JPH05165164A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain a color image forming method possible to stably obtain an high quality image for a short development processing time. CONSTITUTION:In the color image forming method by bleaching, fixation and washing processing a silver halide photographic sensitive material having at least one layer of a high chloride contained silver halide emulsion layer on a supporting body after processed with a color developer containing an aromatic primary amine color developing main chemicals and containing practically no benzil alcohol, the high chloride contained silver halide layer contains a silver halide emulsion particle, which has a part of >=30mol% silver bromide content and is constituted so that at least 95-99.9% of the silver halide emulsion particle reduction sensitized is silver halide, and color developing time is <=25 seconds and sum of total processing time of color developing processing time, bleaching fixation processing time and washing processing time is <=2 minutes.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method using a silver halide photographic light-sensitive material capable of stably obtaining a high quality image by processing in a short time. In particular, a color image using a silver halide photographic light-sensitive material that can stably obtain a photographic image with excellent gradation by high-intensity short-time exposure using a laser or the like from soft information recorded on a magnetic medium or the like. The present invention relates to a forming method.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic light-sensitive materials, especially silver halide color photographic light-sensitive materials are used very much today because of their high sensitivity and excellent gradation. However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes a lot of time to prepare a processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There is a defect that it takes a long time to obtain the first print. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, until now, engineers who were skilled in everything from the development of color negatives to the production of color prints have focused exclusively on a small number of large development laboratories. The method of doing has been adopted.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing from color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular.

In particular, the development processing time has been remarkably shortened by employing a silver halide emulsion containing a high concentration of silver chloride. However, a silver halide emulsion containing silver chloride at a high concentration has a large reciprocity law failure, and has drawbacks such as desensitization in low-intensity long-time exposure, high-intensity short-time exposure, and large gradation change. ..

Further, in the field of electronics today, due to the remarkable progress of image pickup devices such as CCDs and magnetic recording media, photography is as easy as photography using silver halide so far, and immediately photographed on TV. It has made it possible to enjoy it. To obtain an image recorded on paper from such image data, a thermal transfer method,
Various methods such as ink jet method and electrophotographic method have been put to practical use, but even in these fields, the rich gradation of silver halide photographic materials is outstanding and superior to other methods. Has descriptive power. But,
When the exposure time of the silver halide photographic light-sensitive material is microseconds or shorter, the photographic characteristics change such that the sensitivity is lowered or the gradation is softened, and this phenomenon is more remarkable as the exposure time is shortened. there were.

It has been disclosed that the inclusion of a Group VIII metal compound can improve reciprocity law failure and increase sensitivity. In addition, Japanese Examined Patent Publication No. 49-33781, Japanese Unexamined Patent Publication No. 50-23618, No. 52-18310, No. 58-15952, and No. 59-214.
No. 028 and No. 61-67845 disclose that inclusion of a rhodium compound or an iridium compound can improve reciprocity law failure and enhance contrast. Although such a technique improves the reciprocity law failure of silver halide emulsions containing a high concentration of silver chloride, it has the drawback that sufficient sensitivity cannot be obtained yet. It was difficult to obtain a stable finish.

In JP-A-1-183647, 70 mol% or more of all grains are composed of silver chloride, and a silver bromide localized phase having a silver bromide content of less than 70 mol% is present inside or on the grains. Further, it is disclosed that a silver halide photographic light-sensitive material containing iron ions in the grains has high sensitivity, high contrast, and changes in photographic performance due to temperature and humidity during exposure are small.
When this silver halide emulsion was used, high sensitivity was obtained and reciprocity law failure was also improved, but the latent image fluctuated within a very short time after exposure, and an aromatic primary amine color developing agent was used. When a color developing solution was used to develop a color image for 25 seconds or less, the linearity of the characteristic curve was impaired, and the contrast in the highlight area was significantly reduced. In addition, this phenomenon becomes more remarkable as the time from exposure to development becomes shorter,
The resulting finish changed with each development, giving poor reproducibility.

Regarding the reduction sensitization technique, many prior arts are known. For example, JP-A-2-136852 discloses a technique of reduction sensitization in the presence of ascorbic acid or its derivative. -21944, the technology of monodisperse silver halide emulsions reduction-sensitized with ascorbic acid derivatives,
Japanese Unexamined Patent Publication (Kokai) No. 3-168632 discloses a non-exposed sample with high sensitivity and low fog by the technology of a silver halide emulsion which is reduction sensitized with ascorbic acid or a derivative thereof and has a ratio of (100) plane higher than that of (111) plane. It is disclosed that the storage stability of the is improved.
However, each of these publications does not describe a silver halide emulsion containing a high concentration of silver chloride, and also contains a high concentration of silver chloride and has a higher concentration of silver bromide than other portions. In the case of silver halide emulsion in which a portion is localized, the linearity of the characteristic curve is impaired when the color development time is shortened,
No mention has been made of the drawback of softening the legs, nor of any possible improvement.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image forming method using a silver halide photographic light-sensitive material capable of stably obtaining a high quality image by processing in a short time. In addition, a color using a silver halide photographic light-sensitive material that can stably obtain a photographic image with excellent gradation in a short time from an exposure device using a laser etc. from soft information recorded on a magnetic medium or the like. An object is to provide an image forming method.

