 seconds or more. The rinsing (washing or stabilizing) time (that is, the time for performing the rinsing step) is preferably 30 seconds or less (preferably 30 seconds or less and 6 seconds or more), more preferably 25 seconds or less (preferably 25 seconds or less and 6 seconds). More preferably, it is 25 seconds or less and 12 seconds or more. The drying step is within 26 seconds (preferably 26 seconds or less and 6 seconds or more), and more preferably 26 seconds or less and 8 seconds or more.

  The color development time refers to the time from when the light-sensitive material enters the color developing solution until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in a color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleached and fixed in the next processing step. The sum of both the time during which air is conveyed toward the liquid (so-called air time) and the color color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The rinsing (water washing or stabilization) time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the rinse liquid (water washing or stabilization liquid).

In the drying process, drying can be accelerated by absorbing moisture with a squeeze roller or cloth immediately after the rinsing process from the viewpoint of reducing the amount of moisture carried into the image film of the silver halide color photographic material. It is. Of course, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material and by the method of removing the exhaust air.
The processing solution temperature in the color development step, bleach-fixing step, and rinsing step is generally 30 to 40 ° C, but in the present invention, 38 to 60 ° C is preferable, and 40 to 50 ° C is more preferable. The temperature of the drying step is preferably 50 to 90 ° C, more preferably 60 to 85 ° C.

The amount of rinsing liquid in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the temperature of the rinsing liquid (water washing water), the number of rinsing liquids (water washing tank) (number of stages), and various other conditions. A wide range can be set. Among these, the relationship between the number of rinse liquid tanks (water washing tanks) and the amount of water in the multi-stage countercurrent system is the Journal of the Society of Motion Picture and Motion of Picture Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955).
In the present invention, the number of stages in the multistage countercurrent system is preferably from 3 to 15, and particularly preferably from 3 to 10.

  According to the multi-stage counter-current system, the amount of the rinse liquid can be greatly reduced, and the increase of the residence time of water in the tank causes problems such as bacteria breeding and the generated suspended matter adhering to the photosensitive material. As a solution, a rinsing solution containing an antibacterial and antifungal agent described later is preferable.

The components of the treatment composition used in the above-described treatment steps and the treatment liquid prepared from them will be described below.
Constituent components are described collectively without distinction between treatment compositions (treatment agents) and treatment liquids prepared from them, except in special cases. Constituent concentrations are generally determined in the treatment liquids prepared. The concentration of
The treatment composition is mixed with a solvent such as water at a ratio determined at the time of use to prepare a mother liquid (tank liquid) or a replenisher. In this specification, the tank liquid and the replenisher are distinguished. Unless there is a special meaning to do, both are expressed as a working solution.

The color color development processing composition and the color color developer contain a color developing agent.
Preferred examples of the color developing agent include known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4- Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-Amino-3-methyl-N- Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N- (Β-Methanesulfonamidoethylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N- (β-meth Ciethyl) aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 15) N- (4-Amino-3-methylphenyl) -3-hydroxypyrrolidine 16) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

Particularly preferred among the above-mentioned p-phenylenediamine derivatives are Exemplified Compounds 5), 6), 7), 8) and 12), among which Exemplified Compounds 5) and 8) are preferred. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.
The content of the aromatic primary amine developing agent in the processing agent is such that the concentration of the developing agent in the working solution is 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 mmol to 1 L of the developing solution. It is added to 40 mmol.

The color developer may contain a small amount of sulfite ions or may not substantially contain sulfite ions depending on the type of the light-sensitive material to be used. In the present invention, it is preferable that the color developer contains a small amount of sulfite ions.
Moreover, you may contain a small amount of hydroxylamine. Hydroxylamine (usually used in the form of hydrochloride or sulfate, but hereinafter abbreviated as salt) acts as a developer preservative in the same manner as sulfite ion, but at the same time, hydroxylamine itself has silver developing activity. For this reason, the photographic characteristics may be affected. Therefore, it is necessary to keep this addition amount small.

In addition to the hydroxylamine and sulfite ions, an organic preservative may be added to the color developer as a preservative. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being included in the processing solution of the photosensitive material. That is, it is an organic compound having a function to prevent air oxidation of a color developing agent. Among them, the above hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones. Saccharides, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic preservatives.
These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143020, Japanese Patent Publication No. 48-30496, and the like.

For the color developer, for example, a developer for color paper may be added with chlorine ions as necessary. Color developers (especially developers for color print materials) usually contain chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / L, but chlorine ions are usually developed. In many cases, it is unnecessary to add to the replenishment developer.

  In the present invention, the developer is preferably added so that the pH of the developer is 9.0 to 13.5 and the pH of the replenisher is 9.0 to 13.5. An alkali agent, a buffering agent and, if necessary, an acid agent can be included so that the pH value can be maintained.

  In order to maintain the pH when the treatment liquid is prepared, it is preferable to use various buffering agents. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane 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 9.0 or higher, and even if added to a color developer, they adversely affect photographic performance (fogging). It is particularly preferable to use these buffering agents.

Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
The amount of the buffer added to the composition is determined so that the developer and replenisher prepared from the processing agent are 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per liter.

To the color developer, various chelating agents that are other color developer components, for example, calcium or magnesium precipitation inhibitors, or color developer stability improvers can also be added. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexanediaminetetraacetic acid, 1 , 2-diaminopropanetetraacetic 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- And dihydroxybenzene-4,6-disulfonic acid. The
These chelating agents may be used in combination of two or more as required. The amount of these chelating agents may be an amount sufficient to sequester metal ions in the prepared color developer. For example, it is added so as to be about 0.1 to 10 g per liter.

  If necessary, an optional development accelerator can be added to the color developer according to the present invention. Examples of development accelerators 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 the thioether compounds represented in the specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat. No. 3,128,183, JP-B-41-11431, JP-A-42-23883, and U.S. Pat. , 532, 501 and the like, polyalkylene oxides and other 1-phenyl-3-pyrazolidones or imidazoles represented in the respective publications or specifications can be added as necessary. The added amount in the composition is determined so that the concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. .

An optional antifoggant can be added to the color developer according to the present invention, if necessary, in addition to the halogen ion. Examples of organic antifoggants 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, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as necessary. The addition amount in the composition is determined so that the concentration thereof is 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. .

In the present invention, a fluorescent brightener can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available niaminostilbene-based brighteners 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. Examples of commercially available compounds are described in, for example, “Dyeing Note”, 9th edition (Colored dyeing), pages 165 to 168. Among the compounds described therein, Blankophor BSU liq. And Hakkol BRK are preferred.
As the bleaching agent, other known bleaching agents can be used in addition to the iron (III) complex salt of aminopolycarboxylic acid. Examples of bleaching agents that can be used in combination include iron (III) complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, and hydrogen peroxide.

  A preferable iron (III) complex salt of aminopolycarboxylic acid is an iron (III) complex salt of aminopolycarboxylic acid exemplified below. That is, biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, betaalanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1 , 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid. These compounds may be any of sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy Acetic acid is preferable because its iron (III) complex salt has good photographic properties. These iron (III) complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid may be used to form an iron (III) complex salt in a solution. Further, the chelating agent is used in excess as compared with the formation of the iron (III) complex salt.

  The concentration of the bleaching agent in the bleaching agent part is 0.01 to 1.0 mol / L, preferably 0.03 to 0.80 mol / L, more preferably, in the processing solution prepared from the processing composition. Is determined to be 0.05 to 0.70 mol / L, more preferably 0.07 to 0.50 mol / L.

  The bleach part includes various known organic acids (eg acetic acid, lactic acid, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, citric acid, tartaric acid, glutaric acid, lactic acid, etc.), organic A base (for example, imidazole, dimethylimidazole, etc.) or a compound represented by the general formula (Aa) described in JP-A-9-211819 including 2-picolinic acid and kojic acid. It is preferable to contain the compound represented by general formula (Bb) as described in above. The amount of these compounds added is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, and more preferably 0.05 to 1.5 mol, per liter.

  The fixing agent part constituting the bleach-fixing solution processing composition in combination with the bleaching agent part is a known fixing chemical, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, etc. 1 or 2 selected from water-soluble silver halide solubilizers such as thioether compounds such as thiocyanate, ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas The above can be mixed and contained. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing chemical in the fixing agent part is preferably designed to be 0.1 to 3 mol per liter of the prepared solution when the bleach-fixing solution is prepared, and more preferably 0.2 to 2.0. Designed in the molar range.

  Fixing agent part contains sulfite ion releasing compounds such as sulfite, bisulfite and metabisulfite as preservatives, and arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid. It is preferable to do this. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / L (as the concentration of the prepared treatment solution) in terms of sulfite ions or sulfinate ions.

  The following describes the bleach-fix solution prepared by mixing the bleach part and the fixer part, and adding a little water if necessary, but it can be contained in either the bleach part or the fixer part. A good bleach-fixing solution component is also described in this section.

The pH range at the time of dissolution of the bleach-fixing solution processing composition is preferably 3-8, more preferably 4-8. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
In order to adjust the pH, potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, acidic or alkaline buffering agent, etc., which are alkaline are added to the fixing agent part side as necessary. be able to.

