JP2003307810A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost new silver halide photographic sensitive material capable of providing a color print from a photosensitive material for photographing even when image information is photoelectrically read in the undesilvered state using an inexpensive specular scanner by enhancing the suitability of a silver halide photographic sensitive material to a specular scanner. <P>SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support, when the total coating weight (g/m<SP>2</SP>) of silver in silver halide emulsions comprised in the silver halide emulsion layer is represented by A and specular transmission density in the undesilvered state after development as a value represented by the equation B=-logTs (where Ts is specular transmittance at 550 nm measured by integration at an angle of 3° (half angle)) is represented by B, the value of B/A is <0.57. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a novel silver halide photographic light-sensitive material excellent in. [0002] [Prior Art] Known as conventional color photography
In the method, a color light-sensitive material for photographing (for example,
Color negatives usually record blue light to form a yellow image.
The layer that forms, forms a magenta image by recording green light
Layer, a layer that records red light to form a cyan image.
In the development process, the latent image formed by exposure is included.
Developing agent in the process of reducing silver halide grains to silver
Is oxidized and the oxidized form reacts with the dye-donating coupler
A dye image is formed by (coupling reaction). Unexisting
The image's silver halide and developed silver remain in the development process.
The negative dye image obtained by the bleach-fixing process
Project it, expose it to a color print photosensitive material,
The same development and bleach-fixing processes are applied to the print material.
Lint is obtained. In color negative sensitive materials,
Filter for adding spectral sensitivity difference between the three photosensitive layers
For purposes of colloidal silver and dyes, antihalation
Fine silver or dye is contained in the photosensitive material.
Of these, metallic silver such as colloidal silver is bleaching
It will be removed. The image information contained in the color negative
After photoelectric reading, the image is processed and recorded
Information, and this image information can be used for other printing materials.
A method for obtaining a color image is also known. Especially the above image information
The information is converted into a digital signal and the recording light modulated accordingly
Therefore, it is finished by scanning exposure to photosensitive material such as color paper.
Development of digital photo printers for printing
An example is described in JP-A-7-15593.
It is listed. Convert image information into digital signal as above
When converting, in principle the underlying image information is the dye image
Need not be. For example, in EP526,931
Describes a system in which one layer consists of only a silver image.
In Kaihei 6-266066, all three layers contain color materials
To read information on residual silver halide and developed silver
Is described. In recent years, rapid development processing and processing waste liquid
In order to reduce the impact on the environment,
Color developing agent is incorporated in the photosensitive material without using a color developer.
And does not contain a developing agent called activator processing
A method of developing with a processing solution is disclosed in JP-A-5-257225.
, JP-A-57-14939, JP-A-7-13435
No. 5 and Japanese Patent Publication No. 44-18670. Example
For example, JP-A-5-257225 describes a color developing agent.
Widely used paraphenylenediamine derivatives
Is built in a stable form and activated during development processing.
A method for forming a precursor and using it for color development is disclosed.
ing. In either method, after color development processing, bleaching and fixing
Processed to remove developed silver and undeveloped silver halide
This method uses a dye image. On the other hand, the processing of photosensitive materials using silver halide.
As a management method, a simple and quick method using heat development is disclosed.
It is. Japanese Patent Application Laid-Open No. 9-146247 discloses heat development.
There is a description of a color light-sensitive material for photographing. Silver halide photography by various methods as described above.
Image processing after photoelectrically reading image information of photosensitive material
To build a system for recording image information
In recent years, increasing scanning costs have become a problem.
The In order to reduce costs, it is desirable to make scanners cheaper
It is. Rhino type that uses diffused light for reading light
Scanners such as Hell Topaz negative film scanner
-Is the scattered light component in the processed silver halide photographic material.
It is possible to read while removing
However, there is a drawback that it is expensive. Nikon LS
Parallel light (specular light) to reading light such as -4000
If an inexpensive scanner is used,
Silver halide photographic light-sensitive material, especially remaining silver halide,
For silver halide photographic materials that do not remove developed silver
Reads with parallel light (specular light) rather than diffuse light
This method is easier to detect the scattered light component.
Dmin markedly increased during removal, RMS deterioration, scan
Long scanning time or scanning error
There was a drawback that it was easy to handle. [0006] Accordingly, it is an object of the present invention.
Specular scanner of silver halide photographic light-sensitive material
-Improves aptitude and uses an inexpensive specular scanner
Even if the image information is read photoelectrically without desilvering,
Color prints can be obtained from photosensitive materials for photography
A new low-cost silver halide photographic material
It is to provide. [0007] [Means for Solving the Problems] (1) There is little on the support.
Silver halide with at least one silver halide emulsion layer
In a photographic material, it is contained in the silver halide emulsion layer.
Total silver coating amount of silver halide emulsion (g / m²) A,
Specular transmission density without desilvering after development
When the value represented by the following formula is B, the value of B / A
Silver halide copy, characterized in that is less than 0.57
True photosensitive material. B = -logTs Where Ts was measured by integrating at an angle of 3 ° (half angle) 5
It represents the specular transmittance at 50 nm. (2) Fewer silver halide emulsion layers
Both layers have an average primary particle size of 1 treated with silica.
Fine titanium oxide with a particle size of 100 nm to 100 nm
It is characterized by being dispersed and contained while being retained
(1) The silver halide photographic light-sensitive material described in (1). (3) Dispersion stability of the fine particle titanium oxide
Dispersed using low molecular weight gelatin as an agent.
The silver halide photographic light-sensitive material as described in (2) above
Fee. (4) Fewer layers containing titanium oxide.
Silver bromide with a silver chloride content of 50 mol% or more in at least one layer
Grains, silver iodide grains, or halogens containing silver iodobromide grains
(2) or containing a silver halide emulsion
The silver halide photographic light-sensitive material as described in (3). (5) Fewer layers containing titanium oxide.
At least 50% of the total projected area of silver halide grains per layer
% Is less than 0.13 μm and the silver chloride content is 50%.
Halo containing at least mol% silver bromide grains or silver iodobromide grains
(2) or containing a silver halide emulsion
The silver halide photographic light-sensitive material as described in (3). [0012] DETAILED DESCRIPTION OF THE INVENTION A silver halide photographic light-sensitive material of the present invention.
All the silver halide emulsions contained in the light-sensitive material are coated.
Cloth silver amount (g / m²) A spec at 550nm
B / A value is not 0.57
It is characterized by being full. Where the specular transmission density
Degree B is removed from the developed sample by fixing or other methods.
Integral measurement at an angle of 3 ° (half angle) without silver
The specular transmittance at 550 nm is Ts.
And B = −logTs. Specular
-The transmittance is Hitachi C-2000 color analyzer.
It can be measured with any commercially available optical meter. The lower the B / A value
However, Dmin is reduced in an inexpensive specular scanner.