[0010]

DETAILED DESCRIPTION OF THE INVENTION While the inventors of the present invention earnestly studied a silver halide photographic light-sensitive material using a high chloride silver halide emulsion for exposure using a laser, the object of the present invention was to
A silver halide photographic light-sensitive material having at least one high chloride silver halide emulsion layer on a support was processed with a color developing solution containing an aromatic primary amine color developing agent and containing substantially no benzyl alcohol. After that, in the method of forming a color image by bleach-fixing treatment and washing treatment with water, the high chloride silver halide emulsion layer comprises 30 mol.
% Silver bromide content and reduction sensitized, containing 95-99.9 mol% of silver halide emulsion grains consisting of silver chloride, and the color development time is 25 seconds. It was found that the following can be achieved by a color image forming method characterized in that the total processing steps of color development processing time, bleach-fixing processing time and water washing processing time are within 2 minutes in total, and the present invention is completed. Arrived

The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention is characterized by containing 95 to 99.9 mol% of silver chloride, but is substantially free of silver iodide. Silver halide is preferred. The content of silver chloride is more preferably 97 to 99.9 mol%. To reduce the amount of development or replenishment of color developer in a shorter time, 99.5 to 99.9 mol%
Is more preferable.

The silver halide grains according to the present invention are characterized by having a portion having a silver bromide content of 30 mol% or more. The portion containing silver bromide in a high concentration may be epitaxy bonded to silver halide emulsion grains or may be a so-called core-shell emulsion, or may be a partial composition without forming a complete layer. There may be only different areas of. The portion in which silver bromide is present at a high concentration may be formed in the step of forming silver halide grains, the chemical ripening step thereafter, or the coating solution preparation step. Further, when the composition of the inside of the particle is different from that of the surface, the composition may change continuously or discontinuously.

When the silver bromide content is about 1 mol%, the silver bromide content of the portion containing a high concentration of silver bromide is 40% though it depends on the composition of the whole silver halide emulsion grains. It is preferably at least mol%. Examples of such silver halide grains include those described in JP-A-58-95736, JP-A-58-108533, and JP-A-1-183647. The silver bromide content of the portion containing a high concentration of silver bromide can be determined by using the method described in JP-A-1-183647, page 22, upper right column. When the silver bromide content thus obtained has a wide range, the silver bromide content in the portion containing silver bromide at a high concentration as used in the present application means the maximum value.

Heavy metal ions may be contained in the silver halide emulsion according to the present invention. These compounds are useful for improving the reciprocity law failure, but have the drawback that the performance tends to change depending on the time from exposure to development. According to the present invention, this drawback is improved and the advantage of improving the reciprocity law failure is exhibited, and it is a preferred embodiment of the present invention.
Heavy metal ions that can be used for such purposes include iron, iridium, platinum, palladium, nickel,
Vth of rhodium, osmium, ruthenium, cobalt, etc.
Group III metals and Group II metals such as cadmium, zinc and mercury
Examples thereof include group transition metals and ions of lead, rhenium, molybdenum, tungsten, and chromium. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt. Above all, it is preferable to add it to the emulsion in the form of a complex salt because it is easily incorporated into the silver halide emulsion and the effect of the present invention becomes large.

When the heavy metal ion forms a complex, examples of the ligand include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. be able to. Among them, thiocyanate ion, isothiocyanate ion, cyanate ion and the like are preferable.

The heavy metal compounds which can be preferably used in the silver halide emulsion according to the present invention are shown below, but the present invention is not limited thereto.

(1) FeCl ₂ (2) FeCl ₃ (3) (NH ₄ ) Fe (SO ₄ ) ₂ (4) K ₃ [Fe (CN) ₆ ] (5) K ₄ [Fe (CN) ₆ ] (6) K ₂ [IrCl ₆ ] (7) K ₃ [IrCl ₆ ] (8) K ₂ [PtCl ₆ ] (9) K ₂ [Pt (SCN) ₄ ] (10) K ₂ [NiCl ₄ ] (11 ) K ₂ [PdCl ₆ ] (12) K ₃ [RdCl ₆ ] (13) CdCl ₂ (14) ZnCl ₂ (15) K ₂ [Mo (CO) ₄ (CNO) ₂ ] (16) K ₃ [Re ( CNO) ₆ ] (17) K ₃ [Mo (OCN) ₆ ] (18) K ₄ [Fe (CNO) ₆ ] (19) K ₂ [W (CO) ₄ (CNO) ₂ ] (20) K ₂ [ Cr (CO) ₄ (CNO)] (21) K ₄ [Ru (CNO) ₆ ] (22) K ₂ [Ni (CN) ₄ ] (23) PbCl ₂ (24) K ₃ [Co (NH ₃ ) ₆ ] (twenty five) K ₅ [Co ₂ (CNO) ₁₁ ] (26) K ₃ [Re (CNO) ₆ ] (27) K ₄ [Os (CNO) ₆ ] (28) K ₂ [Cd (CNO) ₄ ] (29) K ₂ [Pt (CNO) ₄ ] (30) K ₃ [IrBr ₆ ] In order to add a heavy metal ion to the silver halide emulsion according to the present invention, the heavy metal compound is added to the silver halide grains before the formation of silver halide grains. It may be added at any place in each step during the physical ripening after the formation of the silver halide grains during the formation of the grains. For this purpose, for example, this heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, it may be dissolved together with the halide salt and added continuously during the grain formation process.

