JPH07140600A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in sharpness and whiteness on a background and low in tendency to soften in gradation on a highlight part. CONSTITUTION:The silver halide color photographic sensitive material has photosensitive silver halide emulsion layers on a reflective support and it is characterized by containing in the emulsion layer silver halide grains having an average grain diameter of <=0.75mum and an applied silver amount of <=0.29g/m<2> and having a layer containing a white pigment between the emulsion layer and the support. It is preferred that the total amount of applied silver in the silver halide emulsion layers and hydrophilic colloidal layers from the emulsion layer nearest to the support to the hydrophilic colloidal layer farthest from the support is <=7.5g/m<2> of the photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which is excellent in sharpness and whiteness and is hard to soften the gradation of highlight portions.

[0002]

2. Description of the Related Art In recent years, the printing process and the developing process of color photographic paper have been shortened and speeded up, and the demand for them has been increasing. In such products, silver bromide or silver chlorobromide which does not substantially contain silver iodide is used because of the need to increase the developing speed, and the silver chloride content of the silver halide emulsion used is high. It is known that this leads to a drastic improvement in the developing speed. Techniques for further rapid processing include, for example, reducing the grain size of silver halide grains or reducing the amount of silver coated on a support, but these include reduction of sensitivity and color density, or highlight portion. However, there is a limit to reducing the grain size and reducing the amount of silver.

Along with rapid processing, there is a great demand for high image quality, especially improvement of sharpness, and many studies have been made so far on improvement of sharpness. Since sharpness is remarkably deteriorated by halation from a support, many studies have been conducted to prevent halation. For example, U.S. Pat. Nos. 2,548,564, 3,625,964, JP-A-63-197943, and JP-A-1-188850 disclose techniques for coloring constituent layers of a light-sensitive material with a water-soluble dye or the like. However, in order to further improve the sharpness, the use of a large amount of these results in softer gradation, lower sensitivity,
This is not preferable because problems such as deterioration of whiteness during rapid processing occur.

As a technique for improving the sharpness, white pigments are disclosed in JP-A-58-60738, JP-B-57-53937, JP-B-59-820, JP-B2-29203 and 3-89340. A technique of providing a containing layer is disclosed. Although it is possible to improve the sharpness by using these techniques, there is a drawback that the whiteness is deteriorated.

[0005]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in sharpness and whiteness and is hard to soften the gradation of highlight areas. To provide.

[0006]

It has been found that the above object of the present invention can be achieved by the following silver halide photographic light-sensitive material.

(1) In a color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on a reflective support, the closest emulsion layer from the support comprises 95 mol% or more of silver chloride,
The average particle size is 0.75 μm or less, and the amount of silver is 0.29 g.
/ M ² or less and having a white pigment between the emulsion layer and the support, a silver halide photographic light-sensitive material.

(2) In a color photographic light-sensitive material having a light-sensitive silver halide emulsion and a non-emulsion layer on a reflective support, the halogen closest to the support on the side coated with the silver halide emulsion layer from the support. The total amount of gelatin contained in the photosensitive silver halide emulsion layer from the silver halide emulsion layer to the hydrophilic colloid layer farthest from the support and the non-photosensitive colloid layer is 7.5 g / m ² or less per 1 square meter of the light-sensitive material. The silver halide photographic light-sensitive material as described in (1) above.

The halogen composition of the silver halide grains according to the present invention is the same as that of all the silver halides constituting the silver halide grains.
It is necessary that 95% or more is silver chloride, but preferably 97 mol% or more of the total silver halide, and most preferably 98-99.9.
Mol% is silver chloride.

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 and 4,225,666, JP-A-55-26589
Issue, Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39
(1973) etc., the octahedron,
Particles having a tetradecahedral shape, a dodecahedron shape, or the like can be prepared and used. 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 prepared silver halide emulsion can be measured by various methods generally used in this technical field. A typical method is Loveland's "Particle Size Analysis Method" (ASTM Symposium on Light Microscopy, 94-122, (1955)) or "Theory of Photographic Processes, 3rd Edition" (Mies and The method described in James Co., Chapter 2, Macmillan, (1966)) can be mentioned.

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 monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient representing 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 the apparatus and method for preparing the 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 for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method 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 the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of 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.

