JP2003330134A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method in which a silver halide color photographic sensitive material is rapidly processed under low replenishment after laser scanning exposure and which is suitable particularly for a color print. <P>SOLUTION: In the image forming method, a silver halide emulsion containing at least one selected form the metal complexes represented by the formula [IrXI<SB>n</SB>LI<SB>(6-n)</SB>]<SP>m-</SP>and having ≥90 mol% silver chloride content is comprised in at least one of photosensitive silver halide emulsion layers. In the formula, XI is a halogen ion or a pseudo-halogen ion other than a cyanate ion; LI is an arbitrary ligand different from XI; n is an integer of 3-5; and m is an integer of -4 to +1. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide color photographic light-sensitive material, and more particularly to an image forming method using a silver halide color photographic light-sensitive material suitable for digital exposure. The present invention relates to an image forming method having excellent pressure characteristics and photographic characteristics when subjected to scanning exposure and low replenishment processing.

[0002]

2. Description of the Related Art In recent years, digitalization has been remarkably permeated even in the field of color printing using color photographic paper. For example, the digital exposure method by laser scanning exposure can be applied to a color printer from a processed color negative film which has been conventionally used. Compared to the analog exposure method that directly prints, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that a high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color printing paper. Further, with the rapid spread of digital cameras, it is also an important factor that color prints of high image quality can be easily obtained from these electronic recording media, and it is considered that these will lead to further dramatic spread.

On the other hand, as the color printing method, techniques such as an ink jet method, a sublimation method, and a color xerography have made progress, and the color printing method is being recognized as a color printing method. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image fastness, and these characteristics are further extended to make higher quality photographs easier and easier. It is desired to provide it at a lower cost. In particular, if you receive the recording medium of a digital camera at the store and finish high-quality prints within a short time of about a few minutes and return it on the spot, that is, if you can provide a one-stop service for color printing, color printing paper The superiority of printing is increasing. Further, if the rapid processability of color photographic paper is improved, it is possible to use a printing apparatus that is smaller and cheaper and has high productivity, and it can be expected that the one-stop service for color printing will become more popular. From these points,
In particular, it is important to enhance the rapid processability of color photographic paper.

In order to enable a one-stop service for color printing using color printing paper, the exposure time is shortened, the so-called latent image time from the exposure to the start of processing is shortened, and the time from processing to drying is shortened. It is necessary to study from various viewpoints such as the above, and it has been proposed from each viewpoint from the past. Among these, the time required to expose one print is much shorter than that of the other, and in the case of ordinary printer capacity used in stores, there is almost no problem.
The latent image time is designed to be as short as possible with the printer. Also, the time from processing to drying has been shortened, and proposals for rapid processing have been made by processing solution composition, processing temperature, stirring conditions of processing solution, ironing of photosensitive materials, devising of drying method, etc. ing.

Further, with rapid processing, there are various problems such as jamming with respect to the transportability of the photosensitive material of the automatic development processing apparatus. In JP-A-11-327109, regarding the material of the nip roller, the SEBS elastomer having a high friction coefficient is used. It is disclosed that the transport performance is improved by use.

Incidentally, as a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is usually used because of the demand for rapid processability. It has been disclosed that various metal complexes are contained in this silver halide emulsion having a high silver chloride content. In order to improve the high-illuminance failure of silver chloride emulsion and obtain hard gradation even in high-illuminance I
It is known to dope r complexes. For example, Japanese Patent Publication No. 34103/1995 discloses that the problem of latent image sensitization is solved by providing a localized phase having a high silver bromide content and doping it with an Ir complex. U.S. Pat. No. 4,9
No. 33,272 discloses that low illuminance failure can be reduced by incorporating a metal complex containing NO or NS as a ligand. US Pat. No. 5,360,71
No. 2, No. 5,457,021 and No. 5,46.
No. 2,849 discloses that reciprocity law failure can be reduced by incorporating a metal complex containing a specific organic ligand into the ligand. US Pat. No. 5,372,926
No. 5,255,630, No. 5,255,45
No. 1, No. 5,597,686, No. 5,480,7
No. 71, No. 5,474,888, No. 5,500,
No. 335, No. 5,783,373 and No. 5,7.
No. 83,378 discloses that a combination of an Ir complex and a metal complex containing NO as a ligand can improve performances such as reciprocity law characteristics of a high silver chloride emulsion. JP 2000-
250156, 2001-92066 and 2
No. 002-31866 discloses an emulsion technique which is excellent in latent image stability after exposure by using an Ir complex and a Rh complex together.

Further, JP-A-58-95736 and 58-58
-108533, 60-222844, and 60
-222845, 62-253143, 62-
No. 253144, No. 62-253166, No. 62-2
54139, 63-46440, 63-464.
41, 63-89840, U.S. Pat. No. 4,82.
No. 0,624, No. 4,865,962, No. 5,3
No. 99,475, No. 5,284,743, etc., high sensitivity can be obtained by locally containing a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. Is disclosed.

Further, US Pat. Nos. 5,726,005 and 5,736,310 disclose high sensitivity and high illuminance by using an emulsion containing I having a maximum concentration on the sub-surface of a high silver chloride emulsion. It is disclosed that an emulsion with less failure can be obtained. In the examples of European Patent EP 0,928,988A, reciprocity law failure, temperature dependence during exposure, and pressure dependence were exhibited by incorporating a specific compound into the particles forming the I band at 93% of the time of particle formation. It is disclosed that an excellent emulsion can be obtained.

However, these known techniques have 12 problems.
The improvement of the pressure sensitizer when the laser scanning exposure is performed with a short latent image time of subsecond or less is not discussed.

[0010]

Therefore, in order to meet the requirements of digital exposure, low replenishment, and rapid processing, we have a short latent image time of less than 12 seconds after laser scanning exposure of color photographic paper and low replenishment. A study was conducted to perform the treatment. However, it has become clear that magenta sensitizing muscles are particularly generated when running the photosensitive material to a certain extent or more, which causes a problem. It was also found that such sensitizing muscles were remarkable when laser scanning exposure was performed.

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to solve the above-mentioned conventional problems and achieve the following objects.
That is, the object of the present invention is to carry out a short latent image time and a low replenishment rapid process after laser scanning exposure of a silver halide color photographic light-sensitive material, which is excellent in pressure property and always provides stable photographic performance. An object of the present invention is to provide an image forming method suitable for color printing.

[0012]

Means for Solving the Problems The inventors have conducted various studies to solve the above problems, and have developed a silver halide color photographic light-sensitive material containing a silver halide emulsion containing a specific metal complex with a laser. The present invention was found to have excellent pressure resistance and consistently stable photographic performance by performing a short latent image time and low replenishment rapid processing after scanning exposure and devising the material of the conveying roller. It was That is, the present invention is
(1) A blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a red photosensitive silver halide emulsion layer containing a cyan dye-forming coupler on a support. And a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of at least one of each of a non-photosensitive hydrophilic colloid layer and imagewise exposed, and then subjected to a development process including a color development process, a bleach-fixing process and a rinse process. In the image forming method, at least one of the photosensitive silver halide emulsion layers is
The layer contains a silver halide emulsion having a silver chloride content of 90 mol% or more containing at least one selected from the metal complexes represented by the following general formula (I), and the imagewise exposure is carried out by laser scanning. Exposure is performed, and the color developing step is started within 12 seconds after the end of the laser scanning exposure,
In the color developing step, the replenishing amount of the color developing solution is ^{20 to} 60 ml per 1 m ^{2 of the} light-sensitive material, and the developing process is performed while the silver halide color photographic light-sensitive material is being conveyed by a conveying roller. As at least one of the transport rollers, styrene-ethylene-butadiene-
An image forming method, characterized in that a roller formed of styrene (SEBS) type elastomer is used.

[0013] In the general formula _{^{(I) [IrX I n L}} I (6-n)] m- ( general formula ^(I), X I is, .L ^I representing the pseudohalogen ion other than halide ion or cyanide ion Represents an arbitrary ligand different from X ^I. n represents an integer of 3 to 5 and m represents an integer of -4 to +1.)

(2) At least one of the silver halide emulsion layers contains a silver halide emulsion having a silver iodide content of 0.005 mol% or more and a silver chloride content of 90 mol% or more. The image forming method as described in (1) above.

(3) In the green-sensitive silver halide emulsion layer containing the magenta dye-forming coupler, the following general formula (I
The image forming method as described in (1) or (2) above, which contains a silver halide emulsion containing a compound represented by I) and having a silver chloride content of 90 mol% or more.

[0016]

[Chemical 1]

(In the general formula (II), X represents halogen. R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group.)

(4) Any of the above (1) to (3), wherein the total amount of coated silver in the photographic constituent layer is 0.2 g / m ² or more and 0.5 g / m ² or less. The image forming method described in 1 ..

(5) 0.5 mg of a compound represented by the following general formula (III) is contained in at least one of the photographic constituent layers.
/ M ² or more, characterized in that (1) ~
The image forming method according to any one of (4).

[0020]

[Chemical 2]

(In the general formula (III), R ₁ represents a hydrogen atom, an alkoxy group, a carboxyl group, a hydroxyl group, or a sulfonic acid group.)

(6) Any one of the above (1) to (5), wherein the total amount of coated gelatin in the photographic constituent layers is 3 g / m ² or more and 5.8 g / m ² or less. Image forming method.

(7) The silver halide emulsion contained in the photosensitive silver halide layer is a silver halide emulsion having a sphere-equivalent diameter of 0.6 μm or less.
The image forming method according to any one of (6).

(8) The transport linear velocity of the silver halide color photographic light-sensitive material in the development processing is 25 to 80 m.
The image forming method according to any one of (1) to (7) above, wherein the image forming method is m / sec.

(9) The image forming method described in any one of (1) to (8) above, wherein the color developing step is performed in 28 seconds or less.

(10) The image formation according to any one of (1) to (9), wherein the general formula (I) is selected from the metal complexes represented by the following general formula (IA). Method.