Can prevent RMS deterioration and shorten the scanning time.
Or the effect of preventing scanning errors is great. B / A
Is preferably less than 0.29, 0.17 or more
More preferably, it is below. About the total amount of silver applied
Reduce the amount of silver used in consideration of recent environmental issues
It is preferable. Therefore, the total amount of silver applied is 0.1 g / m.²Less than
Top 10.0g / m²Is preferably less than 1.5 g
/ M²6.0 g / m or more²Even more preferred to be less
Yes. To achieve the above specular performance
And a silver halide emulsion layer of the silver halide photographic material.
The average primary particle size is at least 1 nm and at least 100 n
Fine particle oxidation less than m and surface treated with silica
It is preferable that titanium is dispersed while maintaining transparency.
In that case, low molecular weight gelatin as a dispersion stabilizer
It is further confirmed that fine particle titanium oxide is dispersed using
Is preferred. It is transparent that fine particle titanium oxide is dispersed.
Hydrophilic binder contained in the same layer while maintaining its properties
This will be described later.
The As a preferable application example of the present invention, a support is used.
At least one layer of red-sensitive silver halide milk on each
Agent layer, green light sensitive silver halide emulsion layer, blue light sensitive halogen
A silver halide color photographic material having a silver halide emulsion layer is provided.
Can be mentioned. As another application example, on a support.
At least photosensitive silver halide, binder, and
And dye-donating couplers in the light sensitive wavelength region and before
The hues of the dyes formed from the dye-donating coupler
Silver halide having at least three different photosensitive layers
In color photographic light-sensitive materials, by imagewise exposure and development processing.
After forming a color image of at least three colors
The image information can be optically removed without removing silver halide and developed silver.
Information or electrical information and based on that information
Image forming method for obtaining a color image on another recording material
It is done. In addition, as an application example, there are few on the support.
Both photosensitive silver halide, binder, dye-donating cap
React with this dye-donating coupler
A developing agent that can be formed, its photosensitive wavelength region and said
The hues of dyes formed from dye donors are different from each other.
A silver halide color photograph having at least three photosensitive layers.
In photosensitive materials, at least imagewise exposure and development processing
After forming a three-color image, the remaining silver halide is developed.
Without removing the silver, the image information is optical information or
Converts it into electrical information, and based on that information, another recording material
And an image forming method for obtaining a color image on the material. Furthermore, as an application example, on the support,
At least photosensitive silver halide, binder, dye-donating dye
Puller, and dye reacts with this dye-donating coupler
A developing agent capable of forming a photosensitive wavelength region and
The hues of the dyes formed from the dye donors are different from each other
At least three photosensitive layers and decoloring or
Characterized in that it has a layer containing the dye to be removed
In silver halide color photographic materials, imagewise exposure,
After forming a color image of at least three colors by development processing, it remains
Without removing silver halide and developed silver.
Convert image information into optical or electrical information and
Image form to obtain a color image on another recording material based on the information
The synthesis method is mentioned. Next, in the present invention, titanium oxide is dispersed and the milk is dispersed.
Effect by increasing the refractive index of the hydrophilic binder in the agent layer
Describe the fruit. It is disclosed in JP-A-12-347336.
As the titanium oxide fine particles, the gelatin that constitutes the emulsion layer
Dispersed in a hydrophilic binder such as
By increasing the refractive index of the hydrophilic binder,
Reduces reflected light at the interface between plate particles and hydrophilic binder
Scattering can be reduced. Especially cheap specular
Reduces Dmin in the scanner and prevents RMS deterioration
Scanning time reduction or scanning error
This is a great prevention effect. JP-A-11-265037
In order to reduce the ratio of diffused light to the total transmittance,
Although titanium oxide is dispersed, specular transmission density
There is no mention of measured Dmin, specular scan
An attempt to provide an inexpensive system using a channel
This is different from the gist of the present invention. The substantial refractive index of the hydrophilic binder is
Dry the binder composition using a method such as spin coating.
Apply to a transparent glass plate and JA Woollam
  Can be measured with an ellipsometer such as VASE from Co.
The The substantial refractive index of the binder is 1.6 to 2.7.
It is preferable that it is 1.6 to 1.9.
Good. In order to achieve the above refractive index, especially binder
-Is gelatin, the volume percentage of titanium oxide =
[Sample application area 1m²Titanium oxide occupant
Product (mL) / (Sample application area 1m²Per oxidation
Tan occupied volume + sample application area 1m²Per zera
Chin Occupied Volume)] x 100
The volume% is preferably 5% or more and less than 100%,
It is particularly preferably 5% or more and less than 40%. Fine titanium oxide retains transparency
Dispersed in the emulsion layer includes fine titanium oxide.
, Silver halide grains and water-insoluble photographic useful compounds
The hydrophilic binder composition liquid that makes up the emulsion layer excluding
When filmed, the haze of the film is very small.
The haze of the hydrophilic binder is not particularly limited, but 20
Preferably, it is preferably 10 or less.
And is most preferably 5 or less. Haze
Is a city such as Nippon Denshoku Industries Co., Ltd.'s VG-1D variable angle gloss meter
It can be measured using a commercial haze meter. Composition of the binder
Triacetyl acetate etc. by the method of bar coating etc.
Can be measured after being applied to a transparent base with a thickness of 1μm and dried.
The Also, the cumulative average primary grain of fine particle titanium oxide.
The diameter is not limited, but it is 1 nm or more and less than 100 nm
Preferably, 0.01 μm or more and less than 0.05 μm
More preferably. Where cumulative average primary particle size
(Hereinafter simply referred to as “average primary particle size”)
The particle size distribution of the body is measured and the entire body of the particle population
When the total product is 100%, the body from the smaller particle size
It is the particle size at which the volume is 50% by accumulation. Nikki
By dynamic light scattering method such as micro track UPA
It can be measured by a measuring device. Next, in the present invention, it is dispersed for controlling the refractive index.
A preferred form of the fine particle titanium oxide will be described. Main departure
The primary particle shape of bright titanium oxide is cylindrical or spindle
A shape or a spherical shape is preferable. Used in the present invention
The average primary particle size of the titanium oxide is X-ray diffraction,
Is the strongest interference line on the (1, 0, 1) plane, and rutile is (1,
It can be obtained from the half width of the strongest interference line on the (1,0) plane.
The The surface treatment of the titanium oxide of the present invention is explained.
Light up. Since the isoelectric point of titanium oxide is 6, neutral pH
Dispersion stability in the region is very poor, especially the particle size
Agglomeration by van der Waals force as it becomes finer
Becomes remarkable. In the example of JP-A-11-265037
Is a titanium alkoxide method under strong acidity near pH 0.
The dispersion in which fine particles are formed is used.