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

It is advantageous that the silver halide emulsion according to the present invention contains heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt,
Group 12 transition metals such as cadmium, zinc, and mercury,
Examples include lead, rhenium, molybdenum, tungsten, and chromium ions. Among them, iron, iridium,
Platinum, ruthenium and osmium transition metal ions are preferred.

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 physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. The heavy metal compound may be dissolved together with the halide salt and continuously added over the whole or a part of the grain forming step, or silver bromide may be localized at a high concentration in a localized portion.

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 ⁹ mol or less, per mol of silver halide.
^It is preferably ^-8 mol or more and 5 × 10 ^-5 mol or less.

For the silver halide emulsion according to the present invention, a sensitization method using a sulfur compound and a sensitization method using a sulfur compound and a gold compound in combination can be used. As the sulfur sensitizer applied to the silver halide emulsion according to the present invention, thiosulfate,
Examples include allylthiocarbamidourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid, rhodanine, and inorganic sulfur.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of silver halide emulsion to be applied and the magnitude of expected effect, but 5 × 10 5 per mol of silver halide. The range of ^{-10 to} 5 x 10 ^-5 mol is preferred, and the range of 5 x 10 ^{-8 to} 3 x 10 ^-5 mol is preferred.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above gold compounds can be preferably used.
The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 mol of silver halide.
It is preferably 1 × 10 ^-8 mol. More preferably
It is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

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 (IIb-1) to
Compound of (IIb-7) or 1- (3-methoxyphenyl) -5
-Mercaptotetrazole, 1- (4-ethoxyphenyl)-
Examples thereof include compounds such as 5-mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. 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, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide
An amount of about ⁻² mol is preferable, and 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol is more preferable. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide.
It is more preferably x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is from 1 × 10 ^-9 mol to 1 × 10 ^-3 per square meter.
Amounts on the order of moles are preferred.

The white pigment used in the hydrophilic colloid layer containing the white pigment according to the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin. For example, titanium dioxide is preferable for various reasons. The white pigment is dispersed in a water-soluble binder of a hydrophilic colloid such as gelatin that allows the treatment liquid to penetrate, and is applied as a hydrophilic colloid layer containing the white pigment.

The coating amount of the white pigment is preferably 1 g.
/ M ² to 50 g / m ² , more preferably 2 g
/ M ² to 20 g / m ² .

The hydrophilic colloid layer containing the white pigment according to the present invention can be provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing hydrophilic colloid layer, if necessary, an undercoat layer on the support, or an intermediate layer or the like at an arbitrary position. A non-photosensitive hydrophilic colloid layer can be provided.

To the hydrophilic colloid layer containing the white pigment according to the present invention, in addition to the white pigment, a coloring agent such as yellow, gray, blue, and black colloidal silver, an inorganic colored pigment, an organic colored pigment, and a dye is added. You can do it.

A colorant-containing hydrophilic colloid layer can be coated between the hydrophilic colloid layer containing the white pigment according to the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, particularly preferably 30% or less.

The content of gelatin contained in the silver halide photographic light-sensitive material according to the present invention is determined from the silver halide emulsion layer closest to the support on the side coated with the silver halide emulsion layer. The total amount of gelatin contained in the light-sensitive silver halide emulsion layer and the non-light-sensitive colloid layer up to the hydrophilic colloid layer farthest from the body is 7.5 g / m ² or less per square meter of the light-sensitive material. Although the effect can be obtained, the white background can be further improved by adjusting the amount to 7.0 g / m ² or less.

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, but in particular, as a dye having absorption in the visible region,
The dyes of AI-1 to 11 described in JP-A-3-251840, page 308 are preferably used. Examples of the infrared absorbing dye include JP-A-1-251
General formulas (I) and (II) described in the lower left column on page 2 of 280750,
The compound represented by (III) has preferable spectral characteristics,
It is preferable because there is no influence on the photographic characteristics of the silver halide photographic emulsion and there is no contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

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 to a specific region in the 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, JP-A-3-25 can be used.
BS-1 to 8 described on page 28 of 1840 can be preferably used alone or in combination. As the green light-sensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. Further, when performing image exposure with infrared light using a semiconductor laser, it is necessary to use an infrared-sensitive sensitizing dye,
As the infrared-sensitive sensitizing dye, JP-A-4-285950, 6-8
The dyes IRS-1 to 11 described on the page are preferably used. Further, the supersensitizers SS-1 to SS-1 described in pages 8 to 9 of the publication.
It is preferred to use SS-9 in combination with these dyes.