General formula (IA) [IrX ^IA _n L ^IA _(6-n) ] ^m- (In the general formula (IA), X ^IA represents a halogen ion or a pseudohalogen ion other than a cyanate ion. L ^IA represents X ^IA
Represents any inorganic ligand different from. n; represents an integer of 3 to 5. m represents an integer of -4 to +1. )

(11) The image forming method according to any one of (1) to (9), wherein the general formula (I) is selected from the metal complexes represented by the following general formula (IB). .

General formula (IB) [IrX ^IB _n L ^IB _(6-n) ] ^m- (In the general formula (IB), X ^IB represents a halogen ion or a pseudohalogen ion other than a cyanate ion. L ^IB represents A chain structure or a cyclic structure hydrocarbon is represented by a mother structure or a ligand in which a part of carbon atoms or hydrogen atoms of the mother structure is replaced with other atoms or atomic groups, and n is an integer of 3 to 5.
m represents an integer of -4 to +1. )

(12) The image forming method according to any one of (1) to (9), wherein the general formula (I) is selected from metal complexes represented by the following general formula (IC). .

General formula (IC) [IrX ^IC _n L ^IC _(6-n) ] ^m- (In the general formula (IC), X ^IC represents a halogen ion or a pseudohalogen ion other than cyanate ion. L ^IC represents A 5-membered ring ligand, which is a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, provided that any substituent may be present on the carbon atom in the ring skeleton. . N represents an integer of 3 to 5. m represents an integer of -4 to +1.)

(13) The image forming method according to any one of (1) to (9), wherein the general formula (I) is selected from metal complexes represented by the following general formula (ID). .

General formula (ID) [IrX ^ID _n L ^ID _(6-n) ] ^m- (In the general formula (ID), X ^ID represents a halogen ion or a pseudohalogen ion other than cyanate ion. L ^ID represents A 5-membered ring ligand, which represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, provided that any substituent may be present on a carbon atom in the ring skeleton. . N represents an integer of 3 to 5. m represents an integer of -4 to +1.)

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the image forming method of the present invention, a silver halide color photographic light-sensitive material is imagewise exposed and then developed to form an image.

First, a silver halide color photographic light-sensitive material is imagewise exposed on the basis of image information, and a laser scanning exposure method is applied as an exposure method. Specifically, a monochromatic high density such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A digital scanning exposure method using light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The maximum wavelength of the spectral sensitivity of the photosensitive material can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three 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 10 ^−4.
Seconds or less, more preferably 10 ⁻⁶ seconds or less.

As a semiconductor laser light source, specifically, a blue semiconductor laser (2001) having a wavelength of 430 to 450 nm is used.
March, Nichia presentation at the 48th Joint Lecture on Applied Physics), a semiconductor laser (oscillation wavelength: about 940 nm) with LiNbO ₃ S having a waveguide-like inversion domain structure.
470nm blue laser and semiconductor laser (wavelength: about 1060)
nm) having a waveguide-like inversion domain structure
Approximately 53 wavelength converted by O ₃ SHG crystal
0 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (Hitachi type No.
HL6501MG) and the like are preferably used.

In particular, it is preferable to perform imagewise exposure with coherent light of a blue laser having an oscillation wavelength of 430 to 460 nm, and among the blue lasers, it is particularly preferable to use a blue semiconductor laser.

Then, the imagewise exposed silver halide color photographic light-sensitive material is subjected to development processing. For the developing treatment, a silver halide color photographic light-sensitive material is subjected to a color developing step using a color developing solution, a bleach-fixing step using a bleach-fixing solution, and a rinse solution (washing water and / or stabilizing solution).
Is included in the rinsing step (washing water and / or stabilizing step), and the silver halide color photographic light-sensitive material is subjected to development processing by being successively dipped in each processing solution in each step. These development processes are not limited to these, and auxiliary processes such as an intermediate water washing process and a neutralization process can be inserted between the processes. The bleach-fixing step may be performed in one step using a bleach-fixing solution, or may be performed in two steps including a bleaching step using a bleaching solution and a fixing solution and a fixing step.

Here, the time from the end of exposure of the silver halide color photographic light-sensitive material until the leading edge of the silver halide color photographic light-sensitive material in the conveying direction enters the color developing solution, that is,
The time for starting the color development step after imagewise exposure is 12 seconds or less, preferably 9 seconds or less, and particularly preferably 2 seconds or more and 9 seconds or less.

Each of these processing solutions is used while being replenished, and in the present invention, the replenishing amount of the color developing solution is 20 to 60 ml, preferably 20 ml to 50 ml per 1 m ² of the light-sensitive material. The replenishing amount of the bleach-fixing solution is preferably 25 ml to 45 ml and more preferably 25 to 40 ml per 1 m ² of the light-sensitive material. Further, the replenishing amount of the rinse liquid (washing water and / or stabilizing liquid) is preferably 50 ml to 1000 ml in the whole rinse liquid, and further replenished according to the area of the silver halide color photographic light-sensitive material to be developed. You can also

Here, the color development time (that is, the time for performing the color development step) is preferably 45 seconds or less, more preferably 30 seconds or less, further preferably 28 seconds or less, particularly preferably 25 seconds or less 6 seconds or more, Most preferably, it is 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is preferably 45 seconds or less, more preferably 30 seconds or less, and further preferably 25 seconds.
It is not more than 6 seconds and not more than 6 seconds, particularly preferably not more than 20 seconds and not less than 6 seconds. The rinsing (washing or stabilizing) time (that is, the time for performing the rinsing step) is preferably 90 seconds or less, more preferably 30 seconds or less, and further preferably 30 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The color development time is the sum of the time during which the liquid is conveyed in the air (so-called air time). Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. In addition, rinse (washing or stabilizing)
The time means a time (so-called in-liquid time) during which the light-sensitive material is in the rinsing liquid (washing or stabilizing liquid) and then in the liquid for the drying step.

The developing treatment is carried out while the silver halide color photographic light-sensitive material is being conveyed by a conveying roller. In the present invention, at least one of the conveying rollers is styrene.
Rollers made of ethylene-butadiene-styrene (SEBS) based elastomers are used. As the roller formed of SEBS elastomer, for example, a metal pipe made of stainless steel (such as SUS316) is used.
A roller in which a resin layer made of PPE (for example, "Yupiace" manufactured by Mitsubishi Engineering Plastics) or the like and an elastomer layer made of SEBS elastomer (for example, "Lavalon" manufactured by Mitsubishi Chemical Co., Ltd.) are sequentially coated are mentioned. For example, the roller formed of the SEBS elastomer described in JP-A-11-327108 and JP-A-11-327109 can be applied to the present specification as it is. As a transportation method using a transportation roller, for example, a method of guiding and transporting in a U shape in each processing liquid bath is suitably applied, and specifically, for example, JP-A-11-327109.
The development processing system disclosed in FIG. 2 of the publication can be applied to the present specification as it is. Further, in the transportation method using the transportation rollers, a crossover rack structure with a mixing prevention plate attached is preferable in order to shorten the crossover time between the processing liquid baths and prevent mixing of the processing liquids.

In the development process, the silver halide color photographic light-sensitive material preferably has a transport linear velocity of 100 mm / sec or less. It is more preferably 20 to 80 mm / sec, further preferably 25 to 80 mm / sec, further preferably 25 to 50 mm / sec, and particularly preferably 25.
~ 45 mm / sec.

The amount of rinsing liquid depends on the characteristics of the light-sensitive material (for example, depending on the material used, such as coupler), application, rinsing liquid (washing water) temperature, number of rinsing liquids (washing tank) (number of stages), and various other conditions. It can be set in a wide range. this house,
The relationship between the number of rinse liquid tanks (wash tanks) and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society
Of Motion Picture and Television Visions (Journal of the S
ociety of Motion Picture
and Television Engineers)
Volume 64, p. 248 to 253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of rinsing liquid can be greatly reduced, and the residence time of water in the tank is increased, whereby bacteria propagate and the floating substances formed adhere to the photosensitive material. Therefore, as a solution, a rinse solution containing an antibacterial and antifungal agent described later is preferable.

The developed silver halide color photographic light-sensitive material is then subjected to post-treatments such as a drying step. In the drying process, from the viewpoint of reducing the amount of water carried into the image film of the silver halide color photographic light-sensitive material, it is dried by absorbing the water with a squeeze roller or cloth immediately after the development process (rinsing process). It is also possible to hasten it. Further, as a matter of course, it is possible to accelerate the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Furthermore, JP-A-3-
As described in Japanese Laid-Open Patent Publication No. 157650, the drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material or removing the exhausted air.

In this way, an image is output on the silver halide color photographic light-sensitive material.

Hereinafter, other preferred embodiments of the image forming method of the present invention will be described. The image forming method of the present invention,
It can be preferably used in combination with the exposure and development system described in the following publicly known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000-102.
Japanese Patent Laid-Open No. 11-2 / 1999.
Recording system including the image reading device described in Japanese Patent No. 15312, Japanese Patent Laid-Open No. 11-88619, and Japanese Patent Laid-Open No. 10-8619.
-202950, an exposure system comprising a color image recording system, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and US Pat. No. 6,297,873B1. The photo printing system including the image recording device of

The scanning exposure method is described in detail in the patents listed in Table 1 below.

Further, in imagewise exposure, US Pat.
It is preferable to use the band stop filter described in the specification of No. 80,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. Furthermore, European Patent EP0789270A1 and EP0789480.
As described in the A1 specification, before the image information is given, a yellow microdot pattern is pre-exposed in advance,
Copying restrictions may be applied.

Further, in the developing process, Japanese Patent Laid-Open No. 2072/1990 is used.
No. 50, page 26, lower right column, line 1 to page 34, upper right column, line 9, and JP-A-4-97355, page 5, upper left column 1
The processing materials and processing methods described in line 7 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in this developer, compounds described in the patents listed in Table 1 below are preferably used.

Typically, as a color development processing, a minilab "PP350" manufactured by Fuji Photo Film Co., Ltd. and CP48S chemical as a processing agent are used, and a photosensitive material is subjected to imagewise exposure from a negative film of an average density to prepare a color development replenisher. There is a method in which processing is performed with a processing solution which has been continuously processed until the capacity becomes twice the capacity of the color developing tank.