This is because the titanium oxide dispersion lacks surface treatment.
Agglomerates significantly in the neutral pH region and examines photographic performance
It was found to be inappropriate. The fine titanium oxide of the present invention is silicon oxide.
Surface treatment is preferred for stabilization by charge repulsion
Good. The preferred usage of silicon oxide is relative to titanium oxide.
1-30 mass%, more preferably 2-20 mass%
is there. If the amount of the surface treatment agent is too small, it may cause poor dispersion or aging.
If the amount of titanium oxide is too high
Is substantially reduced, and the desired refractive index is decreased, which is preferable.
No results. Other tables, whether inorganic or organic
It can be preferably used in combination with a surface treatment agent. Inorganic surface
Treatment agents include aluminum oxide and zirconium oxide
Zinc oxide and the like are preferable. In organic matter, siloxane,
Stearic acid, trimethylolpropane, gelatin, etc.
Is mentioned. The total amount of surface treatment agent used is equivalent to that of titanium oxide.
3 to 45% (mass) is preferable, more preferably 5 to 5%.
35% by mass. The larger the amount of treatment agent used, the more dispersed
However, since the refractive index is relatively lowered,
The reduction in tabular grain reflectance is reduced and
The above two performances are compatible.
It is preferable to select appropriately. Next, the surface treatment of titanium oxide is, for example, as follows.
This can be done. Using synthesized titanium oxide
Disperse with phosphate such as sodium oxametaphosphate, pH
Is adjusted according to the solubility of the surface treatment agent. In this, acid
Suspension of aluminum halide and / or silicon dioxide
P after mixing, the solubility of the surface treatment agent decreases after mixing
Adjust to H. As a result, the surface treatment agent is oxidized titanium.
As a result, it deposits on and adheres to the surface of the surface. As needed,
Concentration of surface treatment agent relative to titanium oxide or surface treatment
Appropriate selection of the temperature during processing and the firing temperature after processing
Thus, it is possible to change the amount and form of adhesion. The crystal form of titanium oxide used in the present invention is not limited.
Although there is no limit, the refractive index of anatase type is as low as 2.5
On the other hand, the rutile type is 2.8, which is preferable in terms of refractive index.
Also, the rutile type is less active than the anatase type
In addition, the rutile type is preferable from the viewpoint of weather resistance. The rutile type titanium oxide is added to the titanium oxide of the present invention.
Greatly affects the reflectance reduction effect of tabular grains
The rutile crystallinity will be described. Rutile crystallinity
Is calculated by calculating the mass ratio of silicon and titanium oxide to be measured to 1: 5.
Mix to become. Then by X-ray diffraction, rutile
The peak area of the (1,1,0) plane and the peak area of silica
Take the ratio. As a standard sample, MT600B (Taika Co., Ltd.)
Company-made fine titanium oxide, average primary particle size 50 nm, no surface
Surface treatment), and this is 100% rutile crystallinity.
Then, the ratio with each measurement sample is calculated. In the present invention
Is defined as the rutile crystallinity. When the rutile crystallinity is large, the crystal becomes strong.
Formed, excellent in chemical resistance, weather resistance, etc.
It is preferable because the ratio is high, but the transparency of the film is reduced
It ’s not. Conversely, if the rutile crystallinity is low, chemical resistance and weather resistance
The reflectivity of the tabular grain is reduced.
Reduction is less desirable, but scattering is less likely to occur
As a result, the transparency of the film is improved. In the present invention, rutile
The preferred range of crystallinity is 20-80%, more preferred
A preferable range is 30 to 70%, and a more preferable range is 35 to 70%.
55%. The control of the rutile crystallinity is controlled by a fine method described later.
Of the titanium oxide production process, firing temperature after surface treatment
Temperature, drying temperature and time, post-treatment with acid and alkali
Can be controlled by temperature, concentration, and time. Ma
Although related to this, it can also be controlled by the particle size.
Is possible. Various titanium oxides can be used in the present invention.
Can be used, but neutralization of titanium salt
Solution, neutralization of sodium titanate, addition of titanium alkoxide
Manufactured by water decomposition and gas phase decomposition of titanium alkoxide
Yes, in “Dictionary of Pigments” Asakura Shoten p194-195 etc.
There is a description. The columnar or spindle-shaped that can be used in the present invention.
Titanium oxide is generally prepared by a wet method. Particle size
And the difference in aspect ratio is the purity of raw materials, hydrolysis rate,
Firing temperature, drying temperature, post-treatment with acid and alkali (Lee
Ching) conditions (concentration, time, temperature) and surface treatment agent (type)
And quantity). The fine titanium oxide particles used in the present invention are powders.
It may be prepared by dispersion or a commercially available slurry
May be used. Fine particles, powder or colloidal dispersion
Use as a body. Water is used as the dispersion medium. A dispersion is obtained from powder of titanium oxide fine particles.
For this purpose, a known disperser can be used. Disperser
Examples include ball mills, vibrating ball mills, planetary ball mills
, Sand mill, colloid mill, jet mill and
Includes a miller. For the disperser, see JP-A 52.
No. -92716 and International Patent Publication 88/0747
There is description in 94 specification. Vertical or horizontal media dispersion
Machine is preferred. Polydisperse as a dispersant during or after dispersion
Adding phosphate or polyacrylate is a dispersion
Preferred for stabilization. The silver halide photographic light-sensitive material of the present invention is constituted.
In at least one silver halide emulsion layer, there are fine grains
Titanium oxide with titanium oxide and silver halide grains
Low molecular weight gelatin can be used as a dispersion stabilizer
preferable. Since the surface area of the fine particles is extremely large,
Therefore, a large amount of dispersant is required.
When using other dispersants, salt often precipitates, resulting in poor image quality.
This is not preferable. Especially for heat-developable photosensitive materials
If water-soluble salt is used as a powder, problems such as precipitation
Yes. For example, the oxide oxide disclosed in the example of JP-A-11-265037
Disperse N40 (Allied C)
olloids Ltd.).
Will change the quality of the film, causing salt to precipitate and significantly improving the image quality.
I found it worse. Low molecular weight gelatin alters film quality
This is preferable because there is no problem of crystallization or salt precipitation. The low molecular weight gelatin used in the present invention is:
The weight average molecular weight of gelatin is 60,000 or less, preferably 30,000
Less than, and more than 2000, preferably more than 5000
Something is desirable. Low molecular weight gelatin used in the present invention
Usually, it can be made as follows. For normal use
Dissolve gelatin with a weight average molecular weight of 100,000 in water
Add gelatinolytic enzyme to enzymatically degrade gelatin molecules
To do. R.J.Cox Photographic Gelat for this method
in II, Academic Press, London, 1976, p.233-25
1, p.335-346 can be referred to. This place
Since the binding position where the enzyme degrades is fixed,
Low molecular weight gelatin with a narrow molecular weight distribution is preferred
Yes. In this case, the longer the enzymatic degradation time, the lower the molecular weight.