The replenishing amount of the developer and the bleach-fixing solution of the present invention is preferably 60 ml or less per 1 m ² of photosensitive material, more preferably 25 ml to 45 ml, most preferably 25 to 40 ml. The replenishment amount of the bleach-fixing solution is preferably divided into a bleaching agent part and a fixing agent part. In this case, the replenishment amount of the bleach-fixing solution indicates the total replenishment amount of the bleaching agent part and the fixing agent part. is there. The replenishing amount of the rinsing liquid (washing water and / or stabilizing liquid) is preferably 50 ml to 220 ml, more preferably 50 ml to 200 ml as a whole.

  After completion of fixing or bleach-fixing, a rinsing bath is used. The rinsing bath is also referred to as a water-washing alternative stabilization bath or an image stabilization stabilization bath (simply referred to as a stabilization bath). These baths have a low concentration and the effect of the processing agent is not great, but is necessary. If it exists, a processing agent can be manufactured. As the stabilizing bath treatment agent, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorinated fungicides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-267761 Benzotriazole, copper ion, and other publications described in the gazette, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association, “Microbial Decontamination, Sterilization, Antifungal Technology” (1982) The bactericides described in the “Industrial Antibacterial and Antifungal Encyclopedia” (1986) edited by the Industrial Technology Association of Japan and the Japanese Society for Antibacterial and Antifungal Society may also be used.

Next, a development processing apparatus that performs the development processing will be described.
The development processing method according to the present invention is particularly preferably carried out using an automatic developing machine. The automatic processor preferably used in the present invention will be described below.
In the present invention, the linear speed of conveyance of the automatic developing machine is 40 mm / second or more and 100 mm / second or less, and particularly preferably 45 mm / second to 95 mm / second.

  The color paper automatic processor transports the color paper to the final size and then develops it (sheet-type transport method), and develops it in a long roll and cuts it to the final size after processing (cine) Mold conveyance system). Since the cine type conveyance system wastes about 2 mm of photosensitive material between images, the sheet type conveyance system is used in the present invention.

In the present invention, the treatment liquid is a treatment tank and a replenishment liquid tank, and the area (opening area) where the liquid comes into contact with air is preferably as small as possible. For example, when the value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank is the opening ratio, the opening ratio is preferably 0.01 (cm ⁻¹ ) to 0.02 (cm ⁻¹ ). .

In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means floating on the liquid surface in the treatment tank and the replenishment tank.
Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon and the like are preferable.

  In the present invention, in order to perform processing quickly, the air time when the photosensitive material moves between the processing solutions, that is, the crossover time is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less, More preferably, it is 5 seconds or less.

As a method for eliminating the crossover time at all, it is particularly preferable to use a submerged conveyance structure using a blade described in JP-A-2002-55422. In this method, a crossover time can be reduced to zero by providing a blade between processing tanks to prevent liquid leakage and allowing the photosensitive material to pass therethrough.
It is particularly preferable to install a porous material pleated filter in the liquid circulation structure in which the liquid circulation direction described in JP-A-2002-339383 is flowed downward in the submerged conveyance structure by this blade and the circulation system.

It is preferable to perform so-called evaporation correction in which water corresponding to the evaporation amount of the processing liquid is supplied to each processing liquid according to the present invention. In particular, it is preferable in a color developer and a bleach-fix solution.
A specific method for replenishing such water is not particularly limited. However, a monitor water tank different from the bleach-fixing tank described in JP-A-1-254959 and 1-2254960 is installed. The amount of water evaporation in the monitor tank is calculated, the amount of water evaporation in the bleach-fixing tank is calculated from the amount of water evaporation, and the water level is replenished to the bleach-fixing tank in proportion to the amount of evaporation. An evaporation correction method using a sensor or an overflow sensor is preferable. The most preferred evaporation correction method is to predict and add water corresponding to the amount of evaporation, and is described in the Japanese Institute of Invention and Technology Publication No. 94-49925, page 1, right column, line 26 to page 3, left column, line 28. As described above, the amount of water calculated by a coefficient determined in advance based on the information on the operation time, stop time, and temperature control time of the automatic processor is added.

In addition, a device for reducing the evaporation amount is also necessary.
As means for reducing the evaporation amount, it is particularly preferable to “keep the humidity of the upper space of the treatment tank at 80% RH or more” described in JP-A-6-110171, and the evaporation described in FIGS. It is particularly preferred to have a prevention rack and roller automatic cleaning mechanism. Although the exhaust fan is mounted normal to prevent dew condensation at the temperature control, a preferable exhaust amount per minute 0.1 m ³ to 1 m ^3, particularly ^preferably at 0.2m ³ ~0.4m 3 is there.

The drying conditions of the photosensitive material also affect the evaporation of the processing solution. The drying method, it is preferable to circulate supplying dry air was allowed to warm air blown from the blower by the heater in the drying chamber, preferably every minute 4 to 20 m ³ as feed air volume, particularly 6～10M ³ Is preferred.
As long as the temperature detector mounting position of the drying air is within the circulation path of the drying air, it may be disposed either upstream or downstream of the photosensitive material conveyance path. Moreover, you may arrange | position before and behind a paper passage position on a dry wind circulation path. The temperature of the drying air sprayed on the paper can be adjusted by the water content of the photosensitive material to be processed, but 50 to 90 ° C. is optimal for the color photographic paper of the present invention. The drying time preferable in the present invention is preferably within 26 seconds, more preferably from 26 to 6 seconds, and particularly preferably from 26 to 8 seconds, since it is desirable from the viewpoint of system efficiency that the drying section is compactly designed and finished in an extremely short time. The term “drying time” as used herein refers to the time for completing the constant rate drying of the emulsion surface.

Various component materials are used in the automatic processor, and preferable materials are described below.
The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include “Noryl” manufactured by GE Plastics Japan, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers.

Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.
PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.
PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

High molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products such as “Lubema”, “Hi-Zex Million” manufactured by Mitsui Petrochemical Co., Ltd., “New Light”, Sakushin Kogyo Co., Ltd., “Sun Fine”, etc. Is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000.
The PPS resin is preferably glass fiber or carbon fiber reinforced. Examples of the LCP resin include ICI Japan Co., Ltd. “Victrex”, Sumitomo Chemical Co., Ltd. “Econol”, Nippon Oil Co., Ltd. “Zider”, Polyplastics Co., Ltd. “Vectra”, and the like.
In particular, the material of the conveyor belt is preferably an ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in JP-A-4-151656.
Further, nylon or polyethylene is preferable as the material of the conveying belt used for conveying the photosensitive material in the drying section.
As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd.
EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material.

  Moreover, it is also preferable to add a chemical | medical agent directly to a processing tank, and to add the water according to a dilution rate to a processing tank. Moreover, it is also preferable to use it as a replenishing solution by automatically dissolving and diluting it in a replenishing tank using an automatic preparation device.

The outline of the configuration of the digital printer processor preferably used in the present invention is shown in FIG. 1 and described below, but the present invention is not limited to this.
In FIG. 1, the printer processor 2 includes a printer unit 3 and a processor unit 4. The printer unit 3 includes a magazine 5, a cutter 6, a back printing unit 7, an exposure unit 8, and a sorting unit 9. The strip-shaped photosensitive material 10 set in the magazine 5 is cut by the cutter 6 in accordance with the print size to form a cut sheet-shaped photosensitive material 10a. The photosensitive material 10a is conveyed toward the exposure unit 8 along a conveyance path 15 indicated by a two-dot chain line in FIG. 1, and a frame number, correction data, and the like are printed by the back printing unit 7 on the way. Then, an image based on the image data is exposed and recorded on the light receiving surface of the photosensitive material 10a by the exposure unit 8. Thereafter, the exposed photosensitive material 10 a is sorted by the sorting unit 9 into a single row or a plurality of rows according to the print size and the print quantity, and is conveyed to the processor unit 4.

  The processor unit 4 includes a development processing unit 11, a squeeze unit 12, a drying unit 13, and a sorter unit 14. The development processing unit 11 includes a developing tank 16, a bleach-fixing tank 17, and first to fourth rinsing tanks (water washing tanks) 18 to 21 in order from the upstream side (left side in the drawing) of the photosensitive material 10a in the conveyance direction. . A developing solution is stored in the developing tank 16, a bleach-fixing solution is stored in the bleach-fixing tank 17, and a predetermined amount of rinsing liquid (washing solution) is stored in the first to fourth rinsing tanks (water-washing tanks) 18-21. . Inside the developing tank 16 and the bleach-fixing tank 17, there is provided a transport rack 22 composed of a plurality of transport rollers for transporting the photosensitive material 10a in a substantially U shape within the tank. In the rinsing tanks (water-washing tanks) 18 to 21, a transport roller pair 23 for transporting the photosensitive material 10a in a substantially U shape in the tank is provided. The photosensitive material 10a is sent into the respective tanks 16 to 21 by the transport rack 22 and the transport roller pair 23 and subjected to development processing.