The chemical of the treating agent may be CP47L manufactured by Fuji Photo Film Co., Ltd.

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

The light-sensitive material may have an antihalation layer, an intermediate layer and a coloring layer as a non-photosensitive hydrophilic colloid layer described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

The light-sensitive material has a light-sensitive silver halide emulsion layer in order to obtain stable photographic performance with excellent pressure resistance when subjected to a low replenishment rapid processing (development processing) by laser scanning exposure as described above. In at least one layer of the above contains a silver halide emulsion containing at least one selected from the metal complexes represented by the following general formula (I) and having a silver chloride content of 90 mol% or more.

The metal complex represented by the general formula (I) will be described. In the general formula _{^{(I) [IrX I n L}} I (6-n)] m- general formula (I), X ^I represents a pseudohalogen ion other than halide ion or cyanide ion. L ^I represents any ligand different from X ^I. n represents an integer of 3 to 5.
m represents an integer of -4 to +1.

Here, the pseudohalogen (halogenoid) ion is an ion having a property similar to that of a halogen ion, for example, a cyanide ion (CN ⁻ ), a thiocyanate ion (SCN ⁻ ), a selenocyanate ion ( Sec
N ⁻ ), tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), cyanate ion (OC
N ⁻ ), lanthanide ion (ONC ⁻ ), azide ion (N ₃ ⁻ ), and the like.

In formula (I), X ^I is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or ,
It is an azide ion, particularly preferably a chloride ion and a bromide ion. For L ^I ,
There is no particular limitation as long as it is an arbitrary ligand different from X ^I, and may be an inorganic compound or an organic compound,
It may be charged or uncharged, but is preferably an uncharged inorganic compound or organic compound.

Among the metal complexes represented by the general formula (I), the metal complexes represented by the following general formula (IA) are preferable. In the general formula _{^{(IA) [IrX IA n L}} IA (6-n)] m- formula ^(IA), X IA represents a pseudohalogen ion other than halide ion or cyanide ion. L ^IA represents any inorganic ligand different from X ^IA . n; represents an integer of 3 to 5. m represents an integer of -4 to +1.

In formula (IA), X ^IA has the same meaning as X ^{I in} formula (I), and the preferred range is also the same. L ^IA is preferably water, OCN, ammonia, phosphine,
Carbonyl is preferable, and water is particularly preferable. Here, 3 to 5 X ^IA may be the same or different from each other,
Also, if the L ^IA there are a plurality, a plurality of L ^IA may be the same or different from each other.

Among the metal complexes represented by the general formula (I), the metal complexes represented by the following general formula (IB) are more preferable. In the general formula _{^{(IB) [IrX IB n L}} IB (6-n)] m- formula ^(IB), X IB represents a pseudohalogen ion other than halide ion or cyanide ion. L ^IB represents a ligand in which a chain or cyclic hydrocarbon has a mother structure or a part of carbon or hydrogen atoms of the mother structure is replaced with another atom or atomic group. n represents an integer of 3 to 5. m
Represents an integer of -4 to +1.

In formula (IB), X ^IB has the same meaning as X ^{I in} formula (I), and the preferred range is also the same. L ^IB represents a ligand in which a chain or cyclic hydrocarbon is a parent structure or a part of carbon or hydrogen atoms of the parent structure is replaced with another atom or atomic group, but does not include cyanide ion . A heterocyclic compound is preferable as L ^IB , more preferably a complex having a 5-membered ring compound as a ligand.
Among the member ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in the 5-membered ring skeleton is more preferable. Here, three to five X ^IB may be the same or different from each other, also, if the L ^IB there are a plurality, a plurality of L ^IB may be the same or different from each other.

Among the metal complexes represented by the general formula (I), the metal complex represented by the following general formula (IC) is more preferable. General formula (IC) [IrX ^IC _n L ^IC _(6-n) ] ^{m-In the} general formula (IC), X ^IC represents a halogen ion or a pseudohalogen ion other than a cyanate ion. L ^IC is a 5-membered ring ligand and represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton. However,
It may have optional substituents on carbon atoms in the ring skeleton. n
Represents an integer of 3 to 5. m represents an integer of -4 to +1.

In formula (IC), X ^IC has the same meaning as X ^{I in} formula (I), and the preferred range is also the same. As the optional substituent on the carbon atom in the ring skeleton in L ^IC ,
A substituent having a smaller volume than that of the n-propyl group is preferable. As a substituent, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, a thioformyl group, a hydroxy group, a mercapto group, an amino group, a hydrazino group. Preferred are azido group, nitro group, nitroso group, hydroxyamino group, carboxyl group, carbamoyl group, fluoro group, chloro group, bromo group and iodo group. Here, three to five X ^IC may be the same or different from each other, if the L ^IC there are a plurality, a plurality of L ^IC may be the same or different from each other.

Among the metal complexes represented by the general formula (I), the metal complex represented by the following general formula (ID) is particularly preferable.

General formula (ID) [IrX ^ID _n L ^ID _(6-n) ] ^{m-In the} general formula (ID), X ^ID represents a halogen ion or a pseudohalogen ion other than a cyanate ion. L ^ID is a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton. However,
It may have optional substituents on carbon atoms in the ring skeleton. n
Represents an integer of 3 to 5. m represents an integer of -4 to +1.

X ^ID has the same meaning as X ^{I in} formula (I),
The preferred range is also the same. A compound having a thiadiazole skeleton as the L ^ID is preferable, provided that a substituent other than hydrogen is bonded to the carbon atom in the compound. As the optional substituent on the carbon atom in the ring skeleton in L ^ID , halogen (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group,
Chloroformyl group, mercapto group, methylthio group, thioformyl group, thiocarboxy group, dithiocarboxy group,
Sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyanato group, cyanato group, isocyanato group, thiocyanato group, isocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso group, nitro group, hydrazino group , A hydrazono group or an azido group, more preferably halogen (fluorine, chlorine, bromine, iodine), a chloroformyl group, a sulfino group, a sulfo group, a sulfamoyl group, an isocyano group,
It is a cyanato group, an isocyanato group, a thiocyanato group, an isocyanato group, a hydroxyimino group, a nitroso group, a nitro group, or an azido group. Among them, chlorine, bromine, chloroformyl group, isocyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group and isocyanato group are particularly preferable. n is preferably 4 or 5, and m is preferably -2 or -1. Where 3-5
The X ^IDs may be the same or different from each other, and L ^ID
When there are a plurality of L ^IDs , the plurality of L ^IDs may be the same as or different from each other.

Specific preferred examples of the metal complex represented by the general formula (I) are shown below, but the invention is not limited thereto. [IrCl ₅ (H ₂ O)] ^2- [IrCl ₄ (H ₂ O) ₂ ] ^- [IrCl ₅ (H ₂ O)] ^- [IrCl ₄ (H ₂ O) ₂ ] ⁰ [IrCl ₅ (OH)] ^3- [IrCl ₄ (OH) ₂ ] ^2- [IrCl ₅ (OH)] ^2- [IrCl ₄ (OH) ₂ ] ^2- [IrCl ₅ (O)] ^4- [IrCl ₄ (O) ₂ ] ^5- [IrCl ₅ (O)] ^3- [IrCl ₄ (O) ₂ ] ^4- [IrBr ₅ (H ₂ O)] ^2- [IrBr ₄ (H ₂ O) ₂ ] ^- [IrBr ₅ (H ₂ O)] ^- [IrBr ₄ (H ₂ O) ₂ ] ⁰ [IrBr ₅ (OH)] ^3- [IrBr ₄ (OH) ₂ ] ^2- [IrBr ₅ (OH)] ^2- [IrBr ₄ (OH) ₂ ] ^2- [IrBr ₅ (O)] ^4- [IrBr ₄ (O) ₂ ] ^5- [IrBr ₅ (O)] ^3- [IrBr ₄ (O) ₂ ] ^4- [IrCl ₅ (OCN)] ^3- [IrBr ₅ (OCN)] ^3- [IrCl ₅ (thiazole)] ^2- [IrCl ₄ (thiazole) ₂ ] ^- [IrCl ₃ (thiazole) ₃ ] ⁰ [IrBr ₅ (thiazole)] ^2- [IrBr ₄ (thiazole) ₂ ] ^- [IrBr ₃ (thiazole) ₃ ] ⁰ [IrCl ₅ (5-methylthiazole)] ^2- [IrCl ₄ (5-methylthiazole) ₂ ] ^- [IrBr ₅ (5-methylthiazole)] ^2- [IrBr ₄ (5-methylthiazole) ) ₂ ] ^- [IrCl ₅ (5-chlorothiadizole)] ^2- [IrCl ₄ (5-chlorothiadizole) ₂ ] ^- [IrBr ₅ (5-chlorothiadizole)] ^2- [IrBr ₄ (5-chlorothiadizole) ₂ ] ^- [IrCl ₅ (2-chloro-5-fluorothiadiazole)] ^2- [IrCl ₄ (2-chloro-5-fluorothiadiazole) ₂ ] ^- [IrBr ₅ (2-c hloro-5-fluorothiadiazole)] ^2- [IrBr ₄ (2-chloro-5-fluorothiadiazole) ₂ ] ^- [IrCl ₅ (2-Bromo-5-chlorothiadiazole)] ^2- [IrCl ₄ (2-Bromo-5-chlorothiadiazole) ) ₂ ] ^- [IrBr ₅ (2-Bromo-5-chlorothiadiazole)] ^2- [IrBr ₄ (2-Bromo-5-chlorothiadiazole) ₂ ] ^-

In addition to the metal complex represented by the general formula (I), it is preferable to use a metal complex represented by the following general formula (I ') in combination.

The metal complex represented by the general formula (I ') will be described. General formula (I ') [MX ^II _n L ^II _(6-n) ] ^m-In general formula (I'), M is Cr, Mo, Re, Fe, R.
It represents u, Os, Co, Rh, Pd, or Pt. X ^II represents a halogen ion. L ^II represents any ligand different from X ^II . n represents an integer of 3 to 6. m is -4 to +1
Represents the integer.