Quantify. Other, low pH (pH 1-3) or high (p
H10-12) A method of heating in an atmosphere and hydrolyzing
is there. Titanium oxide water-soluble dispersion
Low molecular weight gelatin as a stabilizer is chemically modified
Also good. Low molecular weight gelatin used as a dispersion stabilizer
Is 0.001 mass% to 200 mass% of the total mass of titanium oxide
% Is preferably contained. 0.001% by mass or less
Is not capable of preventing cross-linking aggregation by low molecular weight gelatin.
Sufficient and causes cross-linking aggregation. The amount of added dispersion stabilizer is
When the content is 200% by mass or more, cross-linking coagulation by an added binder
The collection probability is very high, which is not preferable. Low molecular weight
The mass% of gelatin with respect to the total mass of titanium oxide is 1% or more.
100% or less is more preferable, and 5% or more and 50% or less
Further preferred. The low molecular weight gelatin contains titanium oxide powder.
It may be added in the middle of dispersion, or it may be added later to the dispersion after dispersion.
It may be added. Next, as an application example of the present invention, the remaining halo
The image information can be stored without removing silver
Converted into optical or electrical information and based on that information
And an image forming method for obtaining a color image on another recording material.
The details will be described. A color image obtained by exposure and development is obtained.
Based on this, the color paper is left with both the silver halide and developed silver remaining.
In the case of projection exposure on a super-par, etc., JP-A-9-146247
According to the maximum absorption wavelength of the three color dyes after development.
Transmission Dmin is 2.0 or less, Dmax is 4.0 or less, and Dmax−
Granularity, sharpness, and color reproduction when Dmin is 1.0 or more
It is clear that good prints with almost no problems can be obtained.
I am clear. Where Dmax and Dmin are specular transmission densities
Represents the value of. In the following description, the concentration is special.
Unless otherwise specified, specular-represents transmission density
And Do not bleach or fix conventional photographic materials
If there is a large amount of silver halide applied and anti-ha
Dye or anti-irradiation dye, colloid
Dmin and Dmax are higher due to residual silver and filter dyes.
Exceeding the above values, the amount of light exposed to color paper etc. increases
Therefore, the influence of printout at the time of exposure increases.
In addition, irradiation required for so-called color negative sensitive materials
Dye, filter dye, antihalation dye
If it remains after processing, Dmin and Dmax of image information will be unnecessarily large.
It is preferable to be removed during the development process.
Yes. Color image information including developed silver information is optically processed.
When converting to information or electrical information, read photoelectrically
May be converted into a digital signal. Make this reading transparent
When measuring with excessive light density, the dye pole is determined by the developed silver density.
Desirably, the dye concentration at the large absorption wavelength is 3 times or more.
That's right. Silver halide is the theoretical amount necessary for color image formation.
By using more than 5 times the density of unexposed and exposed areas
Hope to make the difference less than 20% of the original concentration
Good. In addition, the silver halide and developed silver concentrations are the same.
2.0 or less is preferable. When the above conditions are met
The original image is faithfully processed by image processing from the read signal.
Can be reproduced. In this case, the output material is photosensitive material.
For example, sublimation type thermal transfer material, ink jet
Material, full color direct thermal recording material, color CR
T, color LCD, etc. may be used, but heat developed color printing
Materials such as PICTROGRAPHY from Fuji Photo Film Co., Ltd.
 Output to 3000 is simple and prints with good image quality
An image is obtained. Digital image signals can be processed arbitrarily
Since it can be edited, you can freely modify, transform, and add
Can be output after processing. In the present invention, a silver halide developing process is carried out.
As a matter of course, the exposed photosensitive material is reduced with a base or base.
The development temperature is 60 ° C.
A heat development method of 150 ° C. or lower is preferable. This place
Image information of the obtained color negative is converted into a digital signal.
If you print with the above photothermographic material,
Use all processing solutions used in national color photography
You can do everything from shooting to printing. Fuji
Using PICTROSTAT 330 of Photo Film Co., Ltd.
The SE unit optically reads and outputs image information
Even without using any processing solution,
Can be done. Next, the silver halide photographic light-sensitive material of the present invention.
Aqueous dispersions of water-insoluble photographic useful compounds used in
To say. In the present specification, water insolubility means photographically useful
Coating composition when adding the required amount of compound into the photographic element
Even if the product is diluted to the limit concentration that can be applied, it can be used against water.
Coating composition as an aqueous solution due to lack of solubility
It means that the whole amount cannot be added. Usually 20 ° C water 10
Solubility with respect to 0 g is 10 g or less, preferably 5 g or less
Say against things. Water-insoluble photograph useful compound used in the present invention
Products are dye image forming couplers, dye image donor redox compounds
, Anti-stain agent, anti-fogging agent, UV absorber, withdrawal
Anti-coloring agent, anti-color mixing agent, nucleating agent, silver halide solvent, drift
White accelerator, developer, filter dye and before
Precursor, dye, pigment, sensitizer, hardener, brightener, desensitizer,
Antistatic agent, antioxidant, developing agent oxidant scavenger
-Mordant, matting agent, development accelerator, development inhibitor, hot melt
Agent, color regulator, slip agent and for dispersing them
Polymer latex for dispersion used as a medium, water-free
Soluble inorganic salts (such as zinc hydroxide) and film strength improvers
Can be mentioned. These water-insoluble photographically useful compounds are generally
In addition, water of oil-in-water dispersion (emulsion) and solid fine particle dispersion
Or emulsified by mechanical force as hydrophilic colloid dispersion
Or a photographic emulsion layer dispersed in solid fine particles
Used for other layers. Description of the above water-insoluble photographically useful compound
For example, Research Disclosure (R.D.)
No.17643, No.18716, No.307105, No.40145
And so on. As an example of a water-insoluble photographically useful compound, color
An image forming coupler may be mentioned. When used for normal photography
Dye image forming couplers, high-boiling organic solvents (boiling point 60
℃, preferably 175 ℃ or more) and solubility
Low boiling point organic solvent (boiling point 30-160 ° C)
A mixture of this composition and a hydrophilic colloid solution
Is emulsified in the presence of a surfactant. The dye image-forming coupler and the high boiling organic solvent
Higher solubility in the latter is preferred. Of coupler
The melting point is preferably 155 ° C. or less at 1 atm, more preferably
125 ° C or lower, more preferably 100 ° C or lower
Is preferred. Use multiple couplers to reduce melting point
The technology to lower the melting point and improve the solubility is preferably used
I can. In the present invention, a high-boiling organic solvent and dispersion
Melting of a mixture of several water-insoluble photographically useful compounds excluding auxiliary agents
The point is 2 ° C lower than the volume weighted average of the melting points of each compound
Preferably lower than 4 ° C.
preferable. Aqueous content of the water-insoluble photographically useful compound of the present invention
The powder includes the above-mentioned water-insoluble photographically useful compound of the present invention.