The amount of the heavy metal ions added to the silver halide emulsion is more preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly 1 × 10 ^-8 mol, per mol of silver halide.
It is preferably not less than 1 mol and not more than 1 × 10 ^-3 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Also,
U.S. Pat.Nos. 4,183,756, 4,225,666, JP-A-55-26589,
Japanese Examined Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (19
It is also possible to prepare particles having an octahedral shape, a tetradecahedral shape, a dodecahedron shape or the like by the method described in the literature such as 73) and use them. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grain according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2. The range is to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

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

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The coefficient of variation is preferably 0.22 or less, more preferably 0.12 or less.
It is a monodisperse silver halide grain of 5 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area. As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

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

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor as disclosed in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, etc., and taking out the reaction mother liquor outside the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

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

A known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

Examples of the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention include stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sodium sulfite, potassium sulfite and the like. Sulfites, reductones such as ascorbic acid, thiourea dioxide and the like can be used. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added at the time of forming silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents to be added must be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but in general, it is 10 per mol of the silver halide emulsion.
^-7 to 10 ^-2 mol is preferred.

A small amount of an oxidizing agent may be used for modifying the reduction sensitizing nucleus after the reduction sensitization or for deactivating the remaining reducing agent. Examples of compounds used for such purposes include:
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention can be reduction sensitized and used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably 1 × 10 ^-5 mol to 1 × 10 ^-8
It is a mole.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include , (IIa-1) to (IIa-8) and (I
Examples thereof include compounds Ib-1) to (IIb-7) and 1- (3-methoxyphenyl) -5-mercaptotetrazole. These compounds, depending on their purpose,
It is added in the steps of preparing silver halide emulsion grains, chemical sensitization step, chemical sensitization step, coating solution preparation step and the like. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide, and 1 × 10 ^-5 mol to 5 mol.
× 10 ^-3 mol is more preferable. In the coating liquid preparation process,
When added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. Is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-51 is used.
BS-1 to BS-8 described in No. 124, pages 108 to 109 can be preferably used alone or in combination. As the green-sensitive sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. Examples of the red-sensitive sensitizing dye include RS-described in pages 111 to 112 of the same specification.
1-8 are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, IRS-1 to 1 described in Japanese Patent Application No. 3-73619, pages 12 to 14
Eleven dyes are preferably used. In addition, the same specification 14th
The supersensitizers SS-1 to SS-9 described on pages 15 to 15 are preferably used in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed by using a laser, it is advantageous to use an exposing device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial change of the intensity of the light flux, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, and the outer edge of the light flux and the line that is parallel to the scanning line and that passes through the point where the light intensity is the maximum. When the distance between two intersecting points is the diameter of the light beam, the (light beam diameter) / (scanning speed) can be considered as the exposure time per pixel. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-4.
071, JP-A-59-11062, JP-A-63-197947, JP-A
2-74942, Japanese Patent Laid-Open No. 2-236538, Japanese Patent Publication No. 56-14963, Japanese Patent Publication No. 56-40822, European Wide Area Patent 77410, Department of Electronics and Communication Technology Research Report 80, Volume 244, and Movie Television Technical Journal 1984. /
6 (382), pages 34-36. In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used,
In particular, as a dye having absorption in the visible region, Japanese Patent Application No. 2-51
The dyes of AI-1 to 11 described on pages 117 to 118 of the 124th specification are preferably used, and examples of the infrared absorbing dye include the general formula (I) described in the lower left column of page 2 of JP-A 1-280750. The compounds represented by the formulas (II) and (III) have preferable spectral characteristics, are not affected on the photographic characteristics of the silver halide photographic emulsion, and are not polluted by residual color, which is preferable.
As specific examples of preferred compounds, the same publication, page 3, lower left column to 5
Exemplified compounds (1) to (45) listed in the lower left column of the page can be mentioned.

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm through a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength region of 600 to 750 nm.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y-I) described on page 8 of Japanese Patent Application No. 2-234208.
The coupler represented by can be mentioned. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among them, YC-8 and YC-9 described on page 11 of the same specification are preferable because they can reproduce the preferable yellow color tone.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, a general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds are described on pages 13 to 16 of the same specification.
Mention may be made of those described as MC-1 to MC-11. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are excellent in reproduction of colors from blue to purple and red,
It is also preferable because it has excellent detail depiction. As a cyan coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, Japanese Patent Application No. 2-234208
Examples thereof include couplers represented by the general formulas (CI) and (C-II) described on page 17 of the publication. Specific compounds include those described as CC-1 to CC-9 on pages 18 to 21 of the same specification. When the oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. And a low-boiling point and / or water-soluble organic solvent are also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used to dissolve and disperse the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt-
Butyl acrylamide) and the like.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1 on page 35 of the specification). ) Etc. can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁵ mol per mol of silver halide,
More preferably, it is used in the range of 1 × 10 ^-2 to 1 × 10 ^-1 mol.