In the general formula (I '), X ^II is preferably a fluoride ion, a chloride ion, a bromide ion or an iodide ion, and among them, a chloride ion and a bromide ion are particularly preferable. . L ^II may be an inorganic compound or an organic compound as long as it is an arbitrary different ligand, and may have a charge or no charge, but is an uncharged inorganic compound. It is preferable. L ^II is preferably H ₂ 0, NO or NS.

Among the metal complexes represented by the general formula (I ′), the metal complexes represented by the following general formula (I′A) are preferable. Formula ^{(I'A) [M IIA X IIA} n L IIA (6-n)] m- general formula (I'A), M ^IIA; represents a Re, Ru, Os, or Rh. X ^IIA represents a halogen ion. L ^IIA is M
^{When IIA} is Re, Ru or Os, it represents NO or NS, and when M ^IIA is Rh, it represents H ₂ O, OH or O. n
Represents an integer of 3 to 6. m represents an integer of -4 to +1.

In the general formula (I′A), X ^IIA is the same as X ^{II in the} general formula (I ′).

Specific preferred examples of the metal complex represented by the general formula (I ') are shown below, but the invention is not limited thereto. [ReCl ₆ ] ^2- [ReCl ₅ (NO)] ^2- [RuCl ₆ ] ^2- [RuCl ₆ ] ^3- [RuCl ₅ (NO)] ^2- [RuCl ₅ (NS)] ^2- [RuBr ₅ (NS )] ^2- [OsCl ₆ ] ^4- [OsCl ₅ (NO)] ^2- [OsBr ₅ (NS)] ^2- [RhCl ₆ ] ^3- [RhCl ₅ (H ₂ O)] ^2- [RhCl ₄ (H ₂ O) ₂ ] ^- [RhBr ₆ ] ^3- [RhBr ₅ (H ₂ O)] ^2- [RhBr ₄ (H ₂ O) ₂ ] ^- [PdCl ₆ ] ^2- [PtCl ₆ ] ^2-

Here, the metal complexes represented by the general formulas (I) to (I ') are anions, and when forming a salt with a cation, those which easily dissolve in water as the counter cation are preferable. Specifically, sodium ions, potassium ions, rubidium ions, alkali metal ions such as cesium ions and lithium ions, ammonium ions,
Alkyl ammonium ions are preferred. These metal complexes should be used by dissolving them in a mixed solvent of water and an appropriate organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). You can The metal complex represented by the general formula (I) is preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻³ mol per 1 mol of silver during grain formation, and preferably 1 × 10 ⁻⁸ to 1 × 10 3. It is most preferable to add ^-5 mol. The metal complex represented by the general formula (I ′) is a silver complex during grain formation.
It is preferable to add 1 × 10 ⁻¹¹ to 1 × 10 ⁻⁶ mol, and most preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁷ mol per mol.

The metal complexes represented by the general formulas (I) to (I ') are added directly to the reaction solution at the time of silver halide grain formation, or in a halide aqueous solution for forming silver halide grains, Alternatively, it is preferably incorporated into the silver halide grain by adding it to a solution other than that and adding it to the grain forming reaction solution. It is also preferable to physically ripen fine particles in which a metal complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

When the metal complexes represented by the general formulas (I) to (I ') are incorporated into silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-20893
6, JP-A-2-125245, JP-A-3-1884.
As disclosed in JP-A No. 37, it is also preferable to make it exist only in the particle surface layer, and it is also preferable to make the complex exist only inside the particle and to add a layer not containing the complex to the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical aging of fine particles in which a complex is incorporated to modify the surface phase of the particles. Is also preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain.

In the light-sensitive material, the content of silver chloride containing a compound represented by the following general formula (II) as a spectral sensitizing dye in the green light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler. Although it contains 90 mol% or more of silver halide emulsion, it is preferable from the viewpoint of more effectively improving the pressure property and obtaining stable photographic performance. The addition amount of the compound represented by the following general formula (II) is 1 × 10 ⁻⁶ to 1 per mol of silver halide in the emulsion layer containing the compound.
It is preferably × 10 ^-3 mol.

[0081]

[Chemical 3]

In the general formula (II), X represents halogen. R
₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group.

In the general formula (II), X is specifically C
l, Br, I. Preferable examples of the alkyl group represented by R ₁ and R ₂ include an ethyl group, a methyl group, a butyl group, a propyl group and the like, and a preferable example of the substituent substituted on the alkyl group is a sulfo group. And R
_A sulfoalkyl group is preferable as ₁ and R ₂ .

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

[0085]

[Chemical 4]

The silver halide emulsion will be described in more detail below. The grain shape of the silver halide emulsion is not particularly limited, but it is a cubic or 14-sided crystal grain having substantially {100} faces (these grains have rounded vertices and higher-order faces). It is also preferable), octahedral crystal grains, and tabular grains having an aspect ratio of 3 or more whose main surface is a {100} plane or a {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles.

The silver chloride content of the silver halide emulsion must be 90 mol% or more. From the viewpoint of rapid processability,
The silver chloride content is preferably 93 mol% or more, and 95 mol%
The above is more preferable. The silver bromide content is preferably 0.1 to 7 mol% and more preferably 0.5 to 5 mol% because it has a high contrast and excellent latent image stability. The silver iodide content is 0.0 from the viewpoint of improving the magenta sensitizing muscle of the present invention, and because it has high sensitivity and high contrast at high illuminance exposure.
It is preferably 2-1 mol%, and 0.05-0.5.
0 mol% is more preferable, and 0.07 to 0.40 mol% is most preferable. The silver halide grains are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride emulsions (grains) having the above halogen composition.

The silver halide emulsion (grain) 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 that of the surrounding area.
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 is
A layer having a substantially constant concentration may be formed at a certain portion within the particle, or a local maximum point without spreading may be formed. 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 0.3.
It is preferably at least mol%, more preferably from 0.5 to 8 mol%, most preferably from 1 to 5 mol%. Further, such a silver bromide- or silver iodide-containing phase may be present in a plurality of layers in each grain,
The respective silver bromide or silver iodide contents may differ, but each must have at least one contained phase.

It is important that the silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion is in a layered form so as to surround the grains. One of the preferred embodiments is that the silver bromide-containing phase or the silver iodide-containing phase formed in a layer surrounding the grains has a uniform concentration distribution in the orbiting direction of the grains in each phase. However, in the silver bromide-containing phase or the silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when the layer has a silver bromide-containing phase or a silver iodide-containing phase near the surface of the grain so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases. Also,
In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, a silver bromide-containing phase or an iodide that does not completely surround the grain and exists in a specific part of the surface of the grain. There may be a silver halide containing phase.

When the silver halide emulsion contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in layers so that the silver bromide concentration maximum is present inside the grains. When the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in layers so that the grain surface has a maximum silver iodide concentration. Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the amount of silver 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 at the same spot or different spots in the grain, but different spots are preferable from the viewpoint of facilitating the control of grain formation. Also,
The silver bromide-containing phase may contain silver iodide, and conversely the silver iodide-containing phase may contain silver bromide. In general, the iodide added during the formation of high silver chloride grains is more likely to exude to the grain surface than bromide, so that the silver iodide-containing phase is likely to be formed in the vicinity of the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different positions in the grain, it is preferable that the silver bromide-containing phase is 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 the silver iodide content necessary for exhibiting the effects of the present invention such as the enhancement of the sensitivity and the increase in the contrast is determined by the silver bromide-containing phase or the silver iodide-containing phase inside the grain. The more it is formed, the more it increases, and the silver chloride content may be unnecessarily reduced to 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 effect near the surface in the grain. From these points, the silver bromide-containing phase is 50% to 100% of the grain volume measured from the inside.
It is preferable that the silver iodide-containing phase is formed at any of positions from 85% to 100% of the grain volume. Further, it is preferable that the silver bromide-containing phase is formed anywhere from 70% to 95% of the grain volume, and the silver iodide-containing phase is formed anywhere from 90% to 100% of the grain volume. preferable.

The introduction of bromide or iodide ion to contain silver bromide or silver iodide in a silver halide emulsion may be carried out by adding a solution of bromide salt or iodide salt alone or by adding a solution of silver bromide or iodide salt and a high solution. A bromide salt or iodide salt solution may be added together with the addition of the chloride salt solution. 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 the bromide salt or iodide salt and the 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 ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight-Secondary
RYIon Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. TOF-SIM
Regarding the S method, specifically, “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by Japan Surface Science Society, Maruzen Co., Ltd. (19
Issued in 1999). Etching / TOF-
When the emulsion grains are analyzed by the SIMS method, it can be analyzed that the iodide ions are seeping out toward the grain surface even if the addition of the iodide salt solution is completed inside the grains. The emulsion of the present invention is analyzed by an etching / TOF-SIMS method,
It is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration decreases inward, and the bromide ion has a maximum concentration inside the grain. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

The silver halide emulsion preferably comprises grains having a monodisperse grain size distribution. The variation coefficient of the spherical equivalent diameter of all grains of the silver halide emulsion is preferably 20% or less, more preferably 15% or less, and 1
It is more preferably 0% or less. The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. Here, in the present specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle.

The equivalent spherical diameter of the silver halide emulsion is 0.6 μm.
It is preferable that the equivalent spherical diameter of the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is 0.6 μm or less, and especially,
It is more preferably 5 μm or less, and most preferably 0.4 μm or less. The equivalent spherical diameter of the silver halide emulsion in the silver halide emulsion layer containing a magenta dye-forming coupler and the silver halide emulsion layer containing a cyan dye-forming coupler is preferably 0.5 μm or less, and 0.4 μm or less.
The thickness is more preferably below, and most preferably 0.3 μm or below. A particle having a sphere equivalent diameter of 0.6 μm corresponds to a cubic particle having a side length of about 0.48 μm, and a sphere equivalent diameter of 0.5.
A particle of μm corresponds to a cubic particle having a side length of about 0.40 μm, a particle having a spherical equivalent diameter of 0.4 μm corresponds to a cubic particle having a side length of about 0.32 μm, and a particle having a spherical equivalent diameter of 0.3 μm has a side length of This corresponds to a cubic particle of about 0.24 μm. For the silver halide emulsion, the silver halide emulsion defined in the present invention includes
In the silver halide emulsion defined in the present invention, 50% or more of the total projected area of all grains is preferably silver halide grains defined in the present invention, more preferably 80% or more, and 90% or more. % Or more is more preferable.