Is obtained by dispersing the composition in a hydrophilic binder. A set comprising the water-insoluble photographically useful compound of the present invention
The hydrophilic binder that disperses the composition is a water-soluble protective colloid.
It is preferable to include Known as a protective colloid
Can be used, polyvinyl alcohol,
Polyethylene oxide, polyvinyl pyrrolidone, poly
Acrylic acid, polyacrylamide, polysaccharides, casein,
Examples include gelatin. Particularly preferred is gelatin. Aqueous content of the water-insoluble photographically useful compound of the present invention
It is preferable that the dust contains a surfactant. Surfactant
As this, a well-known thing can be used. Conventional disclosure
Dispersing aids that have been used include alkylphenoxyates
Xiethane sulfonate, polyoxyethylene alkyl
Phenyl ether sulfonate, alkyl benzene sulphone
Honates, alkylbenzenesulfonic acid, alkylnaphth
Talen sulfonate, alkyl sulfate ester salt, alkyl
Rusulfosuccinate, sodium oleylmethyl taura
Formaldehyde condensation polymerization of id and naphthalenesulfonic acid
, Polyacrylic acid, polymethacrylic acid, maleic acid
Crylic acid copolymer, carboxymethyl cellulose, sulfuric acid
Anionic dispersants such as cellulose, polyoxyethylene
Alkyl ether, sorbitan fatty acid ester, polio
Xylethylene sorbitan acid fatty acid ester, polyalkyl
Nonionic components such as block polymer of lenoxide
Examples include powders, cationic dispersants and betaine dispersants
It is done. These are materials that are dispersed by conventional methods (high boiling
When using point organic solvents,
Total with high-boiling organic solvent, or water when not used
Less than 30% by weight to the insoluble photographically useful compound)
used. Useful water-insoluble photograph as a photographic material
To provide a layer containing an aqueous dispersion of
Disperse the dispersion thus obtained in a suitable binder.
To prepare a substantially uniform coating composition.
And by applying it on the desired support
Rukoto can. The binder can be a photosensitive emulsion layer or a non-photosensitive layer.
Any hydrophilic colloid that can be used in the hydrophilic layer
There is no limit, but usually gelatin or polyvinyl alcohol
Synthetic polymers such as
The Such a coating composition comprises a dispersion prepared
Is mixed with other coating components immediately, and after mixing for 20 minutes
It is preferable to apply in between. This will create
The dispersion state is unstable, and it is easy to cause aggregation and particle size change.
Even dispersions can be incorporated into membranes with little degradation.
The In order to speed up mixing with other coating ingredients,
Without storing the liquid flow from the liquid outlet,
Direct inline using liquid flow and static mixer
It is preferable to mix closely. Mixing within 10 minutes after creation,
Preferably within 5 minutes, more preferably within 1 minute. Special
Kaihei 3-223839 applies from preparation of coating composition to coating.
An example of defining the time at is. Next, a preferred emulsification method for the present invention will be described.
Bell. The emulsification method includes stirring with a chemistor, homogenization.
High speed shear using a mixer, colloid mill, etc.
Milling is common. Also, the method using ultrasound
is there. And like a Mantry homogenizer, the pressure
The added liquid flow collides with the wall, or the liquid flows collide with each other.
For example, there is a method of miniaturization by impact or share. Also
JP-A-6-308691 discloses the use of a high-pressure homogenizer.
Is disclosed. Other ultrasonic homogenizers
There is also a method using a low jet mixer. US Pat. Nos. 4,933,270 and 49
As described in No. 578757, etc., from a homogeneous system to a dispersion
There has been proposed a method of precipitating. Also porous glass
The method of dividing oil droplets by membranes and milk by electrocapillarity
Chemicalization methods have also been proposed. Aqueous content of the water-insoluble photographically useful compound of the present invention
The average particle size of the dust is from 0.01 μm to 0.1 μm
It is preferable. The average particle size of the aqueous dispersion is Horiba
Measurement equipment using dynamic light scattering, such as LA920
Can be measured. When the average particle size is small, the activity of the coupler is reduced.
And improved disperse dye covering power
The amount used can be reduced. Fine acid by the method described in JP-A-12-347336
When the refractive index of the emulsion layer is increased using titanium fluoride, it is insoluble in water.
The average particle size of an aqueous dispersion of a useful photographable compound is 0.1 μm
If it is larger, water increases when the refractive index of the hydrophilic binder is increased.
Aqueous dispersion of insoluble photographically useful compound and hydrophilic binder
Scattered light is generated between the two and the transparency of the emulsion layer after development is remarkable.
The average particle size is 0.01
An aqueous dispersion of a water-insoluble photographically useful compound of ~ 0.1 μm
Improve the transparency of the coating film after development by using,
It is preferable because haze is lowered. The haze is VG-1D type manufactured by Nippon Denshoku Industries Co., Ltd.
It can be measured using a commercially available haze meter such as a variable angle gloss meter.
In the case of silver halide color photographic light-sensitive materials, the film after desilvering
The haze is preferably 20 or less, and 10 or less.
More preferably it is. Next, the silver halide photographic emulsion of the present invention and
Describes the morphology of silver halide color photographic materials
The In the present invention, the equivalent circle diameter means the parallelism of particles.
The diameter of a circle with an area equal to the projected area of the outer surface
In addition, the equivalent spherical diameter has a volume equal to the volume of the particle.
The diameter of the sphere. The projected area of the particle is the surface on the electron micrograph.
It is obtained by measuring the product and correcting the shooting magnification. The thickness of the particles is the same as the reference latex.
The metal is deposited from the diagonal direction of the particles and the shadow length is
The length of the latex shadow is measured by measuring with an electron microscope.
It is easily obtained by calculating with reference to the above. The equivalent circle diameter of all the grains of the emulsion of the present invention is
The coefficient of variation is preferably 40% or less, more preferably
Or 25% or less, more preferably 15% or less.
The composition of the silver halide grains that can be used in the present invention is chloride.
Silver, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, chloroiodobromide
Any of silver may be used. Other silver salts such as Rhodan silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, organic acid silver are separate
Included as grains or as part of silver halide
It may be. Preferred silver iodide content of the emulsion grains of the present invention
Is in the range of 0.1 to 20 mol%, more preferably
0.3 to 15 mol%, particularly preferably 1 to 10 mol%
Yes, you can choose according to your purpose. Over 20 mol%
In general, the developing speed is delayed, which is not preferable. Silver chloride (refractive index 2.0) is silver bromide (refractive index).