In the rinsing tanks (water washing tanks) 18 to 21, the photosensitive material 10a is sent to the next tank through the submerged squeeze portion 24 provided in the partition wall. The submerged squeeze portion 24 is provided with a blade made of a thin plate that is elastically deformed. The blade allows the photosensitive material 10a to pass therethrough and prevents the washing solution from flowing out. The developed photosensitive material 10 a is removed from the water droplets attached at the squeeze portion 12 and sent to the drying portion 13.
At this time, the photosensitive material 10a passes in the horizontal direction in water. That is, the photosensitive material 10a is conveyed through the blade that partitions the rinsing tank so that the emulsion coating surface is parallel to the liquid surface.
By performing such submerged conveyance, rapid processing is possible without impairing the water washing effect, which is most preferable in the present invention.
The blade according to the present invention relates to a method of processing a photosensitive material with processing solutions stored in a plurality of processing tanks, and conveys the air in the air when the photosensitive material passes from a previous bath tank to the next tank. The partition of the partition for conveying in a liquid between process tanks without being comprised is comprised, Comprising: The member for preventing the liquid leak between process tanks by sealing this partition in a liquid is meant. A preferable material for such a blade is a polyurethane resin having a JIS A hardness of 80 to 99 degrees, and among these, a thermosetting polyurethane and a material based on a polyether-based prepolymer are used in a liquid for a long time. Suitable for blade material.

As shown in FIGS. 2 and 3, the drying unit 13 is for drying the photosensitive material 10a after the rinsing process (after the water washing process), and includes a drying chamber 31, a blower duct 32, a heater 34, a blower 35, and a conveyance. The rack 40 is configured.
The transport rack 40 includes a transport belt 43 and first to third transport roller pairs 46 to 48 in order from the feeding direction of the photosensitive material 10a, and forms a photosensitive material transport path. The squeeze roller pair 41, 42 of the squeeze unit 12 sandwiches and conveys the photosensitive material 10 a sent from the development processing unit 11 and sends it out to the conveyance belt 43. By this nipping and conveying, moisture adhering to the photosensitive material 10a is squeezed out.

  The conveyor belt 43 is composed of an endless belt made of mesh, and is wound around the rollers 44. The photosensitive material 10a sent from the squeeze roller pair 42 is transported by the back surface side (opposite surface of the image recording surface) of the photosensitive material 10a by the dry air blown from the nozzle 38 of the guide plate 33 as will be described later. The paper is conveyed while being pressed against the belt 43, and is sent out to the first conveying roller pair 46. Therefore, the image recording surface 10b of the photosensitive material 10a is conveyed in a state of being separated from the guide plate 33, and the image recording surface 10b is not damaged by the sliding of the photosensitive material 10a and the guide plate 33. In addition, as described in Japanese Patent Application No. 2003-416907, a plurality of skewer rollers protruding from the guide plate 33 are provided to support the vicinity of the side edge of the photosensitive material, whereby the image of the guide plate 33 and the photosensitive material 10a. It is also possible to effectively prevent the return work surface from sliding.

  The air duct 32 includes a guide plate 33 along the photosensitive material conveyance path at a position facing the photosensitive material 10a. The guide plate 33 is made of aluminum and, as described in Japanese Patent Application No. 2003-413560, is configured with a surrounding member that constitutes the drying chamber via a heat insulating material. By adopting such a configuration, the temperature distribution of the guide plate 33 becomes uniform due to the drying air, which is preferable for improving the drying efficiency. In order to further increase the drying efficiency, the photosensitive material side surface 33a of the guide plate 33 may be painted black. Accordingly, the heat conductivity of the guide plate 33 is high and the emissivity with respect to the photosensitive material 10a is also high (total emissivity of 0.9 or more), so that not only drying by hot air but also drying effect by heat radiation is obtained. be able to. The guide plate 33 is provided with a large number of nozzle rows 38 arranged in the photosensitive material transport direction. The nozzle row 38 is configured by providing a large number of nozzles 38a at a predetermined pitch so that the drying air is uniformly blown in a direction orthogonal to the photosensitive material conveyance direction, and a plurality of rows of photosensitive materials 10a conveyed on the conveyance belt 43 are provided. Even if it exists, the difference of the drying progress state of the thermosensitive material 10a between different rows can be suppressed to the minimum.

  As shown in FIGS. 2 and 3, a drying air supply passage 51 is formed in the air duct 32 in order to blow dry air from the nozzle 38 a. A heater 34 and a blower 35 are provided in the dry air supply passage 51. The blower 35 is composed of a cross flow fan, and circulates dry air in the drying unit 13. The heating wire heater 34 is controlled by the temperature controller 36 so that the drying air becomes 80 ° C., for example.

Hereinafter, a silver halide color photosensitive material (hereinafter referred to as a photosensitive material) applied to the image forming method of the present invention will be described.
The light-sensitive material is a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a red-sensitive silver halide emulsion containing a cyan dye-forming coupler on a support. A photographic constituent layer comprising at least one each of a layer and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have.

  In addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer to be described later if desired.

  The photosensitive material contains, as a cyan dye-forming coupler, at least one selected from compounds represented by the following general formula (IA), and as a magenta dye-forming coupler, a general formula (M-I) (particularly, It contains at least one selected from compounds represented by formula (M-III)). Usually, cyan dye-forming couplers are used in red-sensitive silver halide emulsion layers, while magenta dye-forming couplers are used in green-sensitive silver halide emulsion layers.

The silver halide emulsion will be described below.
The grain shape of the silver halide emulsion is not particularly limited, but is substantially a cubic or tetradecahedral crystal grain having {100} faces (these grains have round vertices and higher order faces). It is preferable that the crystal grains are octahedral, and the main surface is composed of tabular grains having an aspect ratio of 2 or more, which are {100} faces or {111} faces. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. In the present invention, cubic or tetrahedral particles are more preferable.

The silver halide emulsion contains silver chloride, and the silver chloride content is preferably 90 mol% or more. From the viewpoint of rapid processability, the silver chloride content is more preferably 93 mol% or more. Preferably, 95 mol% or more is more preferable.
The silver halide emulsion preferably contains silver bromide and / or silver iodide. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and excellent in latent image stability. The silver iodide content is preferably 0.02 to 1 mol%, more preferably 0.05 to 0.50 mol%, more preferably 0.07 to 0.40 mol% is most preferred.
The silver halide emulsion is preferably a silver iodobromochloride emulsion, and more preferably a silver iodobromochloride emulsion having the above-described halogen composition.

  The silver halide emulsion preferably has a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of the minimum It is particularly preferred to have one containing phase, preferably at least one containing phase each.

  The silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion is preferably layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, the silver bromide-containing phase and the silver iodide-containing phase may be in the same place or in different places of the grain, but it is easier to control grain formation if they are in different places. preferable. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content of the silver halide emulsion increases as the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain, and the silver chloride content is reduced more than necessary. This may impair the rapid processability. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic action near the surface in the grain. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  In order to incorporate silver bromide or silver iodide into a silver halide emulsion, bromide or iodide ions can be introduced by adding a bromide salt or an iodide salt solution alone, or by adding a silver salt solution and a high chloride salt. Along with the addition of the solution, a bromide salt or iodide salt solution may be added. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated during a period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining a high sensitivity and low fog emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, whereby an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  The variation coefficient of the equivalent sphere diameter of all the grains contained in the silver halide emulsion is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating. Here, in this specification, the sphere equivalent diameter of a particle is represented by the diameter of a sphere having a volume equal to the volume of each particle. The silver halide emulsion is preferably composed of grains having a monodispersed grain size distribution.

  The equivalent sphere diameter of the grains contained in the silver halide emulsion is preferably 0.6 μm or less, preferably 0.5 μm or less, and more preferably 0.4 μm or less. The lower limit of the equivalent sphere diameter of the silver halide grains is preferably 0.05 μm, more preferably 0.1 μm. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.4 μm, and a sphere equivalent diameter of 0. A 4 μm particle corresponds to a cubic particle having a side length of about 0.32 μm.

  The silver halide emulsion preferably contains iridium. Iridium preferably forms an iridium complex, and a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is preferable, and all six ligands are composed of Cl, Br, or I. More preferred is a hexacoordinate complex having a central metal. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex containing Ir as a central metal having Cl, Br or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of hexacoordination complexes having Ir as a central metal, in which all six ligands are Cl, Br or I, include [IrCl ₆ ] ²⁻ , [IrCl ₆ ] ³⁻ , [IrBr ⁶ ] ²⁻ , Examples include, but are not limited to, [IrBr ₆ ] ³⁻ and [IrI ₆ ] ³⁻ .

As another preferred embodiment of iridium, a hexacoordination complex having at least one ligand other than halogen and cyan as a central metal is preferable, and H ₂ O, OH, O, OCN, thiazole or substituted thiazole, thiadiazole or Preferred is a hexacoordination complex having Ir as a central metal having a substituted thiadiazole as a ligand, and at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligands being Cl, Br or A hexacoordinate complex having Ir as the central metal is more preferable. Furthermore, one or two 5-methylthiazole, 2-chloro-5 fluorothiadiazole or 2-bromo-5 fluorothiadiazole is used as a ligand, and the remaining ligand is Cl, Br or I. Hexacoordination complexes are most preferred.