The silver halide emulsion has the general formula (I) above.
In addition to the metal complex represented by (I ′), all six ligands may further contain a metal complex (iridium complex) consisting of Cl, Br or I. In this case, 6
Cl, Br, or I may be mixed in the coordination complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand be contained in the silver bromide-containing phase in order to obtain a hard gradation by high-intensity exposure.

In the following, all 6 ligands were Cl, Br
Specific examples of the iridium complex consisting of I will be given below.
It is not limited to these. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

Other than the above metal complex (iridium complex), other metal ions can be doped inside and / or on the surface of the silver halide grain. The metal ion used is preferably a transition metal ion, of which iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion. It is preferable to use a nitrosyl ion, and it is also preferable to use it by coordinating to any of the above-mentioned metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and to use a plurality of types of ligands in one complex molecule. It is also preferable to use. Further, an organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. . More preferred organic compounds are nitrogen atoms, phosphorus atoms,
A compound having an oxygen atom or a sulfur atom as a coordination atom to a metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine. , Pyrimidine, and pyrazine, and compounds in which these compounds have a basic skeleton and a substituent is introduced into them are also preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a combination of ruthenium ion and a cyanide ion. In the present invention, it is preferable to use the above-mentioned metal complex in combination with these compounds. In these compounds, the cyanide ion preferably occupies the majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably populated with pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. It is preferable to add 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol of each complex containing cyanide ion as a ligand per 1 mol of silver during grain formation, preferably 1 × 10 ⁻⁶ to 5 × 10 3. It is most preferable to add ^-4 mol.

The silver halide emulsion is preferably subjected to gold sensitization known in the art. This is because the gold sensitization can increase the sensitivity of the emulsion and reduce fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like. 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,
As the gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate compound such as potassium dithiocyanate (I) potassium or a compound such as a gold dithiosulfate compound such as trisodium dithiosulfate (I) sodium is used. it can.

Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, for example, bis (1,4,5-trimethyl). -1,2,4-Triazolium-3-thiolate) aurate (I) tetrafluoroborate, an organic mercapto gold (I) complex described in JP-A-11-218870, for example, potassium bis (1-)
[3- (2-Sulfonatobenzamido) 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. As the gold (I) compound having these organic ligands, those synthesized and isolated in advance are used, and in addition, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) are mixed. Due to
It can be added to the emulsion without being generated and isolated. Further, an organic ligand and an Au compound (for example, chloroauric acid or its salt) may be separately added to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.

For silver halide emulsions, the above gold sensitization can be performed by other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound. May be combined with. Especially, it is preferable to combine with sulfur sensitization and selenium sensitization.

Various compounds or precursors thereof are added to the silver halide emulsion for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can As specific examples of these compounds, those described on pages 39 to 72 of JP-A No. 62-215272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

In order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094 are adjacent to each other, and both ends are amino. A cyclic ketone having a double bond in which a group or a hydroxyl group is substituted (particularly represented by the general formula (S1), paragraph number 00
36-0071 can be incorporated into the specification of the present application. ), Sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011 (for example, 4,
5-dihydroxy-1,3-benzenedisulfonic acid,
2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3
-Dihydroxybenzene sulfonic acid, 2,5-dihydroxybenzene sulfonic acid, 3,4,5-trihydroxybenzene sulfonic acid and salts thereof), and general formula (A) of US Pat. No. 5,556,741. Hydroxylamines represented by (US Pat. No. 5,556,741
The description of column 4, line 56 to column 11, line 22 of the specification is preferably applied to the present application and incorporated as a part of the specification of the present application), JP-A-11-102045.
The water-soluble reducing agents represented by the general formulas (I) to (III) in Japanese Patent Laid-Open Publication No. 1993-301 are 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, which exhibits photosensitivity in a desired light wavelength region. Examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include F.I. M. Harmer's Heterocycle
compounds-Cyanine dyesan
d related compounds (John
Wiley & Sons [New York, Lo]
ndon] 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-123 is known.
The spectral sensitizing dye described in JP-A No. 340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependence of exposure and the like.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

The photosensitive material will be described in more detail below. The photosensitive material has the following general formula (II
The amount of the compound represented by I) of 0.5 mg / m ² or more is suitable from the viewpoint of more effectively improving the pressure property and obtaining stable photographic performance.

[0110]

[Chemical 5]

In the general formula (III), R ₁ represents a hydrogen atom, an alkoxy group, a carboxyl group, a hydroxyl group or a sulfonic acid group.

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

[0113]

[Chemical 6]

For the light-sensitive material, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as the photographic support. As the transparent support, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate film, and a polyester or NDCA of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) are used.
A polyester having terephthalic acid and EG and an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of the water resistant resin layers (laminate layer) is preferable.

The light-sensitive material is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc. Among them, it is preferable to use it as a color photographic paper. The color photographic paper preferably comprises at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer, and at least one cyan color forming silver halide emulsion layer. The silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer in order from the support. However, a layer structure different from this may be adopted.

Silver halide emulsion and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material, and processing methods and processing additives applied for processing the light-sensitive material. As the agent, JP-A-62-2152
72, JP-A-2-33144, European Patent E
Those described in P0,355,660A2, especially those described in European Patent EP0,355,660A2 are preferably used. Furthermore,
JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548 and JP-A-4-145433. No. 2-854,
No. 1-158431, No. 2-90145,
No. 3-19439, No. 2-93641,
The silver halide color photographic light-sensitive material described in European Patent Publication No. 0520457A2 and the processing method thereof are also preferable.

In particular, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, and chemical sensitization method. (Sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, and yellow couplers and their emulsion dispersion method, color image storability improving agent (anti-staining agent or anti-fading agent), dye (colored layer) Regarding the gelatin species, the layer constitution of the light-sensitive material and the coating pH of the light-sensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0118]

[Table 1]

Other cyan, magenta and yellow couplers used in the light-sensitive material are disclosed in JP-A-62-2.
No. 15272, 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, end line and page 30 upper right column. Column line 6 to page 35, lower right column, line 11 and EP0355,660A2
No. 4, page 15, line 27 to page 5, page 30, line 30
Page 28 Last line, Page 45 Lines 29-31, Page 47 23
The couplers described in lines 50 to 63, line 50 are also useful.
Further, 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, which is preferable.

A pyrrolotriazole coupler is preferably used as a cyan dye-forming coupler (sometimes simply referred to as "cyan coupler") usable in a light-sensitive material, and it is represented by the general formula (I) in JP-A-5-313324. Or a coupler represented by (II) and JP-A-6-34796.
The couplers represented by formula (I) of JP-A No. 0, as well as the exemplified couplers described in these patents are particularly preferable. Phenol-based and naphthol-based cyan couplers are also preferable, and for example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. As cyan couplers other than the above, European Patents EP0488248 and EP049119
Pyrroloazole-type cyan couplers described in 7A1 and 2,5-described in US Pat. No. 5,888,716.
Diacylaminophenol coupler, US Pat. No. 4,8
73,183 and 4,916,051 and a pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A-8-1
No. 71185, No. 8-311360, No. 8-
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-339060 is also preferable.

In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers described in European Patent EP 0333185A2 (the couplers listed as specific examples ( 42) A 4-equivalent coupler having a chlorine-eliminating group to make it a 2-equivalent compound, or a coupler (6)
And (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8 and 3 listed as specific examples among them).
4 is particularly preferred), European Patent EP 0456226A1
, A pyrrolopyrazole-type cyan coupler described in
The pyrroloimidazole type cyan coupler described in European Patent EP 0484909 can also be used.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-228138 is particularly preferable, and the paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

Examples of magenta dye-forming couplers (sometimes simply referred to as "magenta couplers") usable in the light-sensitive material include 5-pyrazolone-based magenta couplers and pyrazoloazoles described in the above-mentioned table. A magenta coupler is used. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 has a pyrazolotriazole ring of 2, in terms of hue, image stability, color developability and the like. Pyrazolotriazole couplers directly linked to the 3 or 6-positions, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61-147254. And a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described above and European Patent No. 226,84. A Pat and the first 294,785
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in A specification. Particularly, as a magenta coupler, it is disclosed in Japanese Patent Laid-Open No. Hei 8
Pyrazoloazole couplers represented by formula (M-I) described in JP-A-122984 are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application,
It is incorporated as part of the specification of the present application. In addition to this, European Patent No. 854384 and European Patent No. 88464
Pyrazoloazole couplers having a steric hindrance group at both the 3- and 6-positions described in No. 0 are also preferably used.

As the yellow dye-forming coupler (which may be simply referred to as "yellow coupler") usable in the light-sensitive material, in addition to the compounds described in the above table, the acyl group described in European Patent EP 044969A1 is used. Acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure, malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, EP 953870A1 and EP 953871A1. Calligraphy, ibid. 953872
No. A1, No. 953873, No. 9A1, No. 9
No. 5,118,599. Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide type couplers described in US Pat. No. 5,387,5A1 and No. 953875A1. An acylacetamide type yellow coupler having a dioxane structure is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler used in the light-sensitive material is a loadable latex polymer (for example, US Pat. No. 4,2,4) in the presence (or absence) of the high boiling point organic solvent described in the above table.
No. 03,716) or by dissolving with a water-insoluble and organic solvent-soluble polymer to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

As the binder or protective colloid that can be used in the light-sensitive material, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are 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 m.
g / m ² or less.

The light-sensitive material has a calcium content of 1
It is preferably 5 mg / m ² or less. Here, the content of calcium is represented by the weight of calcium ions, atoms or compounds containing calcium contained in 1 m ^{2 of the} light-sensitive material excluding the support, converted into calcium atoms. A known analysis method is used as a method for quantifying the calcium content. For example, in the field of chemistry, special issue No. 127 (Nankodo 1980), V. A. Fassel
, Anal. Chem. , 46, 1110A (19
74) etc., the ICP analysis method described in detail can be used. Calcium contained in the light-sensitive material is brought in as an impurity in gelatin which is usually used as a binder. Calcium salt derived from raw materials and manufacturing process is several thousand ppm converted to calcium atom in gelatin.
include. The calcium content is more preferably 10
mg / m ² or less, more preferably 5 mg / m ² or less, most preferably 2 mg / m ² or less (including 0 mg / m ² ).