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

As the reflective support according to the present invention, any material may be used, including white pigment-containing polyethylene coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable. As the white pigment used for the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Titanium, zinc oxide, talc,
Examples include clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer, and further 13% by weight. The above content is preferable, and 15% by weight or more is more preferable. The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the dispersity of the white pigment is preferably 0.20 or less as a coefficient of variation described in the above publication, more preferably 0.15 or less,
It is more preferably 0.10 or less.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1 N, N-diethyl-p-phenylenediamine CD-2 2-amino-5-diethylaminotoluene CD-3 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 4- Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6 4-amino -3-Methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8 N, N-dimethyl- p-Phenylenediamine CD-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline When used in the image forming method according to (1), a compound represented by the following general formula (CD-I) is more preferable from the viewpoint of development processing for a short time. Used well.

General formula (CD-I)

[0055]

[Chemical 1]

In the formula (CD-I), R is a linear or branched alkylene group having 3 carbon atoms, and m and n are each 1
Is an integer of 4 and HA represents an inorganic or organic acid,
Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid and the like.

These color developing agents are available from Journal of American Chemical Society, Vol. 73, 3100.
It can be easily synthesized by the method described in (1951). General formula (CD
Specific examples of the compound represented by -I) are shown below.

[0058]

[Chemical 2]

[0059]

[Chemical 3]

The color-developing agent according to the present invention is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of developing solution, and from the viewpoint of rapid processing, it is 1 per liter of color developing solution. It is preferably used in the range of 0.5 × 10 ^{−2 to} 2 × 10 ⁻¹ mol.

The color developing agent used in the image forming method according to the present invention may be used alone or in combination with other known p-phenylenediamine derivatives. In the image forming method according to the present invention, as the compound used in combination with the compound represented by the general formula (I), (CD-5), (CD-6),
(CD-9) is preferred.

These p-phenylenediamine derivatives are
It is generally used in the form of a salt such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate.

The color developer according to the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation. , P
It can be used together within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
In the image forming method according to the present invention, since it is necessary to finish development in a very short time, chloride ions are mainly used, and potassium chloride, sodium chloride, etc. are used.
The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 1 per liter of color developing solution.
It is 0 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and the amount is about 1 liter of color developing solution.
The amount is preferably 1.0 × 10 ⁻³ mol or less, and more preferably 5.0 × 10 ⁻⁴ or less.

Furthermore, if necessary, a development accelerator can be used. As a development accelerator, US Pat.
48604, 3671247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Patents No. 2533990, 253
1832, 2950970, 2577127 and JP-B-44-9504
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-950
The organic solvent, organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine, etc. described in JP-A-9 are included. Further, phenethyl alcohol described in US Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509.
The compounds described in each publication can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of the developing solution. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring a fixed amount of water. In this case, the component having a low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a plurality of components each of which can coexist stably in a concentrated aqueous solution, or a solid state prepared in advance in a small container is added to water, and the color developing solution according to the present invention by stirring. Can also be prepared.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH value is 9.5.
〜13.0 is preferable, more preferably pH9.8
Used in the range of ~ 12.0.

The processing temperature for color development according to the present invention is 35 ° C.
It is preferably 70 ° C or lower. The higher the temperature, the shorter the treatment time is, which is preferable. However, it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment temperature is preferably 37 ° C. or higher and 60 ° C. or lower. Color development time is usually 3 minutes 30
Although it is performed in about 2 seconds, in the present invention, it is within 25 seconds.
Furthermore, it is preferable to carry out in the range of 20 seconds to 3 seconds.

The processing step essentially consists of a color developing step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing), but additional steps or equivalent meanings are provided within a range that does not impair the effects of the present invention. Can be replaced with a process having. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. As the processing step used in the image forming method of the present invention, it is preferable to provide a bleach-fixing step immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is one in which an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid includes
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1-
205262, compounds [2] to [20] described on pages 58 to 59
Can be mentioned.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. A bleach-fixing solution having a composition containing a large amount of a halide such as ammonium bromide in addition to an ethylenediaminetetraacetic acid iron (III) acid bleaching agent and the above-described silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (III) acid It is possible to use a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide or the like can be used in addition to ammonium bromide.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or sodium thiosulfate. Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally 70 to 250 g. The bleach-fix solution contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. They may be contained alone or in combination of two or more. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Also, hydroxylamine,
Preservatives such as hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrate, organic solvents such as methanol, dimethyl sulfonamide, dimethyl sulfoxide, etc. It can be done.

The bleach-fixing solution according to the present invention is described in JP-A-46-2
No. 80, Japanese Patent Publication No. 45-8506, No. 46-556, Belgian Patent 770
910, Japanese Patent Publication No. 45-8836, No. 53-9854, JP 54-7163
Various bleaching accelerators described in No. 4 and No. 49-42349 can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used in the range of pH 4.0 to 9.5, and preferably pH 4.5 to 8.5. Most preferably pH 5.
It is used in the range of 0 to 8.5. The treatment temperature is 80 ° C. or lower, preferably 55 ° C. or lower to prevent evaporation and use. The processing time for bleach-fixing is preferably 3 to 45 seconds, more preferably 5 to
30 seconds.

In the developing treatment according to the present invention, the above-mentioned color developing and bleach-fixing steps are followed by washing with water.
Hereinafter, preferred embodiments of the water washing treatment will be described.