The spectral sensitizing dye according to the present invention may be dissolved in an organic solvent, or added as a solid dispersion for further improving the sharpness and the storage stability of the light-sensitive material over time. You may.

The sensitizing dye according to the present invention may be added before or during the formation of silver halide grains or after the formation of silver halide grains. "Before the start of formation" means that the spectral sensitizing dye is previously introduced into the reaction vessel before the reaction for forming the silver halide crystals is started. "During formation" means that the spectral sensitizing dye is introduced during the crystal growth process of the silver halide grains, and "after the grain formation is completed" means that it is added after the substantial grain formation process is completed.

As a method for obtaining a solid dispersion of the spectral sensitizing dye according to the present invention, other than the method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type disperser, As described in JP-A-58-105141, pH 6-8, 60-
A method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system at 80 ° C., and dispersing in the presence of a surfactant which suppresses the surface tension to 38 dyne / cm or less as described in JP-B-60-6496. The method etc. can be used.

As a dispersing device that can be used for preparing a dispersion, for example, in addition to the high-speed stirring type dispersing machine shown in FIG. 1 of JP-A No. 4-125631, a ball mill, a sand mill, an ultrasonic dispersing machine, etc. Can be mentioned.

When using these dispersing devices, as described in JP-A-4-125632, a method such as performing a pretreatment such as dry pulverization in advance and then performing a wet dispersion may be adopted.

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 region longer than 340 nm by 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 range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The general formulas (CI) and (C) described in JP-A-4-114152, page 17
-II) can be mentioned. Specific compounds include those described as CC-1 to CC-9 on pages 18 to 21 of the same publication.

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 (MI) described in JP-A-4-114152, page 12,
The coupler represented by (M-II) may be mentioned.
Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same publication. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same publication are preferable because they are excellent in the reproduction of colors from blue to purple and red and are excellent in the depiction of details.

Examples of yellow couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include couplers represented by formula (YI) described on page 8 of JP-A-4-114152. You can Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same publication. Among them, YC-8 and YC-9 described on page 11 of the same publication are preferable because they can reproduce the yellow of a preferable color tone.

When the oil-in-water type 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 used in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is 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 for dissolving and dispersing 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. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-1 described in JP-A-4-114152, page 33)
1), compounds such as the compound (A′-1) described on page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compound described in 4,187 can also be used.

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 also be used.

The support used in the present invention is a paper base having a resin layer on both sides thereof, and the resin layer on the side coated with the silver halide emulsion layer contains a white pigment. It is a paper support.

The raw paper used in the paper support of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any type of paper such as neutral paper and acid paper may be used. The paper thickness is preferably 40 μm to 250 μm.

Further, the support may be blended with additives such as sizing agents, fixing agents, tension enhancers, densities, antistatic agents, dyes and antifoggants, which are generally used in papermaking, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

As a method of applying a resin coating layer on the support used in the present invention, a method of laminating a polyolefin resin or a polyethylene terephthalate resin is known.

The olefin resin mainly used for the laminate can be selected from ethylene, α-olefins and a mixture of at least two kinds thereof. Among them, the widely used polyolefin resin is low density polyethylene, high density polyethylene or a mixture thereof.

Generally, a resin laminate can be formed by melt-extruding a resin composition on a support and coating the support. In order to carry out this melt extrusion coating method, usually, a resin composition is melt extrusion coated in a form of a single layer or a plurality of layers from a slit die of an extruder on a running support. Usually, the melt extrusion temperature is preferably 200 to 250 ° C.

The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

Examples of white pigments used in the resin coating layer of the support used in the present invention include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, and the like.
Barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is particularly preferable.