2.25) Since the refractive index is lower than that of silver chloride as much as possible
It is specular transmission density that a lot of emulsion grains contain.
It is preferable for reducing the degree. Therefore, the tabular grains of the present invention are preferred.
The preferred silver chloride content range is more than 50 mol%,
More preferably, it is 75-100 mol%, Most preferably, it is 80
Although it is -98 mol%, you may select according to the objective. When fine particle titanium oxide is dispersed,
At least one of the dispersed emulsion layers of silver is silver chloride
Silver bromide or silver iodide with a content of 50 mol% or more
Contains silver iodobromide to reduce specular transmission density.
Therefore, it is preferable. Next, it is contained in the emulsion layer in which titanium oxide is dispersed.
Preferred grain thickness of silver bromide grains or silver iodobromide grains
Is described. Techniques for improving the sensitivity and image quality of silver halide emulsions
One technique is the use of tabular grains, with sensitizing dyes.
Increased sensitivity including improved color sensitization efficiency, sensitivity / granularity ratio
Shear due to improved relationship and specific optical properties of tabular grains
Benefits such as improved pune and improved covering power
Known in the industry, generally the same volume
A tabular grain with a high yield ratio is more advantageous for improving the sensitivity granularity ratio.
The An example of a method for forming high aspect ratio tabular grains
U.S. Pat. Nos. 5,496,694 and 5,498,516.
As a method for forming tabular grains having a thin grain thickness, for example,
U.S. Pat. Nos. 5,494,789 and 5,503,97
No. 0 discloses the technology. With increasing aspect ratio, the thickness of tabular grains
At this time, the reflected light of tabular grains increases.
Is a problem. Interference between tabular grain thickness and monochromatic light
Research Disclosure (Research D)
isclosure), (No. 25330, May 1985)
Yes. Reflection by changing the thickness of silver iodobromide plate
The reflectivity varies, but the reflectivity of the silver iodobromide plate increases with thickness.
It does not simply decrease, but has a minimum and maximum. this is
The increase in reflectivity of the silver chloride slab is simply due to the scattering effect.
Show that the optical interference effect contributes greatly.
ing. The reflectivity of the silver iodobromide flat plate reaches a maximum, especially 0.
It increases significantly at particle thicknesses below 13 μm. This low
In order to reduce this, it is described in JP-A-12-347336.
It is possible to disperse fine titanium oxide so
Preferred for reduction. Accordingly, the emulsion layer in which titanium oxide is dispersed is formed.
5% of the total projected area of silver halide grains in at least one layer
0% or more has a thickness of less than 0.13 μm and a silver chloride content of 50
It contains silver bromide grains or silver iodobromide grains in an amount of mol% or more.
Is preferred for further specular transmission density reduction
Yes. Emulsion of the present invention and the present invention used in combination therewith
Other than photographic emulsions
Science, published by Paul Montel (P. Glafkides,
Chemie et Physique Photog
raphique, Paul Montel, 196
7) "Duffin" Photographic Emulsion Chemistry, Focal Press
Company publication (GF Duffin, Photographi
c Emulsion Chemistry (Foca
l Press, 1966)), Zerikman et al.
Emulsion production and coating ", published by Focal Press (V.L.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, Focal Press, 1964)
Can be prepared using the method described in US Pat. You
In other words, any of acid method, neutral method, ammonia method, etc.
Well, reacting soluble silver salts with soluble halogen salts
One type of mixing method, simultaneous mixing method, and combinations of these
Any of these may be used. Excess of silver ions
Using the method of forming below (so-called back mixing method)
You can also. Halogene as a form of simultaneous mixing
A method for maintaining a constant pAg in the liquid phase produced by silver halide.
Using the so-called controlled double jet method
You can also. According to this method, the crystal form is regular and
A silver halide emulsion having a nearly uniform grain size can be obtained. Precipitated form in a reaction vessel for emulsion preparation.
A method of adding silver halide grains formed in the United States
No. 4,334,012, No. 4,301,241
The method described in No. 4,150,994 is
More preferred. These can also be used as seed crystals
It is also effective when supplied as silver halide for growth.
It is. In the latter case, it is preferable to add a small emulsion.
As a method of addition, add all at once and divide into multiple times
To choose from adding or continuously adding
Can be used. Also seeds to modify the surface
It may be possible to add grains with various halogen compositions.
It is effective. Most of the halogen composition of silver halide grains
Or a small part is converted by the halogen conversion method
The method is described in U.S. Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent No. 273,429, No. 27
No. 3,430, West German Patent No. 3,819,241
And is an effective particle forming method. More difficult
Soluble halogen solutions or solutions for conversion to soluble silver salts
Can add silver halide grains. Weird at once
Convert, divide multiple times, or convert continuously
You can choose from methods such as conversion. As a particle growth method, a constant concentration and a constant flow are used.
In addition to the method of adding soluble silver salt and halogen salt at high speed,
National Patent No. 1,469,480, US Patent No. 3,65
No. 0,757 and No. 4,242,445
Change the concentration, or change the flow rate
The particle forming method is a preferred method. Increase the concentration
Or by increasing the flow rate.
The amount of silver halide is a linear function, a quadratic function, or
Can be changed with more complex functions. Also needed
The amount of silver halide supplied can be reduced by
preferable. Furthermore, a plurality of soluble silver salts having different solution compositions
Multiple solubles with different solution compositions
When adding a halogen salt, increase one and the other
An addition method that reduces the amount is also an effective method. Dissolve soluble silver salt and soluble halogen salt solution
The mixer when adapted is U.S. Pat. No. 2,996,287.
No. 3,342,605 No. 3,415,65
No. 0, No. 3,785,777, West German patent 2,5
56,885 and 2,555,364.
You can choose from the methods that are available. Silver halide for the purpose of promoting ripening
Solvents are useful. For example, excessive amounts to promote aging
Known to allow halogen ions to exist in the reactor
ing. Other ripening agents can also be used. these
Ripening agents react before adding silver and halide salts
The total amount can be blended in the dispersion medium in the vessel,
Add halide salt, silver salt or peptizer and react
It can also be introduced into the vessel. As another variation, mature
Derivatives are introduced independently during the addition of halide and silver salts.
You can also enter. Examples of ripening agents include ammonia,
Ocynate (eg, Rodankari, Rodan Ammonius)
), Organic thioether compounds (for example, US Patent No.
No. 3,574,628, No. 3,021,215, No.
No. 3,057,724, No. 3,038,805,
No. 4,276,374, No. 4,297,439
Nos. 3,704,130, 4,782,01
3, compound described in JP-A-57-104926
Stuff. ), Thione compounds (for example, JP-A-53-8240).