Specific examples of hexacoordination complexes having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand consisting of Cl, Br or I as a central metal are as follows: [Ir (H ₂ O) Cl ₅ ] ²⁻ , [Ir (OH) Br ₅ ] ³⁻ , [Ir (OCN) Cl ⁵ ] ³⁻ , [Ir (thiazole) Cl ₅ ] ²⁻ , [Ir (5 ^{_{-methylthiazole) Cl 5] 2-, [}} Ir (2-chloro-5-fluorothiadiazole) Cl 5] 2- and [[Ir (2-blomo- 5-fluorothiadiazole) Cl 5] 2- and include, but limited to Not.

In addition to the above iridium complex, the silver halide emulsion is [Fe (CN) ₆ ] ⁴⁻ , [Fe (CN) ₆ ] ³⁻ , [Ru (CN) ₆ ] ⁴⁻ , [Re (CN) ₆ ] ^{4. -,} it preferably contains a six-coordinate complex having a central metal Fe, Ru, and Re or Os having a [Os (CN) _6] CN ligands ^4- like. The silver halide emulsion used in the present invention further has a pentachloronitrosyl complex, a pentachlorothionitrosyl complex having Ru, Re or Os as a central metal, or Rh having Cl, Br or I as a ligand as a central metal. It is preferable to contain a coordination complex. These ligands may be partially aquaated.

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. The optimum amount of these metal complexes varies depending on the type, but it is preferable to add 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁹ mol to 1 × It is most preferable to add 10 ⁻⁵ mol.

  These metal complexes are added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or other solutions, and added to the grain formation reaction solution. It is preferable to incorporate it into the silver halide grains by adding them. It is also preferable to physically ripen the fine particles in which the metal complex has been previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing the complex only inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, the particle surface phase is improved by physical ripening with fine particles incorporating the complex in the particles. It is also preferred that Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.

  Silver halide emulsions are usually chemically sensitized. As the chemical sensitization method, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.

  For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

  Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1). , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfo Natobenzamido) phenyl] -5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example, bis (1 -Methylhydantoinato) gold (I) sodium salt tetrahydrate can be used. The gold (I) compound having these organic ligands may be synthesized in advance and isolated, or may be mixed with an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be added separately to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.

Also described in the gold (I) thiolate compounds described in US Pat. No. 3,503,749, JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554. Of gold compounds, U.S. Pat. Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111. The compounds described in each specification can also be used. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per mol of silver halide. is there.

Colloidal gold sulfide can also be used, and the manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B 263, p. 1328, published in 1966. The addition amount of the gold sulfide colloid may vary widely depending on the case, but 5 × 10 ^-7 ~5 × 10 ^-3 mol as per mole of silver halide gold atoms, preferably 5 × 10 ^-6 ~5 × 10 ^{- 4} moles.

In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule, and a molecule capable of releasing AuCh- can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. Examples of the amount capable of releasing AuCh- include gold compounds represented by AuCh-L. Here, L represents an atomic group constituting a molecule by binding to AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. Specific examples of compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), selenosugar Au (I) salts (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurose, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, or a TeH group, respectively. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol per mol of silver halide. is there.

  The silver halide emulsion may be combined with the above gold sensitization and other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds. Good. It is particularly preferable to combine with sulfur sensitization and selenium sensitization.

  Various compounds or precursors thereof can be added to the silver halide emulsion for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.

  In order to increase the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576, the carbonyl group described in JP-A-11-327094, and both ends are amino groups or Cyclic ketones having a double bond substituted with a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the specification of the present application), JP-A-11- 143011, sulfo-substituted catechol and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzene) Sulfone 1,2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4, -Trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) of US Pat. No. 5,556,741 (of US Pat. No. 5,556,741) The description in the fourth column, line 56 to column 11, line 22 is preferably applied also in the present application, and is incorporated as part of the specification of the present application), general formula (I) of JP-A-11-102045. The water-soluble reducing agent represented by ~ (III) is also preferably used in the present invention.

The silver halide emulsion may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity that exhibits photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for partial sensitization in the blue, green, and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & ons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.
The addition amount of these spectral sensitizing dyes varies widely depending on the case, and is preferably in the range of 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol.

Hereinafter, the photosensitive material of the present invention will be described in more detail.
Gelatin is used as a hydrophilic binder in the light-sensitive material, but other gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, mono- or copolymer as necessary. Hydrophilic colloids such as synthetic hydrophilic polymer materials can also be used in combination with gelatin. The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be either lime-processed gelatin or acid-processed gelatin, or may be gelatin manufactured using any raw material such as cow bone, cow skin, or pig skin. Preferred is lime-processed gelatin made from beef bone and pig skin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  Although any known gelatin hardener can be used in the light-sensitive material of the present invention, it preferably contains at least one vinylsulfone hardener represented by the following general formula (I).

In the general formula (I), X ¹ and X ² each independently represents any of -CH = CH ₂ or -CH ₂ CH ₂ Y, X ¹ and X ² may be different even in the same . Y represents a group that can be substituted with a nucleophilic group or can be eliminated in the form of HY by a base (for example, a halogen atom, a sulfonyloxy, a sulfuric monoester, etc.). L is a divalent linking group and may be substituted.

In the general formula (I), specific examples of X ¹ and X ² include the following groups.

  Among these, (X-1), (X-2), (X-4), (X-7), and (X-12) are preferable, and (X-1) is particularly preferable.

In general formula (I), examples of L include an alkylene group, an arylene group, or a divalent linking group formed by combining these groups with one or more of the bonds shown below. Here, R ^{1 in the} bond shown below represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an aralkyl group having 1 to 15 carbon atoms.

In general formula (I), in particular, when L has two or more of the bonds shown below, R ¹ may be bonded to each other to form a ring.

In general formula (I), L may have a substituent, and examples of the substituent include a hydroxyl group, an alkoxyl group, a carbamoyl group, a sulfamoyl group, an alkyl group, and an aryl group. In addition, the substituent may be further substituted with one or more groups represented by X ³ —SO ₂ —. Here, X ³ has the same meaning as X ¹ and X ^{2 in} formula (I).

In the general formula (I), typical examples of L include the following groups. However, in the examples, a to r represent integers of 1 to 6, and s to w represent 1 or 2. Only e may be 0. Among these, it is preferable that a, e, j, k, and m are 1-3, and it is preferable that it is 1 or 2 except a, e, j, k, and m in a-w. R ^{1 to} R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ¹ and R ² , and R ⁴ and R ⁵ are bonded to each other to form a ring. Yes. R ^{1 to} R ⁵ are preferably a hydrogen atom, a methyl group, or an ethyl group.
Moreover, these L may have a substituent. The following are mentioned as typical examples when L has a substituent and when R ¹ and R ² are bonded.

Moreover, these L may have a substituent. The following are mentioned as typical examples when L has a substituent and when R ¹ and R ² are bonded.

  Hereinafter, although the specific example of the vinyl sulfone type hardener represented by general formula (I) is given, this invention is not necessarily limited to these.

  Among the specific examples of the vinylsulfone hardener represented by the general formula (I), particularly preferred compounds are (H-1), (H-2), (H-3), (H-4). ), (H-6).

  In addition, in combination with the hardener represented by the general formula (I), for example, JP-A-62-215272, paragraph 146, upper right side, line 8 to lower right column, line 2 and 147, lower right side The hardener described in the 6th line to the 155th left lower column, 4th line can be used in combination. Further, in the present invention, the addition amount of the hardening agent is an amount that consists of gelatin substantially hardened with the hydrophilic colloid layer, and is 0.01 to 10% by mass with respect to dry gelatin. More preferably, it is 0.1-5 mass%, Most preferably, it is 0.2-3.0 mass%. The most representative hardener used in combination is a chlorotriazine hardener, but the amount of chlorotriazine hardener used is preferably 0 to 2.0% by mass, more preferably 0 to 1.0%. % By mass, most preferably 0-0.2% by mass.

The total coating amount of gelatin in the photographic composition layer in the light-sensitive material is, i.e., the photosensitive silver halide emulsion layer from the support to the hydrophilic colloid layer farthest from the support on the side where the silver halide emulsion layer is coated. The total amount of the hydrophilic binder contained in the non-photosensitive hydrophilic colloid layer is preferably 4.0 g / m ² or more and 7.0 g / m ² or less, more preferably 4.5 g / m ² or more and 6.5 g. / M ² or less, most preferably 5.0 g / m ² or more and 6.0 g / m ² or less. When the amount of the hydrophilic binder is larger than the above range, the effect of the present invention is reduced by impairing the rapidity of color development processing, deteriorating the Brix fading, and impairing the rapid processability of the rinsing process (washing and / or stabilizing process). May decrease. In addition, when the amount of the hydrophilic binder is less than the above range, it is not preferable because it is liable to cause harmful effects due to insufficient film strength such as pressure covering stripes.