Titanium dioxide may or may not be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like. These white pigments are normally contained in an amount of 16% by weight or less, preferably 13% by weight or less, more preferably 10% by weight or less, based on the resin of the resin coating layer on the side of the reflective support on which the photographic emulsion is coated. Most preferred is 7% by weight or less.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

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-lauryl amino)
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-diethylamino Phenylethyl) methanesulfonamide (CD-8) N, N-dimethyl-p-phenylenediamine (CD-9) 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline (CD-10) 4- Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline (CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline The color developing agent is Usually 1 x 10 ^-2 per liter of developer
It is used in the range of from 2 × 10 ^-1 mol, and from the viewpoint of rapid processing, it is preferably used in the range of from 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the color developing solution. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

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 in combination 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 and borate can be used. Inorganic and organic antifoggants can be added as required.

For the purpose of suppressing development, halide salt ions are often used, but chloride ions are mainly used to complete development in a very short time, and potassium chloride, sodium chloride, etc. are used. Used. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol, per liter of the color developing solution. 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 are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol, per liter of color developing solution. The following is desirable.

Furthermore, if necessary, a development accelerator can be used. As the development accelerator, US Pat.
648,604, 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. Issue, same
No. 2,531,832, No. 2,950,970, No. 2,577,127, and non-ionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc.
Organic solvents described in 44-9509, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. Also, U.S. Pat.
In addition to phenethyl alcohol described in No. 5, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. The compound can be used as an organic solvent to increase the solubility of the developing agent.

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

In processing the silver halide photographic light-sensitive material of the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably Is used in the range of pH 9.8 to 12.0.

The processing temperature for color development according to the present invention is 25 ° C.
It is preferably 70 ° C or lower. The higher the temperature, the shorter the treatment time is, which is preferable, but it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C or higher and 60 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is within 45 seconds. Further, it is preferable to carry out in the range of 20 seconds to 3 seconds.

When the silver halide photographic light-sensitive material of the present invention is subjected to a running process while continuously replenishing the color developing solution, the overflow of the color developing solution is reduced,
In order to reduce the environmental damage caused by the waste liquid, the replenishing amount of the color developing solution is preferably 20 to 150 ml per square meter of the light-sensitive material. Further, it is more preferable that the replenishing amount is such that a waste liquid due to overflow is not substantially generated, and the concrete replenishing amount is more preferably 20 to 60 ml per square meter of the light-sensitive material. Under such conditions, the performance of the silver halide photographic light-sensitive material is likely to change, and the silver halide photographic light-sensitive material according to the present invention can be particularly advantageously used under such conditions.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed to the belt and conveyed, but a method of forming a processing tank in a slit shape and supplying the processing liquid to the processing tank and conveying the photosensitive material is also used. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used.

[0074]

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 paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, dye image stabilizer 3.34 g, stain inhibitor ( HQ-1) 0.33 g, compound A 5.0 g and high boiling point organic solvent (DBP) 5.0 g were dissolved by adding 60 cc of ethyl acetate, and this solution was dissolved in 20% surfactant (S
U-1) 220 cc of 10% gelatin aqueous solution containing 7 cc was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0079]

[Table 1]

[0080]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) -sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium Compound A: Pt-octylphenol

[0082]

[Chemical 1]

[0083]

[Chemical 2]

[0084]

[Chemical 3]

[0085]

[Chemical 4]

[0086]

[Chemical 5]

[0087]

[Chemical 6]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over the course of minutes,
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5.

At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using a sulfuric acid or sodium hydroxide aqueous solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained. The average grain size as used herein is a grain size when a projected image of silver halide grains is converted into a circular image having the same area.

Subsequently, emulsions EMP-2 and EMP-3 were prepared by changing the amounts of sodium chloride and potassium bromide used when preparing the above (solution C) as follows.

(Preparation of EMP-2) Sodium Chloride 98.03 g Potassium Bromide 10.49 g (Preparation of EMP-3) Sodium Chloride 92.87 g Sodium Bromide 20.99 g The grain evaluation of these emulsions revealed that (EMP-2
-2) has an average grain size of 0.85 μm, variation coefficient of grain size distribution of 0.08, silver chloride content of 95 mol%, (EMP-3) has an average grain size of 0.85 μm, variation coefficient of grain size distribution of 0.07, chloride The silver content was 90 mol%.