No. 8, No. 55-77737, US Pat. No. 4,221,
Tetrasubstituted thiourea described in No. 863, and
53-144319) and the like
Halogenation as described in Kaisho 57-202531
Mercapto compounds that can promote the growth of silver particles, amination
Compound (for example, Japanese Patent Laid-Open No. Sho 54-10017)
It is. The protective coating used in the preparation of the emulsion of the present invention.
As a Lloyd and other hydrophilic colloid layer vine
It is advantageous to use gelatin as a catalyst, but
Other hydrophilic colloids can also be used. For example, gelatin derivatives, gelatin and other
Of graft polymer with polymer, albumin, casein
Such as protein; hydroxyethyl cellulose, carbox
Like methylcellulose and cellulose sulfates
Cellulose derivatives, sodium alginate, starch derivatives
Sugar derivatives such as polyvinyl alcohol, polyvinyl alcohol
Lucol partial acetal, poly-N-vinylpyrrolide
, Polyacrylic acid, polymethacrylic acid, polyacrylic
Amide, polyvinyl imidazole, polyvinyl pyrazo
Various synthetic hydrophilics such as mono- or copolymers such as
Can be used. As the gelatin, lime-processed gelatin is used.
Or acid-treated gelatin or Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
Enzyme-treated gelatin as described may be used.
It is also possible to use hydrolyzate or enzyme degradation product of gelatin.
it can. The emulsion of the present invention was washed with water for desalting, and was renewed.
It is preferable to prepare a protective colloid dispersion prepared in advance. water
The washing temperature can be selected according to the purpose, but it is in the range of 5 ° C to 50 ° C.
Is preferable. You can choose the pH for washing according to your purpose
However, it is preferable to select between 2-10. Even more preferred
Or in the range of 3-8. PAg at the time of washing
Although it can choose, it is preferable to choose between 5-10. Water wash
Noodle washing method, dialysis method using semipermeable membrane, centrifugation
Select from separation, coagulation sedimentation, and ion exchange methods
Can be. Use sulfate in the case of coagulation sedimentation
Using organic solvents, using water-soluble polymers
Or a method using a gelatin derivative.
Can do. Described in US Pat. No. 3,772,031
Add chalcogen compounds such as those mentioned during emulsion preparation
This method may be useful. In addition to S, Se, Te
Ansalt, thiocyanate, selenocyanic acid, carbonate, phosphorus
Acid salts and acetate salts may be present. The silver halide grains of the present invention have sulfur sensitization,
Chalcogen sensitization such as ren sensitization; gold sensitization, palladium sensitization
Noble metal sensitization such as halogen; at least one of reduction sensitization is halogen
Can be applied at any stage of the silver halide emulsion production process
The It is preferable to combine two or more sensitization methods. Do
Different types of emulsions depending on whether they are chemically sensitized
Can be prepared. Fills the inside of the particle with a chemical sensitization nucleus
Type that embeds into the shallow position from the particle surface,
Alternatively, there is a type that creates chemical sensitization nuclei on the surface. The present invention
The emulsion can be selected for the location of chemical sensitization nuclei according to the purpose.
But generally preferred is at least one near the surface
This is the case where the chemical sensitization nucleus is made. One of chemical sensitizations that can be preferably carried out in the present invention.
One is a combination of chalcogen sensitization and noble metal sensitization.
The Photo by R. James (TH James)
Graphic Process, 4th edition, published by Macmillan, 1
977, (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, McCillan, 197
7) Use active gelatin as described on pages 67-76
And research and disclosure
Jar, 120, April 1974, 12008; Lisa
March Disclosure, Volume 34, June 1975,
13452, U.S. Pat. No. 2,642,361, ibid.
3,297,446, 3,772,031,
No. 3,857,711, No. 3,901,714, No.
Nos. 4,266,018 and 3,904,41
5 as well as British Patent No. 1,315,755
PAg 5-10, pH 5-8 and temperature 30-8
Sulfur, selenium, tellurium, gold, platinum, para-dioxide at 0 ° C
Um, iridium or combinations of these sensitizers and
can do. In precious metal sensitization, gold, platinum,
It is possible to use noble metal salts such as palladium and iridium.
In particular, gold sensitization, palladium sensitization, and both
Is preferred. For gold sensitization, chloroauric acid, potassium
Chloroaurate, potassium auric thiocyanate
Using known compounds such as gold sulfide, gold selenide
Can. Palladium compounds are palladium divalent salts
Or a tetravalent salt is meant. Preferred palladium compounds
Is R₂PdX₆Or R₂PdX ₄It is represented by This
Where R is a hydrogen atom, an alkali metal atom or ammonium.
Represents a group. X represents a halogen atom and represents chlorine, bromine or
Or represents an iodine atom. Specifically, K₂PdCl₄, (NH₄)
₂PdCl₆, Na₂PdCl₄, (NH₄)₂PdC
l₄, Li₂PdCl₄, Na₂PdCl₆Or K₂
PdBr₄Is preferred. Gold compounds and palladium compounds
Use in combination with thiocyanate or selenocyanate
It is preferable. Hypo and thiourea based sulfur sensitizers
Compounds, rhodanine compounds and US Pat. No. 3,857,
No. 711, No. 4,266,018 and No. 4,0
Using sulfur-containing compounds described in 54,457
Can. Chemistry in the presence of so-called chemical sensitization aids
It can also be sensitized. Useful chemical sensitization aids include aza
Like indene, azapyridazine, azapyrimidine,
Suppresses fog and increases sensitivity in the process of chemical sensitization
Known compounds are used. Chemical sensitization aid
Examples of modifiers are disclosed in U.S. Pat. No. 2,131,038.
3,411,914, 3,554,757, special
Kaisho 58-126526 and Duffin's "Photograph"
Emulsion Chemistry ", pages 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization.
Good. As a preferred amount of gold sensitizer, 1 mol of silver halide
1 × 10 per le^-4~ 1x10^-7Is a mole, and even
1 × 10 is preferred^-5~ 5x10^-7Is a mole.
The preferred range of the palladium compound is 1 × 10^-3To 5
× 10^-7It is. Thiocyanate or selenoshi
The preferred range of the an compound is 5 × 10^-2To 1 × 10
^-6It is. Used for the silver halide grains of the present invention
The preferred amount of sulfur sensitizer is 1 × per mole of silver halide.
10^-4~ 1x10^-7More preferred
Is 1 × 10^-5~ 5x10^-7Is a mole. As a preferred sensitizing method for the emulsion of the present invention,
There is selenium sensitization. In selenium sensitization, a known defect
Using stable selenium compounds, specifically colloidal metals
Selenium, selenoureas (for example, N, N-dimethyl)
Selenourea, N, N-diethylselenourea), selenoke
Selenium compounds such as tons and selenoamides are used.
be able to. Selenium sensitization is sulfur sensitization or noble metal sensitization
When it is preferable to use in combination with feeling or both
There is a match. During grain formation of the silver halide emulsion of the present invention,
After grain formation and before or during chemical sensitization
Alternatively, reduction sensitization after chemical sensitization is preferred. here
Reduction sensitization means adding a reduction sensitizer to a silver halide emulsion.