  The photosensitive material can be decolorized by processing as described in pages 27 to 76 of EP 0337490A2 in the hydrophilic colloid layer for the purpose of preventing irradiation and halation, and improving safetylight safety. It is preferable to add various dyes (especially oxonol dyes and cyanine dyes). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As the dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  For the light-sensitive material, a colored layer that can be decolored by processing in combination with a water-soluble dye or in combination with a water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install colored layers corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3, upper right column to page 8 and those described in JP-A-3-7931, page 3, upper right column to page 11, lower left column, can be used for solid fine particle dispersions. Described in JP-A-1-239544, a method of incorporating a hydrophilic colloid layer in a state, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing in the layer For example, a method using colloidal silver. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. Methods for preparing colloidal silver as a light absorber are shown in US Pat. Nos. 2,688,601 and 3,459,563. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The light-sensitive material preferably has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. The silver halide emulsion layer is a yellow color-developing silver halide emulsion layer, a magenta color-developing silver halide emulsion layer, and a cyan color-developing silver halide emulsion layer in order from the support.

However, a different layer structure may be used.
In the light-sensitive material, the silver halide emulsion contained in the blue-sensitive silver halide emulsion layer is a green-sensitive silver halide emulsion or a red-sensitive material because of the spectral characteristics of the negative yellow mask and the halogen used as the light source during exposure. It is preferable that the sensitivity is relatively high with respect to the silver halide emulsion. Therefore, it is preferable that the grain side length of the blue-sensitive emulsion is larger than the grain side length of the other layer. Furthermore, the molar extinction coefficient of a generally known yellow coupler coloring dye is lower than that of a magenta coupler coloring dye or a cyan coupler coloring dye, and the amount of blue-sensitive emulsion coating increases as the yellow coupler coating amount increases. There is a tendency. For this reason, the yellow-colored blue-sensitive silver halide emulsion layer is disadvantageous compared to other layers in consideration of resistance to pressure from the surface of the photosensitive material, such as scratching, and is preferably located on the side closer to the support. .

  That is, the silver halide emulsion layer containing the yellow coupler may be disposed at any position on the support. If the silver halide emulsion layer contains silver halide tabular grains, the magenta coupler It is preferably coated at a position farther from the support than at least one of the silver halide emulsion layer or the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of color development acceleration, desilvering acceleration, and reduction of residual color by sensitizing dye, the yellow-coupler-containing blue-sensitive silver halide emulsion layer is farthest from the support than the other silver halide emulsion layers. It is preferable that it is coated at the position. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is The lowest layer is preferred. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers.

  Examples of silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied to the photosensitive material, and processing methods and processing additives applied to process this photosensitive material Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854. No. 1-158431, 2-90145, 3-194539, 2-93641, European Patent Publication No. 0520457A2, etc. Treatment methods are also preferred.

  In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) Layer), gelatin type, layer structure of photosensitive material, coating film pH of photosensitive material, etc., those described in each part of the patents shown in the following table are particularly preferably applicable.

In the light-sensitive material, a dye-forming coupler (also referred to as a coupler in the present specification) is emulsified and dispersed together with a photographically useful substance and other high-boiling organic solvents, and is incorporated into the light-sensitive material as a dispersion. This liquid is emulsified and dispersed in a fine particle form in a hydrophilic colloid, preferably an aqueous gelatin solution, together with a surfactant dispersing agent, using a known apparatus such as ultrasonic wave, colloid mill, homogenizer, manton gourin, high-speed dissolver, etc. Get.
The high-boiling organic solvent is not particularly limited, and ordinary solvents are used, and examples thereof include those described in US Pat. No. 2,322,027 and JP-A-7-152129.
An auxiliary solvent can be used together with the high boiling point organic solvent. Examples of cosolvents include acetates of lower alcohols such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, s-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate and cyclohexanone. Etc.

Furthermore, if necessary, an organic solvent that is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide, and the like can be partially used together. Moreover, these organic solvents can also be used in combination of 2 or more types.
From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final composition for coating mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, noodle washing or ultrafiltration.
The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics).

  In the oil-in-water dispersion method using a high-boiling organic solvent, the mass of the high-boiling organic solvent relative to the total amount of cyan coupler used can be arbitrarily selected, but is preferably 0.1 or more and 10.0 or less, more preferably 0.3. It is 7.0 or less and most preferably 0.5 or more and 5.0 or less. Moreover, it is also possible to use it without using any high-boiling organic solvent.

  In addition, a tinting pigment may be co-emulsified in the emulsion used in the present invention to adjust the color of a white background, and an organic solvent that dissolves a photographic useful compound such as a coupler used in the photosensitive material of the present invention. It may be co-emulsified and co-emulsified to prepare an emulsion.

Other examples of cyan, magenta and yellow couplers used in the light-sensitive material include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.

In the present invention, at least one selected from compounds represented by the following general formula (IA) is used as a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”). A cyan coupler may be used in combination.
The compound represented by the following general formula (IA) will be described below.

  In the general formula (IA), R ′ and R ″ each independently represent a substituent, and Z is a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. Represents.

  Here, unless otherwise indicated, the term “alkyl” below refers to an unsaturated or saturated, linear or branched alkyl group (including alkenyl and aralkyl), and a ring having 3 to 8 carbon atoms. Including the formula alkyl groups (including cycloalkenyl), the term “aryl” specifically includes fused aryl.

  In general formula (IA), R ′ and R ″ are unsubstituted or substituted alkyl, aryl, amino, or alkoxy groups, or one selected from nitrogen, oxygen, and sulfur It is preferably selected independently from a 5-10 membered heterocycle containing the above heteroatoms, which ring is unsubstituted or substituted.

  In the general formula (IA), when R ′ and / or R ″ are amino or alkoxy groups, they may be substituted, for example, with a halogen, aryloxy, or alkyl- or aryl-sulfonyl group. Preferably, however, R ′ and R ″ are independent of an unsubstituted or substituted alkyl or aryl group, or a 5-10 membered heterocycle such as a pyridyl, morpholino, imidazolyl, or pyridazolyl group. Chosen.

  In general formula (IA), R ′ is, for example, a halogen atom, an alkyl group, an aryloxy group, or an alkyl group substituted with an alkyl- or aryl-sulfonyl group (which may be further substituted). Is more preferable. When R ″ is an alkyl group, it may be substituted as well.

  However, R ″ is preferably an unsubstituted aryl group or, for example, a cyano group, a halogen atom (chloro, fluoro, bromo, iodo), an alkyl- or aryl-carbonyl group, an alkyl- or aryl-oxy Carbonyl group, acyloxy group, carbonamido group, alkyl- or aryl-carbonamido group, alkyl- or aryl-oxycarbonamido group, alkyl- or aryl-sulfonyl group, alkyl- or aryl-sulfonyloxy group, alkyl -Or aryl-oxysulfonyl group, alkyl- or aryl-sulfoxide group, alkyl- or aryl-sulfamoyl group, alkyl- or aryl-sulfamoylamino group, Kill- or aryl-sulfonamido group, aryl group, alkyl group, alkoxy group, aryloxy group, nitro group, alkyl- or aryl-ureido group, or alkyl- or aryl-carbamoyl group (which may be further substituted) A good). Preferred substituents are a halogen atom, cyano group, alkoxycarbonyl group, alkylsulfamoyl group, sulfonamido group, alkyl-sulfonamido group, alkylsulfonyl group, carbamoyl group, alkylcarbamoyl group, or alkylcarbonamido group. When R ′ is an aryl group or a heterocyclic group, it may be similarly substituted.

  Preferably R ″ is 4-chlorophenyl, 3,4-dichlorophenyl, 3,4-difluorophenyl, 4-cyanophenyl, 3-chloro-4-cyano-phenyl, pentafluorophenyl, or 3- or 4-sulfone. Each group of amide-phenyl.

  In the general formula (IA), Z represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. Z is preferably a hydrogen atom, a chloro atom, a fluoro atom, a substituted aryloxy group or a tetrazolylthio group, more preferably a hydrogen atom or a chloro atom.

  Z determines the chemical equivalent of the coupler, that is, whether it is a 2-equivalent coupler or a 4-equivalent coupler, and the reactivity of the coupler can be changed depending on the type of Z. Such groups, after release from the coupler, perform functions such as dye formation, dye hue adjustment, development acceleration or development inhibition, bleach acceleration or bleach inhibition, electron transfer facilitation, and color correction, for example. The layer in which the coupler in the material is applied, or other layers, can be beneficially affected.

  Representative classes of such coupling-off groups include, for example, halogen atoms, alkoxy groups, aryloxy groups, heterocyclyloxy groups, sulfonyloxy groups, acyloxy groups, acyl groups, heterocyclyl groups, sulfonamido groups, heterocyclylthios. Groups, benzo-thiazolyl groups, phosphonyloxy groups, alkylthio groups, arylthio groups, and arylazo groups. These coupling-off groups include, for example, U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,467,563, and 3, 617,291, 3,880,661, 4,052,212, and 4,134,766, and British Patent 1,466,728, Nos. 1,531,927 and 1,533,039, and GB Patent Publication Nos. 2,066,755A and 2,017,704A (the disclosures of which are cited) Incorporated herein). Most preferred are halogen atoms, alkoxy groups, and aryloxy groups.