The above emulsions (EMP-1) to (EMP-3)
In contrast, the following compounds were optimally chemically sensitized at 60 ° C. to obtain blue-sensitive silver halide emulsions (EmB-1) to (EmB-1).
-3) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 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 Subsequently, the emulsion (EMP-) was added except that the addition time of (A solution) and (B solution) and the addition time of (C solution) and (D solution) were changed.
Same as 1), average particle size 0.75μm, coefficient of variation 0.07,
Monodisperse emulsion with silver chloride content of 99.5 mol% (EMP-1S)
Got Also for the emulsion (EMP-2), the monodisperse emulsion (EMP-2S) having an average grain size of 0.75 μm, a coefficient of variation of 0.08 and a silver chloride content of 95 mol% was obtained by changing the addition time. Similarly, for (EMP-3), the addition time was changed to obtain a monodisperse emulsion (EMP-3S) having an average grain size of 0.75 μm, a coefficient of variation of 0.07 and a silver chloride content of 90 mol%.

The above emulsions (EMP-1S) to (EMP-3)
S) is optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion (EmB-1S) to
(EmB-3S) was obtained.

Sodium thiosulfate 0.9 mg / mol AgX chloroauric acid 0.57 mg / mol AgX stabilizer STAB-3 9 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4.5 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1.1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
The average particle size is 0.43μ in the same manner as in (EMP-1) except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
A monodisperse cubic emulsion (EMP-4) having m, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The emulsion (EMP-2) is (solution A) and (B).
The average particle size is 0.43 μm and the coefficient of variation is 0.0
8. Monodisperse cubic emulsion with silver chloride content of 95% (EMP-
5) was obtained.

Emulsions (EMP-3) are (A liquid) and (B
The average particle size is 0.43 μm and the coefficient of variation is 0.0
7. Monodisperse cubic emulsion with 90% silver chloride content (EMP-
6) was obtained.

The above emulsions (EMP-4) to (EMP-6)
In contrast, the following compounds were optimally chemically sensitized at 55 ° C. to obtain green-sensitive silver halide emulsions (EmG-1) to (EmG-1)
-3) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
0.50μ in average particle size in the same manner as in (EMP-1) except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
A monodisperse cubic emulsion (EMP-7) having m, a coefficient of variation of 0.07 and a silver chloride content of 99.5% was obtained.

Emulsions (EMP-2) are (A liquid) and (B
The average particle size is 0.50 μm, the coefficient of variation is 0.0
8. Monodisperse cubic emulsion with silver chloride content of 95% (EMP-
8) was obtained.

Emulsions (EMP-3) are (A liquid) and (B
The average particle size is 0.50 μm, the coefficient of variation is 0.0
7. Monodisperse cubic emulsion with 90% silver chloride content (EMP-
9) was obtained.

The above emulsions (EMP-7) to (EMP-9)
In contrast, the following compounds were optimally chemically sensitized at 60 ° C. to obtain red-sensitive silver halide emulsions (EmR-1) to (EmR-1)
-3) 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 stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX STAB-1: 1- (3- acetamidophenyl) -5-mercaptotetrazole STAB-2: 1- Phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0105]

[Chemical 7]

Using the emulsion prepared as described above, a sample (10
1) to (113) were created. Emulsion composition used for each sample preparation,
The amount of coated silver, the presence or absence of a layer containing titanium dioxide described below, and the content thereof are summarized in Tables 3 and 4.

[0107]

[Table 3]

[0108]

[Table 4]

Samples (104) to (108) were S-1 having the following structure between the support and the first layer under the following conditions.
Layer and S-2 layer were applied.

S-2 layer gelatin 0.5 g / m ² (intermediate layer) S-1 layer gelatin 0.5 g / m ² (white pigment layer) anatase type titanium dioxide 2.0 g / m ² Samples (109) to (113) For the S-1 layer gelatin,
The amount of titanium dioxide applied was changed as follows.

S-1 layer Gelatin 1.5 g / m ² (white pigment layer) anatase type titanium dioxide 7.0 g / m ² For sample (111), the non-emulsion farthest from the emulsion layer closest to the support Samples were prepared by reducing the amount of gelatin contained in the layer as shown in Table 5.