As the compound preferably used in the washing solution, a chelating agent having a chelate stabilizing constant for iron ions of 8 or more is preferable. Here, the chelate stabilization constant is defined by LG Sillen and AEMartell, “Stability Consta.
nts of Metalion Complexes, The Chemical Societ
y, London (1964), S.Chaberek, AEMartell, `` O
rganic Sequestering Agents ”, Wiley (1959), and other commonly known constants.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions, which is preferably used in the washing solution, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Be done. The iron ion means ferric ion. As a specific compound of the chelating agent having a chelate stability constant of 8 or more with ferric ion, there is disclosed in JP-A 1-2051.
The compounds described in No. 62, page 63, line 15 to page 64, line 17 can be mentioned. The amount of the chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution. Further, as a compound added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds. Specifically, JP-A 1-205162, page 65, line 5,
The compounds described on page 66, line 11 can be mentioned. Addition amount of ammonium compound is 1.0 × 10 ^-5 per 1 liter of washing water.
The amount is preferably mol or more, more preferably 0.001 to 5.0 mol, and further preferably 0.002 to 1.0 mol.

Further, it is desirable that the washing solution contains sulfite within the range where bacteria are not generated. The sulfite salt contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and as a preferable specific compound,
Sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, succinic acid Aldehyde bis sodium bisulfite etc. are mentioned.

The above sulfite is preferably added in an amount of at least 1.0 × 10 ^-5 mol per liter of the washing solution, and 5.0 ×
More preferably, it is 10 ^{−5 to} 1.0 × 10 ⁻¹ mol. It may be added directly to the washing solution, but it is preferably added to the washing replenisher.

The water-washing solution used in the present invention preferably contains a mildew-proofing agent, which can prevent sulfidation and improve image storability. Examples of the mildew-proofing agent that can be used in the washing liquid according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, and quaternary phosphonium compounds. ,
They are ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds. Specific compounds are described in JP-A 1-205162.
The compounds described on page 68, line 10 to page 72, line 16 are mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds, sulfamide compounds and pyronone compounds.

The amount of the antifungal agent added to the washing liquid is preferably 0.001 to 30 g, and more preferably 0.003 to 5 g, per liter of the washing liquid.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Such metal compounds include Ba, Ca, Ce, Co, In, La, Mn, Ni, B
Examples thereof include compounds of i, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr. These metal compounds are halide salts,
It can be supplied as an inorganic or organic salt such as a sulfate, a carbonate, a phosphate or an acetate, a hydroxide or a water-soluble chelate compound. The amount of these compounds added is preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol, and 4.0 × 1
More preferably, it is 0 ^{−4 to} 2.0 × 10 ⁻² mol.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution according to the present invention. Specific compounds include JP-A 1-205162, No. 73
Exemplified Compound 1 to Exemplified Compound 32 described on pages 75 to 75 can be mentioned.

The compound having an aldehyde group is preferably used in an amount of 0.1 to 50 g, and particularly preferably 0.5 to 10 g, per liter of the washing solution. Further, as the washing water according to the present invention, ion-exchanged water treated with an ion-exchange resin may be used.

The pH of the wash water applicable to the present invention is 5.5.
The range is from ~ 10.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Further, the time of the water washing treatment is preferably 5 to 60 seconds, more preferably 5 to 50 seconds.

When the washing treatment is carried out in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. Particularly, it is preferable to sequentially perform the treatment with a treatment time of 20% to 50% longer than that in the previous tank.

When the multi-tank counter flow current system is used as the method for supplying the washing liquid in the washing treatment step according to the present invention, it is preferable that the washing liquid is supplied to the post-bath and overflowed to the pre-bath. Of course, it can also be processed in a single tank. As a method for adding the above compound, various methods such as adding as a concentrated solution to the washing tank or adding the above compound and other additives to the washing solution supplied to the washing tank and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, and particularly preferably 0.5 to 50 times the carry-in amount of the pre-bath (usually bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
30 times is preferable. The washing tank in the washing treatment according to the present invention is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As a developing processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. Specifically, it may be a roller transport type in which the photosensitive material is conveyed by sandwiching it between rollers arranged in a processing tank, or an endless belt method in which the photosensitive material is fixed and conveyed in a belt, The processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the web method by contact with the carrier impregnated with the processing solution A method using a viscous treatment liquid can also be used.

In the image forming method of the present invention, the time from exposure to development may be any time, but a shorter time is preferable in order to shorten the entire processing time. The silver halide photographic light-sensitive material according to the present invention is
Even when the time from exposure to development is 30 seconds or less, the change in image density is small and a high-quality image can be stably obtained, so that it can be advantageously used.

[0096]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high 60 ml of ethyl acetate was added to 6.67 g of the boiling point organic solvent (DNP) and dissolved, and this solution was dissolved in 9.5 ml of 15% surfactant (SU-1).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing a using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

The layer structure is as shown in the table below.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Chemical 4]

[0103]

[Chemical 5]

[0104]

[Chemical 6]

[0105]

[Chemical 7]

[0106]

[Chemical 8]

(Preparation of blue-sensitive silver halide emulsion) The following (solution A) was added to 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C.
And (B solution) are simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and further (C solution) and (D solution) below.
Was simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water was added to 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) Addition time of (A solution) and (B solution) and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.0 mol% was obtained.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for Preparing Sensitive Silver Halide Emulsion) Addition Time of (A Solution) and (B Solution) and (C Solution) and (D Solution)
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.0 mol% was obtained.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0115]

[Chemical 9]

[0116]

[Chemical 10]

1000% 2% gelatin aqueous solution kept at 40 ° C
The following (Solution E) and (Solution F) were simultaneously added into 30 ml over 30 minutes while controlling pAg = 6.5 and pH = 3.0.
Liquid) and (H liquid) are controlled to pH = 7.3 and pH = 5.5.
Co-added over 0 minutes. At this time, pAg control is described in JP-A-59-4.
According to the method described in No. 5437, the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide. Then (I
Solution) and (J Solution) were added simultaneously over 2 minutes. Thus, a monodisperse cubic emulsion EMP-4 having an average grain size of 0.43 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.0 mol% was obtained. Analysis using X-ray revealed that the maximum value of the silver bromide content in the portion containing a high concentration of silver bromide was 61 mol%.