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

[0129] in the photosensitive material, the total Coating amount of gelatin photographic constituent layers may be is preferably 3 g / m ² or more 5.8 g / m ² or less, 3 g / m ² or more 5 g / m ² or less More preferable. Further, even in the case of ultra-rapid processing, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be evaluated by measuring the change in film thickness before and after peeling of the dry film or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and further 9 μm in order to achieve both the development progress and the drying speed.
It is preferably -18 μm. The swollen film thickness can be measured by a dot method when the dried photosensitive material is dipped in an aqueous solution at 35 ° C., swollen and sufficiently equilibrated. The total amount of silver coated on the light-sensitive material is 0.2 g.
/ M ^{2 to} 0.5 g / m ² , preferably 0.2 g
Further preferably /m2~0.45g/m ^2,
And most preferably ^{0.2g / m 2 ~0.40g / m 2} .

The developing treatment liquid (color color developing liquid, bleach-fixing liquid, rinsing liquid) applied to the image forming method of the present invention will be described below.

The color developing solution will be described. The color developing solution contains a color developing agent, and preferred examples of the color developing agent are known aromatic primary amine color developing agents, especially p-phenylenediamine derivatives, and typical examples thereof are shown below. It is not limited.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline 6) 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline 7) 4-amino-3-methyl-N-ethyl-N- (4-
Hydroxybutyl) aniline 8) 4-amino-3-methyl-N-ethyl-N- (β-
Methanesulfonamidoethyl) aniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N- (β
-Methoxyethyl) 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-N
-N-Propyl-3-methylaniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypiglysine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroquinmethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Of the above p-phenylenediamine derivatives, the exemplified compounds 5), 6), 7), 8) and 12) are particularly preferable, and among them, the compounds 5) and 8) are preferable. Further, these p-phenylenediamine derivatives are
In the state of solid materials, usually sulfate, hydrochloride, sulfite,
It is in the form of salts such as naphthalene disulfonate and p-toluene sulfonate. The concentration of the aromatic primary amine developing agent is 2 mmol to 200 per liter of the developing solution.
Mmol, preferably 6 to 100 mmol, more preferably 10 to 40 mmol.

A bleach-fixing solution (including a bleaching solution and a fixing solution) will be described. As the bleach used in the bleach-fix solution,
Known bleaching agents can also be used, especially iron (III)
The organic complex salts (for example, complex salts of aminopolycarboxylic acids) or organic acids such as citric acid, tartaric acid, malic acid, persulfates, hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid treatment and prevention of environmental pollution. The addition amount thereof is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter, more preferably 0.10 to 0.50 mol / liter, further preferably 0.15 to 0. It is 0.40 mol / liter.

The fixing agents used in the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, and ethylenebisthioglycolic acid. , 3,6-dithia-1,8-octanediol and other thioether compounds and thioureas and other water-soluble silver halide solubilizers.
One kind or a mixture of two or more kinds can be used. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The rinse liquid (wash water and / or stabilizing liquid) will be described. Bacteria propagate in the rinse solution,
The isothiazolone compounds and siabendazoles described in JP-A-57-8542 and 61-120 are used for the purpose of preventing the produced floating substances from adhering to a light-sensitive material.
Chlorinated germicides such as sodium chlorinated isocyanurate described in JP 145, benzotriazole, copper ions described in JP-A-61-267761, and others by Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal" (1986). "Sankyo Publishing, edited by Sanitary Technology Society," Microbial sterilization, sterilization, and fungicide technology "(1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986). Further, with respect to the above problem, Japanese Patent Laid-Open No. 62-2888
The method of reducing calcium and magnesium described in Japanese Patent No. 38 can be used very effectively.

In the rinse solution, arsehydrides such as formaldehyde, acetaldehyde, and pyruvaldehyde, which inactivate the remaining magenta coupler to prevent the fading of dyes and the formation of stains, the methylol compound described in US Pat. Methylene tetramine, hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seizure patent publication No. 50
Azolylmethylamines described in Nos. 4609 and 519190 can be added.

For the rinse liquid (particularly washing water), a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used. A compound having an image stabilizing function is added to the rinse liquid (particularly the stabilizing liquid). For example, an aldehyde compound typified by formalin, a buffering agent for adjusting the membrane pH suitable for dye stabilization, and And ammonium compounds. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

[0140]

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

[Example 1] (Preparation of emulsion G-1) Lime-treated gelatin 3% aqueous solution 10
00 ml was adjusted to pH 3.3 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were added and mixed at 56 ° C. at the same time with vigorous stirring. However, from the point of 80% addition of silver nitrate,
Over the time of 0%, potassium bromide was added with vigorous mixing in an amount of 2 mol% per mol of finished silver halide. In addition, from the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had an Ru amount of 5 × per mol of the finished silver halide.
An amount of 10 ⁻⁵ mol was added. 83% addition of silver nitrate
From the time point of 1 to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added in an amount such that the Ir amount was 5 × 10 ⁻⁸ mol per mol of the finished silver halide. After desalting at 40 ° C, add 168 g of lime-processed gelatin and adjust the pH.
It was adjusted to 5.7 and pCl 1.8. The obtained grains were cubic silver chloride emulsions having an equivalent spherical diameter of 0.5 μm and a coefficient of variation of 11%. When the bromide ion concentration distribution of the obtained emulsion was analyzed by the etching / TOF-SIMS method, it was found that the bromide ion had a maximum concentration inside the grains. It is shown that the silver bromide-containing phase is formed inside the grains to which the bromide salt solution was added (at a position of 80% to 90% by the addition of silver nitrate). It is considered that this emulsion B-1 contains silver chlorobromide grains in which the silver bromide-containing phase is layered inside the grains. This emulsion was dissolved at 40 ° C., and sodium thiosulfonate was added in an amount of 1.8 × 10 ⁻⁵ mol per mol of silver halide. Sodium thiosulfate pentahydrate as a sulfur sensitizer and gold sensitizer ( It was aged using S-2) at 60 ° C. so as to be optimum. After cooling to 40 ° C., the sensitizing dye C was added at 3 × 10 ⁻⁴ per mol of silver halide.
Mol, 1-phenyl-5-mercaptotetrazole is 2 × 10 ⁻⁴ mol per mol of silver halide, and 1- (5-methylureidophenyl) -5-mercaptotetrazole is 4 × 10 ⁻⁴ per mol of silver halide. Mol and potassium bromide were added in an amount of 7 × 10 ⁻³ mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion G-1.

[0142]

[Chemical 7]

(Preparation of Emulsion G-2: Comparative Example) Emulsion G-1
Respect, instead of K ₂ [IrCl _6] aqueous K ₂ [I
rBr ₆ ] aqueous solution added to the emulsion G in such an amount that the Ir amount becomes 5 × 10 ⁻⁸ mol per mol of the finished silver halide.
-2 was prepared.

(Preparation of Emulsion G-3: Present Invention) Emulsion G-1
Against K₂[IrCl₆] K instead of aqueous solution₂[I
rCl_Five(H ₂O)] Aqueous solution of finished silver halide
Ir amount is 1 × 10 1 per mol^-6Add the amount to be molar
Emulsion G-3 was prepared.

(Preparation of Emulsion G-4: The Present Invention) Emulsion G-1
Respect, instead of K ₂ [IrCl _6] aqueous K ₂ [I
An emulsion G-4 was prepared by adding an aqueous solution of r (thiazole) Cl ₅ ] to an amount of Ir of 1 × 10 ⁻⁶ mol per mol of the finished silver halide.

(Preparation of Emulsion G-5: The Invention) Emulsion G-1
Respect, instead of K ₂ [IrCl _6] aqueous K ₂ [I
r (5-methylthiazole) Cl ₅ ] aqueous solution with an Ir amount of 1 per mol of the finished silver halide.
Emulsion G-5 was prepared by adding an amount of × 10 ^-6 mol.

(Preparation of Emulsion G-6: Present Invention) Emulsion G-1
On the other hand, from the time of addition of silver nitrate of 92% to the time of 98%, K ₂ [IrCl ₅ (2-chloro-5-
The amount of Ir is 1 × 10 ⁻⁶ per mol of the finished silver halide.
Emulsion G-6 was prepared by adding a molar amount.

(Preparation of Emulsion G-7) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 3.3 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred at 56 ° C.
And mixed at the same time. However, the addition of silver nitrate is 80%
From the time point of 90 to 90%, potassium bromide was added with vigorous mixing in an amount of 2 mol% per mol of the finished silver halide, and the addition of silver nitrate was 90%.
Upon completion, an aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.2 mol% per mol of the finished silver halide. Also, the addition of silver nitrate is 8
From 0% to 90%, K ₄ [Ru (C
N) ₆ ] aqueous solution was added in an amount such that the Ru amount became 5 × 10 ⁻⁵ mol per mol of the finished silver halide. When the addition of silver nitrate was 83% to 88%, K ₂
An aqueous solution of [Ir (thiazole) Cl ₅ ] was added in such an amount that the Ir amount was 1 × 10 ⁻⁶ mol per mol of the finished silver halide. After desalting at 40 ° C, 168 g of lime-processed gelatin was added, pH 5.7, pCl
Adjusted to 1.8. The obtained particles have an equivalent spherical diameter of 0.5μ.
m was a cubic silver chloride emulsion having a coefficient of variation of 11%. When the iodide ion and bromide ion concentration distribution of the obtained emulsion was analyzed by the etching / TOF-SIMS method, it was found that the iodide ion had a maximum concentration on the grain surface, and the concentration decreased inward. On the other hand, it was found that the bromide ion has a maximum concentration inside the grain. Even when the addition of the iodide salt solution is completed inside the grain (at the position of 90% by the addition of silver nitrate), the iodide ion exudes toward the grain surface, but the silver bromide-containing phase is the bromide salt solution. It is shown that the particles are formed inside the particles (80% to 90% by the addition of silver nitrate) to which the addition of (1) has been made. This emulsion B-1
Is considered to contain silver chlorobromoiodide grains in which the silver bromide-containing phase is formed in a layered form inside the grain and the silver iodide-containing phase is formed in a layered form on the outermost surface of the grain.