[0112]

[Table 5]

<Gradation Evaluation of Highlight Area> Samples (101) to (113) thus prepared were subjected to optical wedge exposure by a conventional method, and then developed in the following developing process.

Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 30 seconds Development processing The composition of the liquid is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter.
Adjust to 10 and replenisher to pH = 10.60.

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

Stabilizing solution tank solution and replenishing solution o-phenylphenol 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 Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to bring the total volume to 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

Using the PDA-65 densitometer (manufactured by Konica Corporation), the obtained sample was measured for blue density, green density and red density, respectively, and the exposure amount giving a density of 0.3 and a density of 0.8 on the characteristic curve was measured. The reciprocal of the difference was defined as the gradation of the highlight part. The results are summarized in Table 6.

In the sample (101) having a low silver chloride content, softening is observed at each concentration. On the other hand, the softening is slightly improved in the sample (104) in which the coated silver amount of the emulsion layer closest to the support and the grain size of the silver halide emulsion grains are reduced. On the other hand, by providing a titanium dioxide-containing layer and increasing the silver chloride content as in Samples (105) and (106), softening is suppressed, but it is not sufficient. On the other hand, in Samples (107) to (113) of the present invention, softening of the highlight portion was not observed despite the reduction of the coated silver amount.

[0120]

[Table 6]

<Evaluation of Whiteness> The blue reflection density (DminB) and the red reflection density (DminR) of the unexposed area were measured with Xrite-31.
It was measured and determined using 0 (manufactured by X-Light).

The smaller DminB and DminR, the better the whiteness. When DminB and DminR are each 0.020 or less, the level is acceptable. When DminB and DminR exceed 0.020, the deterioration of the whiteness is conspicuous visually, and when it exceeds 0.025, the deterioration of the photographic quality is serious.

<Evaluation of Sharpness> A resolution test chart was printed on each sample with red light, and the following development processing step A was carried out. Then, the obtained cyan image was taken as a microdensitometer PDM-5D (Konica Corporation). Concentration), and the value represented by the following formula was defined as the sharpness.

Sharpness (%) = (Dmax-Dmin of 3 lines / mm dense line printed image) / (Dmax-Dmin in large area) where Dmax: maximum density Dmin: minimum density This value is large. The better the sharpness is.

[0125]

[Table 7]

As is clear from Table 7, in the samples (104) to (106) having the titanium dioxide-containing layer, the samples (101) to (103)
Although a slight improvement effect on the white background is seen as compared with, the effect is insufficient. On the other hand, in samples (107) to (110) of the present invention having a titanium dioxide-containing layer and having a reduced coating silver amount, an improvement in whiteness is recognized. Further, in Samples (111) to (113), further improvement in whiteness could be achieved by reducing the amount of gelatin contained in the light-sensitive material.

Regarding the sharpness, in the samples (109) to (113) in which the silver halide grains in the emulsion layer closest to the support were reduced in size to reduce the coated silver amount and the titanium dioxide containing layer was provided. It can be seen that the sharpness improving effect is remarkable.

From the results of Tables 6 and 7, the sharpness and whiteness of the samples having the titanium dioxide-containing layer were determined by defining the silver chloride content, the coating silver amount and the grain size of the silver halide emulsion grains. It can be seen that it was possible to improve and prevent softening of the gradation in the highlight portion.

[0129]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in sharpness and whiteness and is hard to soften the gradation of the highlight portion.

Claims (2)

[Claims] 1. A color photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-emulsion layer on a reflective support,
The emulsion layer closest to the support is composed of 95 mol% or more of silver chloride, the average grain size of silver halide grains constituting the emulsion layer is 0.75 μm or less, and the coated silver amount is 0.29 g / m ² The following is a silver halide color photographic light-sensitive material having a white pigment between the emulsion layer and the support. 2. A color photographic light-sensitive material having a light-sensitive silver halide emulsion and a non-emulsion layer on a reflective support, which is closest to the support on the side coated with the silver halide emulsion layer. The total amount of gelatin contained in the photosensitive silver halide emulsion layer from the silver emulsion layer to the hydrophilic colloid layer farthest from the support and the non-photosensitive colloid layer is 7.5 g / m ² or less per 1 square meter of the light-sensitive material. The silver halide color photographic light-sensitive material according to claim 1, which is present.