(Solution E) Sodium chloride 3.44 g Water was added to 200 ml (Solution F) Silver nitrate 9.9 g Water was added to 200 ml (Solution G) Sodium chloride 103.2 g (Solution K) 50 ml Water was added to 600 ml (Solution H) Silver nitrate 297g Water added 600ml (liquid I) Potassium bromide 2.17g Water added 15ml (solution J) Silver nitrate 3.1g Water added 15ml (solution K) 1-phenyl-5-mercaptotetrazole methanol solution (1% ) In preparing the green-sensitive emulsion (Em-G1), the emulsion (EM
A green-sensitive emulsion (Em-G2) was prepared in the same manner except that the emulsion (EMP-4) was used instead of P-2).

Next, the green-sensitive emulsions (Em-G1) and (E
m-G2) was similarly prepared except that 0.3 mg of thiourea dioxide was added (Em-G3), (Em-G4).
Was prepared. The contents of each emulsion are shown in Table 3 below.

[0120]

[Table 3]

Samples 102 to 104 were prepared in the same manner as in the preparation of Sample 101, except that the green photosensitive emulsion (Em-G1) was changed to (Em-G2) to (Em-G4).

Two samples each were prepared and the exposure time was set by the usual method.
After light wedge exposure for 0.5 seconds, development processing was performed in the following development processing steps A and B.

(Treatment Step A) Treatment Step Treatment Temperature Time Replenishment Amount Color Development A 38.0 ± 0.3 ° C. 20 seconds 80 ml / m ² Bleach-fix A 35.0 ± 0.5 ° C. 20 seconds 120 ml / m ² Wash A 30-34 ° C. 60 seconds 150 ml / m ² Drying 60 to 80 ℃ 30 seconds (Processing step B) Processing step Processing temperature Time Color development B 35.0 ± 0.3 ° C 45 seconds 162ml / m ² Bleach-fixing B 35.0 ± 0.5 ° C 45 seconds 216ml / m ² Wash B 30 ~ 34 ° C. 90 seconds 248 ml / m ² dry 60 to 80 ° C. 60 seconds The composition of the developing solution is shown below.

Color developer A tank liquid Pure water 800 ml Tritylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 6.0g N, N-diethylhydroxylamine 6.8g Triethanolamine 10.0g Diethylenetriamine pentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.0g Potassium carbonate 30g Add water Adjust the total volume to 1 liter and adjust to pH = 10.10.

Color developer A replenisher Pure water 800 ml Triethylenediamine 3 g Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.0 g N, N -Diethylhydroxylamine 6.0g Triethanolamine
10.0 g Diethylenetriaminepentaacetic acid sodium salt
2.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.60.

Color developer B tank liquid Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediamine Tetraacetic acid 1.0 g Catechol-3,5-diphosphonate disodium 1.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4 '-Diaminostilbene sulfonic acid derivative) 1.0g Potassium carbonate 27g Add water to bring the total volume to 1 liter and adjust the pH to 10.60.

Color developer B replenisher Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium sulfite 0.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3, 5-Diphosphonate disodium 1.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.3g Carbonic acid Add 30 g of potassium water to make the total volume 1 liter and adjust the pH to 10.60.

Bleach-fixing solution A Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65g Diethylenetriamine pentaacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml 5-Amino-1,3,4-thiadiazole-2-thiol 2.0g Ammonium sulfite (40% aqueous solution) 27.5ml Add water to make the total volume 1 liter and adjust the pH to 6.5 with potassium carbonate or glacial acetic acid.

Bleach-fix solution B tank solution and replenisher solution Ethylenediaminetetraacetate ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Adjust to 1 liter and adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

Washing solution A Tank solution and replenishing solution Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescence enhancement brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H2O 0.2g PVP} ( polyvinylpyrrolidone) 1.0 g of ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g nitriloacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

Washing solution B Tank solution and replenishing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5g Add water to make the total volume 1 liter and adjust to pH = 7.0 with sulfuric acid or potassium hydroxide. To do.

The green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is density
It was defined based on the reciprocal of the exposure dose giving 0.75, and the leg gradation was defined by the average slope between the density curve 0.3 and the density curve 0.75. The results are shown in Table 4 below.

[0133]

[Table 4]

A silver halide photographic light-sensitive material according to the present invention,
Comparing the sample 104 with the comparative samples 101, 102 and 103, it can be seen that in the case of the development for 45 seconds, when the emulsion sensitized by reduction is used, although slight softening is observed, almost no difference in performance can be obtained. A tendency toward softening was generally observed at 20 seconds development, and as seen in the comparison between Samples 101 and 102, the tendency was remarkable in 102 using an emulsion having a portion containing a high concentration of silver bromide. .. In the comparison between Samples 101 and 103, the softening becomes large in the emulsion subjected to the reduction sensitization, but no softening is observed in the light-sensitive material of the present invention, Sample 104.
It was also confirmed that the sensitivity was high.