Examples of preferred coupling-off groups are as follows. -Cl, -F, -Br, -SCN, -OCH 3, -OC 6 H 5, -OCH 2 C (= O) NHCH 2 CH 2 OH, -OCH 2 C (O) NHCH 2 CH 2 OCH 3, _{-OCH 2 C (O) NHCH 2} CH 2 OC (= O) OCH 3, -P (= O) (OC 2 H 5) 2, -SCH 2 CH 2 COOH,

  In general, the coupling-off group is a chlorine atom, a hydrogen atom, or a p-methoxyphenoxy group.

  Specific examples of the compound represented by formula (IA) are shown below, but the present invention is not limited thereby.

Examples of magenta dye-forming couplers that can be used in light-sensitive materials (sometimes simply referred to as “magenta couplers”) include 5-virazolone-based magenta couplers and pyrazoloazole-based magenta couplers as described in the publicly known literatures in the above table. Is used.
In the present invention, a compound represented by the following general formula (MI) is used.
Hereinafter, the compound represented by the following general formula (MI) will be described in detail.

In general formula (MI), R ₁ , R ₂ , and R ₃ each independently represents a hydrogen atom or a substituent. Substituents include halogen atoms, aliphatic groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, carboxy groups, sulfo groups, amino groups, alkoxy groups, aryloxy groups, acylamino groups, alkylamino groups , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy Represents a group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group or azolyl group, and among these groups, further substitution Having a group Groups may be substituted with the described substituent groups.

  More specifically, a halogen atom (for example, a chlorine atom or a bromine atom), an aliphatic group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, A cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4 -(4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-tert-amylphenoxy) propyl), aryl groups (eg , Phenyl, 4-tert-butylphenyl, 2,4-di-tert- Milphenyl, 2,4,6-trimethylphenyl, 3-tridecanamido-2,4,6-trimethylphenyl, 4-tetradecanamidophenyl, tetrafluorophenyl), a heterocyclic group (for example, 2-furyl, 2- Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2- Methanesulfonylethoxy), aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-tert-butoxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), acylamino groups (for example, Acetami , Benzamide, tetradecanamide, 2- (2,4-di-tert-amylphenoxy) butanamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide, 2- [4- (4-hydroxyphenylsulfonyl) Phenoxy] decanamide), alkylamino groups (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),

  Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- [2- (3-tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino), carbamoylamino group (for example, N-phenylcarbamoylamino, N-methylcarbamoylamino, N, N-dibutylcarbamoylamino), sulfamoylamino group (For example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio , 3- (4-tert-Buchi Phenoxy) propylthio), arylthio groups (eg, phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino groups ( For example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butyl Benzenesulfonamide),

  Carbamoyl groups (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert -Amylphenoxy) propyl] carbamoyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfa) Moyl, N, N-diethylsulfamoyl), sulfonyl groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxy) Rubonyl), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2 -Hydroxy-4-propanoylphenylazo), acyloxy groups (eg acetoxy),

  Carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide, 3-octadecenyl succinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6) Thio, 2-pyridylthio), sulfinyl groups (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl groups (eg, phenoxyphosphonyl, octylphosphonyl, phenylphospho) ), Aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg imidazolyl, pyrazolyl, 3-chloro-pyrazole) -1-yl, triazolyl).

  Among these substituents, preferred substituents are alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, carbamoylamino groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, alkylacylaminos. And arylacylamino group.

In general formula (MI), one of Za and Zb represents a hydrogen atom or a carbon atom having a substituent, the other represents a nitrogen atom, and the substituent of Za or Zb further represents a substituent. You may have.
Examples of the substituent that any one of the carbon atoms of Za and Zb may have include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an amino group, and an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, azolyl Groups, These may further have a substituent.
Examples of each of these groups include the groups mentioned in the description of the substituents in R _{1 to} R ₃ described above.
The substituent which the carbon atom of any one of Za and Zb can further have is a group further having an organic substituent or halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Furthermore, you may have. Specific examples of these substituents include the substituents in R _{1 to} R ₃ described above.
Preferred substituents of any one of Za and Zb include an alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, alkoxycarbonylamino group, and acylamino group. Is a group having a total carbon number of 6 to 70 containing an alkyl group or aryl group having a carbon number of 6 to 70 as a partial structure, and is preferable for making the coupler represented by the general formula (MI) non-diffusible. .
In the general formula (M-I), X represents a detachable group in the reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamido group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, There are a 5-membered or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group and the like, and these groups may be further substituted with a group allowed as a substituent for R _{1 to} R ₃ .

  More specifically, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy group ( For example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, , Acetoxy, tetradecanoyloxy, benzoyloxy),

  Alkyl or arylsulfonyloxy groups (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg dichloroacetylamide, heptafluorobutyrylamino), alkyl or arylsulfonamide groups (eg methanesulfonamino, trifluoromethane) Sulfoneamino, p-toluenesulfonylamino), alkoxycarbonyloxy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg , Dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio, 2-benzyloxy (Rubonylaminophenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5-membered or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl, 1-pyrazolyl, 1 , 2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-1-pyrazolyl, 1 , 2-dihydro-2-oxo-1-pyridyl), imide group (for example, succinimide, hydantoinyl), arylazo group (for example, phenylazo, 4-methoxyphenylazo) and the like. X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, particularly preferably a halogen atom or a substituted group. An aryloxy group, a substituted arylthio group or a substituted 1-pyrazolyl group.

  Of the general formula (M-I), preferred magenta couplers are represented by the following general formula (M-II) or (M-III). Particularly preferred is a compound represented by formula (M-III).

(In the general formula (M-II), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. X is as defined above for X in the general formula (MI). is there.)

(In the general formula (M-III), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. X is as defined above for X in the general formula (MI). is there.)
Preferred groups in the general formulas (M-II) to (M-III) are as follows. Preferred groups for X include a halogen atom, an alkoxy group, and an aryloxy group, with a chlorine atom being particularly preferred. Preferred examples of the substituent for R _{1 to} R ₄ include an alkyl group, an aryl group, an anilino group, and an alkoxy group. Among them, an alkyl group or an aryl group is preferable, and R ₁ , R ₂ , and R ₃ are particularly methyl groups. , R ₄ is preferably an alkyl group or an aryl group (these are preferably substituted). R ₄ is most preferably an aryl group in the general formula (M-II) and an alkyl group in the general formula (M-III). The magenta coupler used in the present invention is used in the range of 0.001 to 1 mol, preferably 0.003 to 0.3 mol, per mol of the photosensitive silver halide in the same layer. The molecular weight of the coupler is preferably 600 or less. Specific examples of the magenta coupler represented by formula (M-I) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (M-I) does not contain a lot of unnecessary yellow and cyan components than the pyrazolone-type magenta coupler, so the color purity is high and the temporal stability of the white background is also good. A color image can be obtained stably.

  Examples of yellow dye-forming couplers that can be used in the light-sensitive material (in this specification, simply referred to as “yellow couplers”) include, in addition to the compounds described in the above table, acyl compounds described in EP 0447969A1. Acylacetamide type yellow coupler having a 3-5 membered cyclic structure in the group, Malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Nos. 935870A1, 953871A1, Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide-type coupler described in each specification of 953872A1, 953873A1, 953874A1, 953875A1, etc., US Pat. No. 5,118,599 Placing acyl acetamide type yellow couplers or JP acetanilide type yellow couplers heterocyclic acyl group is substituted as described in 2003-173007 JP having a dioxane structure is preferably used. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred. These couplers can be used alone or in combination.

  Couplers that can be used in the light-sensitive material are impregnated into a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence (or absence) of the high-boiling organic solvent described in the above table. It is preferable that the polymer is dissolved or dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

As the light-sensitive material, known color mixing inhibitors can be used. Among them, those described in the following patents are preferable.
For example, a high molecular weight redox compound described in JP-A-5-333501, a phenidone or hydrazine compound described in each specification of WO98 / 33760, US Pat. No. 4,923,787, and the like. White couplers described in JP-A No. 249637, JP-A-10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case of increasing the pH of the developer and speeding up the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 8429975A1, German Patent No. 1980646A1 and French Patent No. 2760460A1 It is also preferable to use the redox compound described in each specification.

  In the light-sensitive material, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber. For example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-2111813, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in the specification or publication of 501291 can be used.

  An antibacterial / antifungal agent as described in JP-A-63-271247 is added to the photosensitive material in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

A surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the photosensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper.
As the photographic support that can be used for the photosensitive material, a transmissive support or a reflective support can be used. As a transmissive support, a permeable film such as a cellulose triacetate film or polyethylene terephthalate, a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), a polyester of NDCA, terephthalic acid, and EG, etc. Those provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminate layers) is preferable.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. The fluorescent brightening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based optical brighteners are more preferable. Specific examples of the optical brightener contained in the water-resistant resin layer include 4,4′-bis (benzoxazolyl) stilbene and 4,4′-bis (5-methylbenzoxazolyl) stilbene. And a mixture thereof. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water-resistant resin is preferably 0.0005 to 3 mass%, more preferably 0.001 to 0.5 mass%, based on the resin.

  The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular reflective or second-type diffuse reflective metallic surface.