(Preparation of Emulsion G-8: The Invention) Emulsion G-4
On the other hand, Emulsion G-8 was prepared by adding sensitizing dye D instead of sensitizing dye C in an amount of 3 × 10 ⁻⁶ mol per mol of silver halide.

[0150]

[Chemical 8]

(Preparation of Emulsion G-9: The Invention) Emulsion G-4
On the other hand, Emulsion G-9 was prepared by adding sensitizing dye E instead of sensitizing dye C in an amount of 3 × 10 ⁻⁶ mol per mol of silver halide.

[0152]

[Chemical 9]

(Preparation of Emulsion B-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 50 ° C.
And mixed at the same time. From the time of addition of silver nitrate of 80% to the time of 90%, potassium bromide was added so as to be 3 mol% per mol of the finished silver halide. Similarly, from the time of addition of silver nitrate of 80% to the time of 90%, K ₄ [Ru (CN) ₆ ] aqueous solution was added in such an amount that the amount of Ru became 3 × 10 ⁻⁵ mol per mol of the finished silver halide. . 8 from the point when the addition of silver nitrate is 82%
By the time of 8%, the K ₂ [IrCl ₆ ] aqueous solution had an Ir amount of 1.2 × 10 4 per mol of the finished silver halide.
^-8 mol was added. 92% addition of silver nitrate
From the time point of 98% to the time point of K ₂ [Ir (5-m
Ethylthiazole) Cl ₅ ] aqueous solution having an Ir content of 1.0 × 10 6 per mol of the finished silver halide.
^-6 mol was added. When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added so that the amount of I was 0.3 mol% per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained particles have an equivalent spherical diameter of 0.51 μm and a coefficient of variation of 9
% Cubic chlorobromochloroiodide emulsion. This emulsion at 40 ° C
And sodium thiosulfonate was added in an amount of 2 × 10 ⁻⁵ mol per mol of silver halide. Sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-
It was aged at 60 ° C. using 2) so as to be optimum. 40
After the temperature was lowered to ° C, the sensitizing dye A was 2.7 x 10 ^-4 mol per mol of silver halide, the sensitizing dye B was 1.4 x 10 ^-4 mol per mol of silver halide, and 1-phenyl-5. -2.7x mercaptotetrazole per mol silver halide
10 ^-4 mol, 1- (5-methylureidophenyl) -5
-Mercaptotetrazole was added in an amount of 2.7 x 10 ^-4 mol per mol of silver halide, and potassium bromide was added in an amount of 2.7 x 10 ^-3 mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion B-1.

[0154]

[Chemical 10]

(Preparation of Emulsion R-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were vigorously stirred at 40 ° C.
And mixed at the same time. From the point of time when the addition of silver nitrate was 60% to the point of 80%, the K ₃ [RhBr ₆ ] aqueous solution had an Rh amount of 5.8 × per mol of the finished silver halide.
An amount of 10 ⁻⁹ mol was added. 80% addition of silver nitrate
From the time point of 100 to 100%, potassium bromide was added with vigorous mixing in an amount of 4.3 mol% per mol of the finished silver halide. 8 additions of silver nitrate
From 0% to 90%, K ₄ [Ru (C
N) ₆ ] aqueous solution was added in an amount such that the Ru amount was 3 × 10 ⁻⁵ mol per mol of the finished silver halide. When the addition of silver nitrate was 83% to 88%, K ₂
[IrCl _6] per mol of silver halide Ir amounts of the finished aqueous solution is 5 × 10 ^- was added in an amount of ⁹ mol.
When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.1 mol% per mol of the finished silver halide.
From the time of addition of silver nitrate of 92% to the time of 95%, K ₂ [Ir (5-methylthiazole)]
Cl ₅ ] aqueous solution was added in such an amount that the Ir amount became 5 × 10 ⁻⁷ mol per mol of the finished silver halide. Furthermore,
From the time when the addition of silver nitrate was 95% to the time when 98% was added, the amount of the K ₂ [Ir (H ₂ O) Cl ₅ ] aqueous solution was adjusted to 5 × 10 ⁻⁷ mol per mol of the finished silver halide. Was added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added, pH 5.5, pCl 1.8
Adjusted to. The obtained grains were cubic silver chlorobromoiodide emulsions having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 9%. This emulsion was dissolved at 40 ° C., sodium thiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (S- It was aged at 60 ° C. using 2) so as to be optimum. After cooling to 40 ° C., the sensitizing dye H was 2 × 10 ⁻⁴ mol per mol of silver halide, the 1-phenyl-5-mercaptotetrazole was 2 × 10 ⁻⁴ mol per mol of silver halide, 1- (5 -Methylureidophenyl) -5-mercaptotetrazole was added in an amount of 8 x 10 per mol of silver halide.
^-4 mol, compound I is 1 x 10 per mol of silver halide
^-3 moles, potassium bromide 7 x per mole silver halide
10 ⁻³ mol was added. The emulsion thus obtained,
This was Emulsion R-1.

[0156]

[Chemical 11]

[0157]

[Chemical 12]

Corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The photographic constituent layers of No. 1 were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer constitution. The coating liquid for each photographic constituent layer was prepared as follows.

-Preparation of coating liquid for first layer-Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

-Preparation of Second Layer to Seventh Layer Coating Liquid-The coating liquids for the second to seventh layers were prepared in the same manner as the first layer coating liquid. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Also,
Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² and 60.0 mg / m ² , respectively.
m ² , 5.0 mg / m ² and 10.0 mg / m ² were added.

[0161]

[Chemical 13]

[0162]

[Chemical 14]

In the red-sensitive emulsion layer, 0.05 g / copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000-400000) was used.
m ² was added. 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. Also, to prevent irradiation,
The following dyes (the amount in parentheses represents the coating amount) were added.

[0164]

[Chemical 15]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by weight, ZnO; content 4%) and optical brightener (4,4'-bis (5-methylbenzoxazolyl) stilbene. Content 0.03% by weight), bluish dye ( Ultramarine)] First layer (blue sensitive emulsion layer) Emulsion B-1 0.24 Gelatin 1.25 Yellow coupler (ExY-1) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

[0166]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0167]   Third layer (green sensitive emulsion layer)     Silver chlorobromide emulsion G-1 0.15     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0168]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0169]   Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion R-1 0.13     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0170]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.25   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0171]

[Chemical 16]

[0172]

[Chemical 17]

[0173]

[Chemical 18]

[0174]

[Chemical 19]

[0175]

[Chemical 20]

[0176]

[Chemical 21]

[0177]

[Chemical formula 22]

[0178]

[Chemical formula 23]

[0179]

[Chemical formula 24]

[0180]

[Chemical 25]

The sample obtained as described above was used as Sample 1
It was set to 01. Sample 101 is Sample 1 in which the emulsion G-1 of the green-sensitive emulsion layer (GL layer) is changed from G-2 to G-9.
02 to 109 were similarly prepared. In addition, with respect to the sample 104, a sample 110 in which 1-phenyl-5-mercaptotetrazole was added at 0.89 mg / m ² in the sixth layer was manufactured.

(Exposure / Development Processing) Each of the above-mentioned samples is 127 m.
Half gray exposure by laser scanning exposure using a machine modified into a processing unit of the mini photo printer processor PP728AR manufactured by Fuji Photo Film Co., Ltd. so that it can be processed into a roll width of m and processed by the following development processing A. Then, continuous processing (running test test) was carried out until the volume of the color developing replenisher used in the developing processing A below became a replenishing amount of 4 times the capacity of the color developing tank, and the magenta sensitizer was evaluated. . The results are shown in Table 2. The construction of the development processing section of the minilab printer processor PP728AR manufactured by Fuji Photo Film Co., Ltd. is described in JP-A-11-3.
2, which is similar to FIG. 2 described in No. 27109, in which a surface layer (elastomer layer) is formed by a SEBS elastomer material (“Lavalon” manufactured by Mitsubishi Chemical Co., Ltd.) as a conveying roller in a P1 (color developing solution) tank. Is installed, and the transport linear velocity is 4
It was set to 5.0 mm / s. Further, the exposed sample was subjected to color development processing in the following development processing 8 seconds after the exposure.

-Development processing A-Processing step 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 20 seconds-Rinse (2) 38.0 ° C 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 20 seconds 121 ml Dry 80 ° C 30 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Phosphorus screening system RC manufactured by Fujifilm
50D is attached to the rinse (3), the rinse liquid is taken out from the rinse (3), and the reverse osmosis module (RC
50D). The permeated water obtained in the same tank is rinsed (4)
And the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of water permeated to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day (temperature control). Rinse 4 from (1) to (4)
The tank countercurrent system was adopted.

The composition of each processing liquid is as follows. [Replenisher for color developer] Optical brightener A-1 7.5 g Optical brightener B-1 12.0 g Dimethylpolysiloxane surfactant 0.35g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Ethylenediaminetetraacetic acid 15.0 g Tri (isopropanol) amine 30.0 g Potassium hydroxide 18.5 g Sodium hydroxide 24.0 g Sodium sulfite 0.60g Potassium bromide 0.04g Polyethylene glycol 300 40.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfoamide Ethyl) aniline / 3/2 sulfuric acid hydrate / monohydrate 60.0 g Potassium carbonate 100.0 g pH 13.0 1 L including water

[0185]

[Chemical formula 26]

The above-prepared replenisher was diluted 4-fold to adjust the pH to 12.50 to obtain a color developer replenisher.