Although the cause of this phenomenon is not clear, in the case where the reduction sensitization, which gives only a soft image in the case of mild development, causes the development reaction to proceed rapidly in a short time, the potential generated in the developing solution is increased. It is considered that it contributes to the formation of latent image nuclei that are highly resistant to changes in the image.

Next, an emulsion was prepared by replacing the reduction sensitizer with sodium sulfite and ascorbic acid and evaluated in the same manner. It was confirmed that the effects of the present invention were obtained.

Next, an emulsion containing a high concentration of silver bromide was prepared in the same manner as the emulsions for the blue-sensitive emulsion and the red-sensitive emulsion layer, and an emulsion sensitized by reduction was prepared and evaluated in the same manner. It was confirmed that the effects of the present invention can be obtained regardless of the chromaticity.

Example 2 In the preparation of the color developing solution of Example 1, a color developing agent was used.
N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (exemplified compound (CD-
6)) to equimolar exemplified compounds (I-2) and (CD-
5), (CD-9), and (I-2) and (CD-6) were replaced by an equal amount of the mixture, and a color developer was prepared in the same manner, and evaluated in the same manner as in Example 1. The results are shown in Table 5 below.
It was shown to.

[0139]

[Table 5]

Color developing agents (I-2), (CD-5),
Both (CD-9) and the exemplified compound (CD
It was found that the developing activity was superior to that of (6) and the effects of the present invention could be obtained. Among them, it was confirmed that the color developing agent (I-2) had a large effect, and that the mixture with (CD-6) also showed an excellent effect.

Example 3 EMP-5 was prepared in the same manner as in the preparation of EMP-2 of Example 1, except that the exemplary compound (5), which was a heavy metal compound, was added to (C liquid) in an amount of 10 ⁻⁶ mol per mol of silver halide. EMP-6 was prepared in the same manner, except that Exemplified Compound (6) was added in an amount of 10 to 8 mol per mol of silver halide.

Next, in the preparation of EMP-4 of Example 1, EMP-7 was prepared in the same manner as in (solution G) except that the compound (5), which was a heavy metal compound, was added in an amount of 10 ⁻⁶ mol per mol of silver halide. EMP-8 was prepared in the same manner except that Exemplified Compound (6) was added in an amount of 10 ⁻⁸ mol per mol of silver halide.

This emulsion was used as in Example 1 (Em-G1),
Chemical ripening is performed in the same manner as (Em-G3) (Em-G3).
5) to (Em-G12) were prepared. Table 6 below shows the emulsion numbers, presence / absence of portions containing silver bromide in a high concentration, presence / absence of reduction sensitization, and types of heavy metal compounds.

[0144]

[Table 6]

Using this sample, the same processing as in Example 1 was carried out and the gradation of the legs was examined. The results are shown in Table 7 below.

[0146]

[Table 7]

By adding a heavy metal compound, the softening of the legs in the treatment step A tends to be slightly increased, but the effect of the present invention is clearly recognized, and the effect of sufficiently supplementing the softening is obtained. .. Example 4 The samples 101 to 104 of Example 1 and the samples 301 to 308 of Example 3 were exposed and then developed in the processing step A while changing the standing time. Changes in sensitivity due to changes in standing time are
It was expressed as a relative value based on the sensitivity at the time of development in minutes. The results are summarized in Table 8 below.

[0148]

[Table 8]

Comparing Samples 101 to 104 with Samples 301 to 304, it can be seen that the sensitivity variation increases by containing the heavy metal compound. Samples 101 and 102 or Samples 301 and 3
Comparing 02 with 303 and 304, it can be seen that whether or not there is a portion containing a high concentration of silver bromide has little influence on this sensitivity variation. From the comparison between Samples 101 to 102 and 103 to 104, and the comparison between Samples 301 to 302 and 305 to 306, it can be seen that sensitivity sensitization reduces the reduction in sensitivity. However, the effect is not yet sufficient. It is understood that sufficient effects can be obtained only by using the silver halide photographic light-sensitive material according to the present invention.

Example 5 In the preparation of EMP-4 of Example 1, the amount of potassium bromide added to (solution I) was changed, or potassium bromide and sodium chloride were used, and accordingly, silver nitrate of solution (J) was added. Was adjusted to be equimolar to the halide salt, and the changes were adjusted by the amounts of sodium chloride of (G solution) and silver nitrate of (H solution), respectively. The prepared emulsion (E
m-G1) and (Em-G3) were chemically ripened to obtain emulsions shown in Table 9 below.

[0151]

[Table 9]

Samples 501 to 509 were prepared in the same manner except that the above-mentioned emulsion was used in place of the green-sensitive emulsion (Em-G1) in the preparation of Sample 101 of Example 1. Evaluation was performed in the same manner as in Example 1, and the results are summarized in Table 10 below.