  More preferably, the reflective support includes a polyolefin layer having fine pores on the paper substrate on the side where the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg polypropylene, polyethylene) and is close to the paper substrate More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, and more preferably 0.50 to 0.7 g / ml. The thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 10 to 100 μm, more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are described in JP-A Nos. 10-333277, 10-333278, 11-52513, 11-65024, EP0880065, and Examples are described in the specification or publication of EP0880066.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 of the present invention were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 having compound 2 or 3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), Compound -4 and potassium bromide were added to complete the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In preparation of emulsion BH-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride at the same time were changed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
In preparation of Emulsion GH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride is changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.35 μm and a coefficient of variation of 9.8%. After redispersing this emulsion, Emulsion GL-1 was similarly prepared except that the amount of various compounds added was changed from that of Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-8, compound-5, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
In preparation of emulsion RH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. Emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion RH-1 after precipitation desalting treatment and maximum dispersion.

First layer coating solution preparation 45 g yellow coupler (Ex-Y), 7 g color image stabilizer (Cpd-1), 4 g color image stabilizer (Cpd-2), 7 g color image stabilizer (Cpd-3), color image 2 g of stabilizer (Cpd-8) is dissolved in 21 g of solvent (Solv-1) and 80 ml of ethyl acetate, and this solution is stirred at a high speed in 220 g of 23.5% by weight gelatin aqueous solution containing 4 g of emulsifier (SF-1). The mixture was emulsified and dispersed with an emulsifier (dissolver), and water was added to prepare 900 g of an emulsified dispersion A.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As a gelatin hardening agent for each layer, 1.4 mass% of (Ex-H) was used. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{14.0mg / m 2, 62.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m It added so that it might become ² .

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth and sixth layers, 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ^{2 respectively.} It added so that it might become. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is respectively 1 × 10 ⁻⁴ mol, 2 ×, per mol of silver halide. ^10-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer of the sample 100 is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.33% by mass) The amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.24
Gelatin 1.25
Yellow coupler (EX-Y) 0.45
Color image stabilizer (Cpd-1) 0.07
Color image stabilizer (Cpd-2) 0.04
Color image stabilizer (Cpd-3) 0.07
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.21

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
Magenta coupler (Ma-29) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.15
Gelatin 0.95
Cyan coupler (ExC-1) 0.038
Cyan coupler (ExC-2) 0.005
Cyan coupler (ExC-3) 0.14
Color image stabilizer (Cpd-1) 0.22
Color image stabilizer (Cpd-7) 0.003
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (UV-5) 0.10
Solvent (Solv-10) 0.05

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
AM (trademark) manufactured by Ludox (Colloidal silica) 0.08
Surfactant (Cpd-13) 0.02

-Preparation of samples 101-108-
In sample 100, the magenta coupler of the third layer is changed to another magenta coupler of the same molar amount, or the cyan coupler of the fifth layer is changed to another cyan coupler of the same molar amount, and the hardener is kept in the same amount. Samples 101 to 108 shown in Table 2 below were prepared by changing to the following hardeners.

Processing A
Each of the above samples was processed into a 127 mm width roll, and a standard photographic image was exposed using a digital minilab having a configuration shown in FIG. 1 (sheet conveyance speed of 45 mm / second). Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank.

Processing step Temperature Time Replenishment amount Color development 45.0 ° C 17.8 seconds 45mL / m ²
Bleach fixing 40.0 ° C. 17.8 seconds 35 mL / m ²
Rinse 1 45.0 ° C. 5.4 seconds −
Rinse 2 45.0 ° C. 2.7 seconds −
Rinse 3 45.0 ° C. 2.7 seconds −
Rinse 4 45.0 ° C. 5.5 seconds 175 mL / m ²
Drying 80 ° C 26 seconds

The drying time of the processing step A represents a total time of a squeeze time after rinsing of 3 seconds, a drying air blowing time of 13 seconds, and a transport time of 10 seconds to the drying section outlet.
The treatment liquid used in each process has the following composition.

[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-3) 4.0g 8.0g
Residual color reducing agent (SR-1) 3.0 g 5.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 7.0 g 19.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.6

[Bleaching Fixer] [Tank Solution] [Replenisher]
800 ml of water 800 ml
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
Succinic acid 29.5g 59.0g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH
(Adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5

(Exposure of each sample)
Each sample was subjected to gradation exposure to give gray by the above processing with the following exposure apparatus, and color development processing was performed by the above processing 5 seconds after the exposure was completed. As a laser light source, a blue laser of about 470 nm, a semiconductor laser (oscillation wavelength of about 1060 nm) extracted by converting the wavelength of a semiconductor laser (oscillation wavelength of about 940 nm) with a LiNbO ₃ SHG crystal having a waveguide inversion domain structure. A green laser with a wavelength of about 530 nm and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG) extracted by wavelength conversion using a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.

(Evaluation 1) <Live preservation photograph performance in processing step A>
Samples were prepared in two different storage states: a sample stored for 10 days at 25 ° C. and 55% RH after application (Control), and a sample stored for 3 days under 40 ° C. and 75% RH (Aging).
These samples were subjected to gray gradation exposure by the above-described exposure, developed by the processing apparatus of processing step A, and sensitometry was obtained. The magenta and cyan densities of the Aging sample were measured at an exposure amount at which the magenta and cyan densities of the control sample gave the lowest density +1.8. The concentration difference (ΔG and ΔR) of the Aging sample relative to the Control sample was determined. The smaller ΔG and ΔR, the smaller the photographic change in the preferred rapid processing system of the present invention, and the better.

(Evaluation 2) <Photo gradation processing variation>
In the magenta colorimetric sensitometry of the Control sample obtained in Evaluation 1, the logarithmic value of the exposure amount giving low density +0.2 (logE1) and the logarithmic value of the exposure amount giving the minimum density +1.8 (logE2) are read, and SE = LogE2-logE1 was determined. The large to small SEs represent so-called gray tones of soft tones.
Next, sensitometry of the Control sample was determined in the same manner as in Evaluation 1 except that the color developer and bleach-fix were replaced with new solutions. The gradation was obtained in the same manner as above, and this was designated as SE ′, and the ratio of SE ′ to SE and SE ′ / SE (gradation ratio) was obtained and shown in the G column of Table 1. Similar gradation ratios were obtained for cyan color sensitometry and are shown in the R column of Table 1.
As the gradation ratio SE / SE ′ is closer to 1, the gradation change due to the deterioration of the processing solution in the running process is smaller, indicating that stable photographic performance can be obtained.
The above evaluation results are shown in Table 3.

  In the composition of the sample of the present invention using the magenta and cyan couplers according to the present invention, the combination with the rapid processing composition of the present invention has a feature that the high-concentration part is not easily lowered even after raw sample storage, and the running process Small changes in photographic gradation that sometimes occur.

Example 2
Process B
Samples 100 and 105 of Example 1 were processed into a 127 mm wide roll, and a standard photographic image was exposed using a minilab printer processor Frontier 340 (sheet transport speed of 28 mm / second) manufactured by Fuji Photo Film Co., Ltd. Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank.

Evaluation according to Example 1 was performed except that the sample of Example 1 was developed under the following conditions.
Processing step Temperature Time Replenishment amount Color development 43.0 ° C 25.5 seconds 45 mL / m ²
Bleach fixing 40.0 ° C. 25.5 seconds 35 mL / m ²
Rinse 1 40.0 ° C. 7.3 seconds −
Rinse 2 40.0 ° C. 3.5 seconds −
Rinse 3 40.0 ° C 3.5 seconds-
Rinse 4 40.0 ° C. 7.2 seconds 175 mL / m ²
Drying 80 ° C 26 seconds

Process C
Samples 100 and 105 of Example 1 were processed into a 127 mm width roll, and Fuji Photo Film Co., Ltd. minilab printer processor Frontier 340 (sheet conveyance speed set to 16 mm / second, processing time for each step is shown below. ) Was used to expose a standard photographic image, and then subjected to continuous processing (running test) in the following processing steps until the volume of the color developer replenisher was twice the volume of the color developer tank.

Processing process Temperature Time Replenishment amount Color development 38.5 ° C 45 seconds 45 mL
Bleach fixing 38.0 ° C 45 seconds 35 mL
Rinse 1 38.0 ° C 13 seconds-
Rinse 2 38.0 ° C. 6.2 seconds −
Rinse 3 38.0 ° C. 6.2 seconds −
Rinse 4 38.0 ° C 12.7 seconds 175 mL
Drying 80 ° C 45.9 seconds

  For sample 100 and sample 105, one set of samples was stored at 25 ° C. and 55% RH for 5 days after application, and then stored frozen at −5 ° C. Similarly, another set of samples was stored at 25 ° C. and 55% RH for 7 days after coating, and then stored frozen at −5 ° C. Another set of samples was stored at 25 ° C. and 55% RH for 10 days after application. The above samples were evaluated simultaneously.

(Evaluation 3) <Scratch resistance when wet>
Each sample was exposed to uniform white light. The exposed sample was immersed in a color developer, and after 30 seconds, the coated surface was scratched by applying a load in increments of 10 g from 50 to 200 g with a sapphire needle having a spherical tip of 0.8 mm. The minimum mass damaged by this test was taken as the evaluation value of the film strength. A larger value indicates higher film strength.