[0187] [Tank liquid for color developer] 800 ml of water Dimethyl polysiloxane surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.)                                             0.1 g Polyethylene glycol     (Molecular weight 300) 10.0 g Optical brightener A-1 1.0 g Optical brightener B-1 2.0g Ethylenediaminetetraacetic acid 4.0 g Tri (isopropanol) amine 8.8g 4,5-dihydroxybenzene-1,3               -Sodium disulfonate 8.5g Potassium chloride 10.0g Sodium sulfite 0.1g N-hydroxy-N, N-di (sulfo         Ethyl) amine disodium salt 8.5 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfone Amidoethyl) aniline ・ 3/2 sulfate ・ monohydrate                                             5.0 g 26.3 g potassium carbonate 1000 ml with water pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                           10.15

[0188] [Bleach fixer] [Tank solution] [Replenisher] 800 ml of water 800 ml Ammonium thiosulfate (750g / L)                                     107.0 ml 214.0 ml m-carboxymethylbenzenesulfinic acid                                           8.3g 16.5g Ethylenediaminetetraacetate Iron (III) ammonium                                         47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water 1000ml 1000ml pH (adjusted with 25 ° C / acetic acid and ammonia) 6.5 6.5

[0189] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μs / cm or less) 1000ml 1000ml pH 6.5 6.5

—Evaluation of Magenta Sensitizer— Regarding the occurrence of magenta sensitizer per 30 m of sample, 1
Five evaluators rated it on a 5-point scale and averaged it. The following criteria were evaluated. It should be noted that 3 or more is a level at which there is no practical problem. 5: The generated streaks cannot be seen at all 4: When you look closely, you can see thin streaks, but it is good level 3: Thin streaks are visible, but there is no practical problem. 2: Practically a little problematic level 1: Quite awful level

[0191]

[Table 2]

As is clear from the results in Table 2, a light-sensitive material containing a specific dopant (metal complex) in the emulsion layer (Sample 103) was used.
It is understood that the magenta sensitizing muscles are improved by subjecting (1) to (106) to the exposure / development treatment under the above specific conditions. In particular, it can be seen that the improvement effect is remarkable in the samples 105 and 106. Further, a light-sensitive material containing an emulsion using iodine, a light-sensitive material using a specific sensitizing dye, 1-phenyl-5-
It can be seen that the use of the light-sensitive materials (Samples 107, 108, and 109) in which mercaptotetrazole was used up to a specific usage amount further improved the sample 104.

[Example 2] The light-sensitive material (Samples 101 to 110) produced in Example 1 was subjected to half gray exposure by laser scanning exposure using a minilab printer Frontea 330 manufactured by Fuji Photo Film Co., Ltd., and the following development was performed. By the process B, the magenta sensitizer was evaluated by continuous processing until replenishing with 6 times the amount of the color developing solution in the tank. The results are shown in Table 3. The standard transport speed of the above Mini Photo Printer Frontea 330 manufactured by Fuji Photo Film Co., Ltd. was set to double, and the treatment rack of the rinse treatment tank was modified. Further, as a conveying roller in the P1 (color developing solution) tank, a roller having a surface layer (elastomer layer) made of SEBS type elastomer material (“Lavalon” manufactured by Mitsubishi Chemical Corporation) was provided. Further, the exposed sample was subjected to color development processing within 8 seconds after the exposure.

-Development processing B-Processing step Temperature time Replenishment amount Color development 45.0 ° C 25 seconds 45 ml / m ² Bleach fixing 40.0 ° C 25 seconds A: 17.5 ml / m ² B: 17.5 ml / m ² rinse (1) 40.0 ° C. 7 seconds − rinse (2) 40.0 ° C. 4 seconds − rinse (3) 40.0 ° C. 4 seconds − rinse (4) 40.0 ° C. 7 seconds 175 ml dry 80 ° C. 20 Second

[0195]

[0196] [Color developer] [Tank solution] [Replenisher]   Cation-exchanged water 800 ml 800 ml   Dimethylpolysiloxane-based surfactant 0.05g 0.05g     (Silicone KF351A, manufactured by Shin-Etsu Chemical Co., Ltd.)   Potassium hydroxide 4.0g 9.0g   Sodium hydroxide 2.0g 6.0g   Ethylenediaminetetraacetic acid 4.0 g 4.0 g   Tyrone 0.5g 0.5g   Potassium chloride 19.0g-   Potassium bromide 0.036 g-   P-1 (compound below) 1.5 g 2.9 g   S-1 (compound below) 3.5 g 9.0 g   Sodium p-toluenesulfonate 15.0 g 15.0 g   Sodium sulfite 0.2g 0.2g   m-carboxysulfinic acid 2.0 g 3.6 g   Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                       5.0 g 10.8 g   N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-a     Minoaniline ・ 3/2 sulfuric acid ・ monohydrate 6.7g 17.3g   Potassium carbonate 26.3g 26.3g   Add water 1000ml 1000ml   pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                     10.12 10.26

[0197] [Bleach fixer] [Tank solution] [Replenisher A] [Replenisher B]   Water 650ml 300ml 300ml   Ammonium thiosulfate (750 g / l)                               97.0 ml-376.0 ml   Ammonium bisulfite solution (65%)                               13.0g-185.5ml   Ammonium sulfite 21.0 g − −   Ethylenediaminetetraacetate Iron (III) ammonium                               37g 184.0g-   Ethylenediaminetetraacetic acid 1.6g 0.4g 10.0g   m-carboxysulfinic acid 3.0 g 14.0 g-   Nitric acid 5.2g 25.0g-   Succinic acid 6.7 g 33.0 g-   Imidazole 1.3 g − −   Ammonia water (27%) 3.4 g-36.0 g   Add water 1000ml 1000ml 1000ml   pH (adjusted with 25 ° C / nitric acid and ammonia water)                                 5.9 2.5 5.75

[0198] [Rinse solution] (common to tank solution and replenisher)   Chlorinated sodium isocyanurate 0.02g   Deionized water (conductivity 5μs / cm or less) 1000ml

[0199]

[Chemical 27]

[0200]

[Table 3]

As is clear from the results in Table 3, Example 1
When the light-sensitive material prepared in 1. was exposed and developed under the above conditions, it was found that the magenta sensitizing muscle was improved as in Example 1.

[Example 3] As sample 101, a sample in which the photographic constituent layers were changed as follows was prepared. First layer (blue-sensitive emulsion layer) Emulsion B-1 0.14 Gelatin 0.75 Yellow coupler (ExY-2) 0.34 Color image stabilizer (Cpd-1) 0.04 Color image stabilizer (Cpd-2) ) 0.02 color image stabilizer (Cpd-3) 0.04 color image stabilizer (Cpd-8) 0.01 solvent (Solv-1) 0.13

[0203]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0204]   Third layer (green sensitive emulsion layer)     Emulsion G-1 0.12     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0205]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0206]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.10     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0207]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

[0208]

[Chemical 28]

The sample thus obtained was used as Sample 2
It was set to 01. Sample 201 is Sample 2 in which the emulsion G-1 of the green-sensitive emulsion layer (GL layer) is changed from G-2 to G-9.
02 to 209 were similarly prepared. In addition, with respect to the sample 204, a sample 210 in which 1-phenyl-5-mercaptotetrazole was added at 0.63 mg / m ² in the sixth layer was manufactured.

(Exposure / Development Processing) The photosensitive materials (Samples 101 to 110) prepared in Example 1 were replaced by the development processing A instead of the development processing A.
Exposure and development processes were performed in the same manner as in Example 1 except that the development process C described below was performed, and the magenta sensitizing muscles were evaluated. The results are shown in Table 4.

-Development processing C-Processing step Temperature time Replenishment amount * Color development 45.0 ° C 16 seconds 45mL Bleach fixing 40.0 ° C 16 seconds 35mL Rinse 1 40.0 ° C 8 seconds-Rinse 2 40.0 ° C 8 seconds -Rinse 3 ** 40.0 ° C for 8 seconds-Rinse 4 ** 38.0 ° C for 8 seconds 121mL dry 80.0 ° C for 16 seconds (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Fuji Photo Film Co., Ltd. Rinse screening system RC50D is attached to the rinse (3), and rinse (3)
The rinse liquid is taken out from the pump and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse, and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and temperature control (temperature control) circulation was performed for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0213] [Bleach fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL)                                   107 mL 214 mL Succinic acid 29.5g 59.0g Ethylene diamine tetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0214] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

[0215]

[Chemical 29]

[0216]

[Table 4]

As is clear from the results shown in Table 4, sample 20
In the case of using 3 to 209 and performing the ultra-rapid processing as the developing processing, the magenta sensitizing muscle was hardly generated and a good effect was recognized.

As described above, according to the present invention, a silver halide color photographic light-sensitive material is subjected to low replenishment and rapid processing by laser scanning exposure, excellent pressure resistance, and stable photographic performance can always be obtained, which is particularly suitable for color printing. An image forming method can be provided.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 7/44 G03C 7/44

Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a red photosensitive silver halide containing a cyan dye-forming coupler on a support. After imagewise exposure of a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of at least one emulsion layer and at least one non-light-sensitive hydrophilic colloid layer, development including a color development step, a bleach-fixing step and a rinse step In the image forming method of applying a treatment, in at least one of the photosensitive silver halide emulsion layers,
A silver halide emulsion having a silver chloride content of 90 mol% or more containing at least one selected from the metal complexes represented by the following general formula (I) is used, and the imagewise exposure is performed by laser scanning exposure. And, after the laser scanning exposure is finished, the color developing step is started within 12 seconds, and the color developing step is performed at a replenishing amount of the color developing solution of ^{20 to} 60 ml per 1 m ^{2 of the} light-sensitive material, The developing process is performed while the silver halide color photographic light-sensitive material is being conveyed by a conveying roller, and a roller formed of a styrene-ethylene-butadiene-styrene (SEBS) type elastomer is used as at least one of the conveying rollers. An image forming method characterized by the following. In the general formula _{^{(I) [IrX I n L}} I (6-n)] m- ( general formula (I), X ^I is, .L ^I is X ^I representing a pseudohalogen ion other than halide ion or cyanide ion Represents an arbitrary ligand different from, n represents an integer of 3 to 5, and m represents an integer of -4 to +1.) 2. The total coated silver amount in the photographic constituent layers is 0.2.
The image forming method according to claim 1, wherein g / m ² or more and 0.5 g / m ² or less. 3. The image forming method according to claim 1, wherein the color developing step is performed in 28 seconds or less.