[0153]

[Table 10]

When the silver bromide content of the portion containing a high concentration of silver bromide is low, the softening in the short-time development is small but not sufficient, and the gradation when subjected to reduction sensitization is small. It can be seen that the effect of increasing the contrast is small. In particular, it was surprising that a great effect can be obtained even though the silver bromide content of the whole grain is as low as 0.3 mol%.

Example 6 The silver halide emulsions (EMP-1), (EMP-1) of Example 1 were used.
In the preparation of -3), the concentration and amount of the additive solution are adjusted so that a portion containing a high concentration of silver bromide is prepared, and the exemplified heavy metal compound (6) is added at 1 × 10 ^-8 mol per mol of silver halide. A silver halide emulsion was prepared in the same manner as described above, except that thiourea dioxide was added in an amount of 0.3 mg per mol of silver halide (Em-B1) and (Em-R1).
A red sensitive silver halide emulsion was prepared. Sample 601 was prepared in the same manner as Sample 101 except that the blue-sensitive and red-sensitive silver halide emulsions were replaced with those described above and the green-sensitive emulsion was replaced with (Em-G12). Prints were prepared by laser exposure using samples 101 and 601.

As image data, a 4 × 5 inch size color slide image (portrait) was digitalized into a size of 80 × 80 μm per pixel by a scanner and used.

The exposure apparatus uses helium.
The cadmium laser (about 442 nm), the helium-neon laser (about 544 nm) as the green light source, and the helium-neon laser (about 633 nm) as the red light source were prepared and the optical system was assembled. The light emitted from the three lasers is modulated according to the image data and then focused into one beam,
For silver halide photographic light-sensitive materials transported at a speed of
Scanning exposure was performed at a main scanning speed of 160 m / sec at a right angle to the carrying direction. The beam diameter at this time was about 80 μm, and the exposure time per pixel was 500 nanoseconds.

When Sample 601 was used, an excellent image could be obtained, but in the case of Sample 101, the sensitivity to red light was particularly insufficient and only an image with a low cyan density was obtained. I couldn't. In addition, when comparing the print developed immediately after exposure and the print developed 10 minutes after exposure, not only the density decrease occurs in Sample 101, but pseudo contours are generated in various places on the face, and the quality is remarkably high. Only a reduced image of was obtained. On the other hand, with the sample 601 according to the present invention, an excellent image could be obtained with almost no change in density.

The exposure apparatus was continuously operated, and two hours after the first print was made, the next print was exposed and immediately developed. At this time, it was found that in Sample 101, a pseudo contour was generated on the face, though slightly compared with the first print. On the other hand, sample 601 showed a slight increase in density, but there was no change in color balance, and an excellent image was obtained.

Next, an infrared-sensitive silver halide photographic light-sensitive material was prepared and evaluated in the same manner. (Preparation of infrared-sensitive silver halide emulsion (Em-IR1)) In the same manner as in the method for preparing the green-sensitive emulsion (Em-G12) of Example 1, except that the sensitizing dye was changed to (IRS-1). Infrared sensitive silver halide emulsion (Em-IR1)
An infrared-sensitive silver halide emulsion (Em-IS2) was prepared in the same manner except that the sensitizing dye was changed to (IRS-2).

[0161]

[Chemical 11]

In the preparation of Sample 101 of Example 1, the blue-sensitive silver halide emulsion was replaced by an infrared-sensitive silver halide emulsion (E
m-IR1), the green-sensitive silver halide emulsion was changed to the infrared-sensitive silver halide emulsion (Em-IR2), and the red-sensitive silver halide emulsion was changed to the red-sensitive silver halide emulsion used for preparing Sample 601. Sample 602 was prepared in the same manner except that the above was performed.

An aluminum / gallium / indium / phosphorus semiconductor laser (about 6
70 nm), gallium-aluminum-arsenic semiconductor laser (about 780 nm), and gallium-aluminum-arsenic semiconductor laser (about 830 nm) were prepared and the optical system was assembled. The specifications of the diameter of the light beam, the transportation speed, etc. were matched with those of the laser printer. When an image was output to the sample 602 using this apparatus, a color print with excellent image quality could be obtained. Comparison was made between the case where development processing was carried out immediately after exposure and the case where development processing was carried out after about 10 minutes, but the difference was slight, and even when used in an infrared-sensitive silver halide photographic light-sensitive material, It was confirmed that the effect was effectively obtained.

[0164]

The silver halide photographic light-sensitive material according to the present invention uses a high chloride silver halide photographic emulsion, and a high quality image can be obtained by processing for a very short time.
Since the photographic characteristics rarely change due to the change in the time from exposure to development, this image is characterized by being stably obtained. Furthermore, even when a photographic image is obtained by high-intensity short-time exposure using a laser or the like from software information recorded on a magnetic medium or the like, an image having excellent gradation can be stably obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/407

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one high chloride silver halide emulsion layer on a support, and a color development containing an aromatic primary amine color developing agent and containing substantially no benzyl alcohol. In the method of forming a color image by subjecting to a developing solution, bleach-fixing treatment, and washing treatment with water, the high chloride silver halide emulsion layer has a portion having a silver bromide content of 30 mol% or more. Then
And containing reduction-sensitized silver halide emulsion grains in which 95 to 99.9 mol% is composed of silver chloride, and the color development time is 25 seconds or less, color development processing time, bleach-fix processing time and A color image forming method, wherein the total treatment time of the water washing treatment is within 2 minutes in total.