(Evaluation 4) <Film surface scratch evaluation with actual machine>
Each sample was exposed to uniform white light. As the sample after the exposure, a black sample was prepared by the processing steps of processing A and processing C shown in Example 1. The scratch on the black surface of this sample was visually observed.

(Evaluation 5) <Difference between processing of maximum gray density>
Two exposures were given to each sample with uniform white light. The sample which completed exposure produced the black sample by the process process of the process A, the process B, and the process C. FIG. The G concentration of these black samples was measured by X-rite (status A). The change rate (DA / DC) of the density | concentration of the process A with respect to the process C and the change rate (DA / DC) of the density | concentration of the process A with respect to the process B were calculated | required. The closer these values are to 1.0, the more constant the black density is between processes.
The results are shown in Table 4.

  In the processing C in which the development processing time and the drying time are longer than the preferable time of the present invention, scratch evaluation is the same in both of the present invention and the comparative sample, but in the processing A which is a preferred embodiment, the present invention. This sample was superior in scratch evaluation to the comparative sample. Further, the maximum density (gray) obtained by developing the sample of the present invention by the processing A is almost the same as the processing B or the processing C, and the difference between the processings is small. When the length was short, the difference between the treatments was large.

Example 3
Samples 301 and 302 described below were prepared. As a result of development processing according to processing A shown in Example 1 and evaluation according to Example 1, the same effect as that of the present invention example in Example 1 was obtained.
-Preparation of sample 301-
A sample 301 was manufactured by changing the configuration of the third layer and the fifth layer in the sample 105 as follows.

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
Magenta coupler (Ma-48) 0.21
Oleyl alcohol 0.33
Color image stabilizer (ST-1) 0.04
Color image stabilizer (ST-2) 0.28

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.15
Gelatin 0.95
Cyan coupler (IC-23) 0.30
Ultraviolet absorber (UV-5) 0.36
Dibutyl sebacate 0.44
Tris (2-ethylhexyl) phosphate 0.15

-Preparation of sample 302-
A sample 302 was manufactured by changing the configuration of the third layer and the fifth layer as follows with respect to the sample 105.

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
AI-2 0.01
Magenta coupler (Ma-49) 0.20
Color image stabilizer (ST-1) 0.10
Color image stabilizer (ST-3) 0.02
Di-i-decyl phthalate 0.10
Dibutyl phthalate 0.10

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.15
Gelatin 0.95
Cyan coupler (ExC-4) 0.20
Cyan coupler (IC-29) 0.10
Color image stabilizer (ST-4) 0.06
2,5-di-t-octylhydroquinone 0.003
Dibutyl phthalate 0.10
Dioctyl phthalate 0.20

It is the schematic which shows an example of the printer processor used for this invention. It is a schematic front view which shows the structure of an example of the drying part of the printer processor used for this invention. It is a schematic side view which shows the structure of an example of the drying part of the printer processor used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 2 Printer processor 3 Printer part 4 Processor part 5 Magazine 6 Cutter 7 Back printing part 8 Exposure part 9 Sorting part 10 Strip | belt-shaped photosensitive material 10a Photosensitive material 10b Image recording surface 11 Development processing part 12 Squeeze part 13 Drying part 14 Sorter part 15 Conveyance Route 16 Developing tank 17 Bleach fixing tank 18 First water washing tank 19 Second water washing tank 29 Third water washing tank 21 Fourth water washing tank 22 Conveying track 23 Conveying roller pair 24 Submerged squeeze part 31 Drying chamber 32 Blower duct 33 Guide plate 33a Photosensitive material side surface 34 Heater 35 Blower 36 Temperature controller 37 System controller 38 Nozzle 38a Nozzle 40 Conveying track 41 Squeeze roller pair 42 Squeeze roller pair 43 Conveying belt 44 Roller 46 First conveying roller 47 Second conveying roller 48 Third conveying roller 52 Degree sensor 55 key input unit 56 display 61 photosensitive material arrival time search section 62 memory 63 comparison section 64 drying set temperature arrival time search section 65 timing controller 67 external temperature and humidity sensor 68 optimum drying temperature setting retrieval unit

Claims (10)

Blue-sensitive silver halide emulsion layer containing yellow dye-forming coupler, green-sensitive silver halide emulsion layer containing magenta dye-forming coupler, red-sensitive silver halide emulsion layer containing cyan dye-forming coupler, and non-photosensitive hydrophilic A silver halide color photographic light-sensitive material having a photographic composition layer composed of at least one colloid layer is subjected to sheet-shaped cutting and imagewise exposure, and then conveyed by a pair of conveyance rollers while being developed by a color color development process and a bleach-fixing process. , A color image forming method formed through a development process including a rinsing step and a drying step, wherein the silver halide color photographic light-sensitive material is represented by the following general formula (M-I) and a dye-forming coupler represented by the following general formula Each containing at least one dye-forming coupler represented by the formula (IA) and 40.0 m in the development processing step A color image characterized in that the photosensitive material is transported at a speed of not less than 100 mm / second and the color color development process is completed within 18 seconds, the bleach-fixing process is completed within 18 seconds, and the drying process is completed within 26 seconds. Forming method.

(In the general formula (MI), R ₁ , R ₂ , and R ₃ each independently represents a hydrogen atom or a substituent. Za and Zb are either a hydrogen atom or a carbon atom having a substituent, The other represents a nitrogen atom, and the substituent of Za or Zb may further have a substituent, and X is a hydrogen atom or a group capable of leaving in the reaction with an oxidized form of an aromatic primary amine color developing agent. Represents.)

(In the general formula (IA), R ′ and R ″ each independently represent a substituent, and Z is removable in a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group.)   The tank used in the rinsing step is a tank having a multi-chamber structure partitioned by a blade-like member for allowing the photosensitive material cut into a sheet shape to pass in the horizontal direction in the liquid. 2. A color image forming method according to 1.   The color image forming method according to claim 1, wherein a conveyance speed in the development processing is a speed of 45.0 mm / second or more and 95 mm / second or less. The dye-forming coupler represented by the general formula (M-I) is a dye-forming coupler represented by the following general formula (M-III). Color image forming method.

(In the general formula (M-III), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. X represents a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group capable of leaving in the reaction.) 5. The hydrophilic colloid layer of the silver halide color photographic light-sensitive material is made of gelatin substantially hardened by a hardener represented by the following general formula (I). A color image forming method according to claim 1.

(In the general formula (I), X ¹ and X ² each independently -CH = CH ₂ or, represents one of -CH ₂ CH ₂ Y, X ¹ and X ² are different even in the same Wherein Y represents a group that can be substituted by a nucleophilic group or can be eliminated in the form of HY by a base, L is a divalent linking group and may be substituted.) After the imagewise exposure, a color color developing process of 18 seconds or less, a bleach-fixing process of 18 seconds or less, a rinsing process and 26 while being conveyed in a sheet form by a conveying roller at a conveying speed of 40.0 mm / second to 100 mm / second. A silver halide color photographic light-sensitive material for high-speed sheet conveyance that forms a color image through a development processing step including a drying step within a second, wherein the silver halide color photographic light-sensitive material is represented by the following general formula (M-I) A silver halide color photographic light-sensitive material for conveying a high-speed sheet, which contains at least one dye-forming coupler represented by the following general formula (IA):

(In the general formula (MI), R ₁ , R ₂ , and R ₃ each independently represents a hydrogen atom or a substituent. Za and Zb are either a hydrogen atom or a carbon atom having a substituent, The other represents a nitrogen atom, and the substituent of Za or Zb may further have a substituent, and X is a hydrogen atom or a group capable of leaving in the reaction with an oxidized form of an aromatic primary amine color developing agent. Represents.)

(In the general formula (IA), R ′ and R ″ each independently represent a substituent, and Z is removable in a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group.)   The high speed according to claim 6, wherein the tank used in the rinsing step is a tank having a multi-chamber structure in which the chambers are partitioned by a blade-like member, and passes through the tank in a horizontal direction in the liquid. Silver halide color photographic material for sheet conveyance.   The silver halide color photographic light-sensitive material for high-speed sheet conveyance according to claim 6 or 7, wherein the conveyance speed is 45.0 mm / second or more and 95 mm / second or less. The dye-forming coupler represented by the general formula (M-I) is a dye-forming coupler represented by the following general formula (M-III). Silver halide color photographic light-sensitive material for high-speed sheet conveyance.

(In the general formula (M-III), R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a substituent. X represents a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Represents a group capable of leaving in the reaction.) 10. The hydrophilic colloid layer of the silver halide color photographic light-sensitive material is made of gelatin substantially hardened with a hardener represented by the following general formula (I). 2. A silver halide color photographic light-sensitive material for high-speed sheet conveyance according to item 1.

(In the general formula (I), X ¹ and X ² each independently -CH = CH ₂ or, represents one of -CH ₂ CH ₂ Y, X ¹ and X ² are different even in the same Wherein Y represents a group that can be substituted by a nucleophilic group or can be eliminated in the form of HY by a base, L is a divalent linking group and may be substituted.)

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