A low pAg atmosphere with a pAg of 1-7, called silver ripening
A method of growing or aging in the atmosphere, called high pH aging
Grow or mature in a high pH atmosphere of pH 8-11
You can choose any of the methods. More than one way
Can also be used together. The method of adding a reduction sensitizer is the reduction sensitization method.
This is a preferable method in that the bell can be finely adjusted. Examples of reduction sensitizers include stannous salts,
Ascorbic acid and its derivatives, amines and polya
Mines, hydrazine derivatives, formamidine sulfine
Acids, silane compounds, and borane compounds are known. The present invention
These known reduction sensitizers are selected and used for reduction sensitization.
It is also possible to use two or more compounds in combination.
Yes. Reduction sensitizers include stannous chloride and thiourine dioxide
Elemental, dimethylamine borane, ascorbic acid and its
Derivatives are preferred compounds. The amount of reduction sensitizer added is
Since it depends on the emulsion production conditions, it is necessary to select the addition amount
Is 10 per mole of silver halide.^-7-10^-3Molar
The range is appropriate. The reduction sensitizer is, for example, water or alcohol.
, Glycols, ketones, esters, amides
It is dissolved in an organic solvent such as No. 1 and added during grain growth.
It may be added to the reaction vessel in advance,
A method of adding at an appropriate time is preferable. Also water-soluble silver salt
Or in advance to the water solubility of water-soluble alkali halide
Add a reduction sensitizer and use these aqueous solutions.
Silver halide grains may be precipitated. Also for particle growth
Along with this, the reduction sensitizer solution can be added several times.
It is also a preferable method to add it for a long time. Acid for silver during the production process of the emulsion of the present invention
It is preferable to use an agent. What is an oxidizing agent for silver?
Acts on metallic silver and converts it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very fine silver particles by-produced during chemical sensitization
A compound capable of converting to silver ions is effective. here
The silver ions produced in
It may form a slightly soluble silver salt in water such as silver or silver selenide
It is also possible to form a readily soluble silver salt in water such as silver nitrate.
Yes. The oxidizing agent for silver is organic, even if it is inorganic.
There may be. Examples of inorganic oxidizing agents include ozono
, Hydrogen peroxide and its adducts (eg NaBO₂
・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, N
a₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂
・ 2H₂O), peroxyacid salts (eg K₂S
₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex
Body compounds (eg, K₂[Ti (O₂) C₂O₄] ・ 3
H₂O, 4K₂SO₄・ Ti (O₂) OH / SO₄・ 2
H₂O, Na₃[VO (O₂) (C₂H₄)₂] 6H
₂O), permanganate (eg KMnO)₄),Black
Mumate (eg, K₂Cr₂O₇) Oxylate,
Halogen elements such as iodine and bromine, perhalogenates (eg
For example, potassium periodate), high valent metal salts (eg
For example, potassium hexacyanoferric acid) and thiosulfur
There is oxalate. As an organic oxidizing agent, p-quinone is used.
Quinones, such as peracetic acid and perbenzoic acid.
Oxides, compounds that release active halogens (eg N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidizing agents of the present invention are ozone and peracid.
Hydrogen fluoride and its adducts, halogen elements, thiosulfo
Inorganic oxidizers of phosphates and organic oxidants of quinones.
It is preferable to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.
This is a new aspect. How to apply post-reduction sensitization with an oxidizing agent
Method, the reverse method, or the method of coexisting both at the same time
You can choose from among them. These methods are grain
It can be selected and used in both the child formation process and the chemical sensitization process.
Yes. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the production process, storage, or photo processing
To stop or stabilize photographic performance,
Compounds can be included. Ie thiazole
Such as benzothiazolium salt, nitroimidazole
, Nitrobenzimidazoles, chlorobenzimi
Dazoles, bromobenzimidazoles, mercapto
Thiazoles, mercaptobenzothiazoles, merca
Putobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; examples
For example, a thioketo compound such as oxadrine thione;
Zaindenes, such as triazaindenes, tetraa
Zaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes), Pentaazaindene
Known as antifoggants or stabilizers, such as
Many compounds can be added. For example, US patents
3,954,474, 3,982,947,
Use the one described in Japanese Patent Publication No. 52-28660.
You can. One preferred compound is disclosed in JP-A-63-21.
There are compounds described in No. 2932. Antifoggant
And stabilizers before and during particle formation, after particle formation,
During the washing process, after dispersion with water, before chemical sensitization, during chemical sensitization,
After sensitization, add according to purpose at various times before application
can do. Add to the original fog during emulsion preparation
In addition to preventing and stabilizing,
Control, reduce particle size, decrease particle solubility
Control chemical sensitization, control dye arrangement, etc.
Can be used for purposes. The photographic emulsion used in the present invention has a methine color.
The effect of the present invention is spectral sensitization by elements and others
Is preferable. The dye used is cyani
Dye, merocyanine dye, composite cyanine dye, composite dye
Russianine dye, holopolar cyanine dye, hemicia
Nin dye, styryl dye and hemioxonol dye
Is included. Particularly useful dyes are cyanine dyes, merosi
Dyes belonging to anine dyes and complex merocyanine dyes
It is. These dyes have a basic heterocyclic nucleus as
Any of the nuclei normally used for anine pigments can be applied.
The That is, for example, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole
Nucleus, selenazole nucleus, imidazole nucleus, tetrazole
Nucleus, pyridine nucleus; alicyclic hydrocarbon ring fused to these nuclei
Nuclei; and aromatic nuclei fused to these nuclei
Nucleus, for example, indolenine nucleus, benzoindoleni
Nucleus, indole nucleus, benzoxador nucleus, naphtho
Xazole nucleus, benzothiazole nucleus, naphthothiazole
Nucleus, benzoselenazole nucleus, benzimidazole nucleus, key
Norin nucleus is applicable. These nuclei are substituted on carbon atoms
It may have a group. Merocyanine dyes or complex merocyanines
As a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thio
Oxazolidine-2,4-dione nucleus, thiazolidine-
2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid
A 5-6 membered heterocyclic nucleus of the nucleus can be applied. These sensitizing dyes may be used alone.
However, combinations of these may be used, and combinations of sensitizing dyes
Is often used for the purpose of supersensitization. That generation
Examples are U.S. Pat. Nos. 2,688,545 and 2,973.
No. 7,229, No. 3,397,060, No. 3,5
22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No.
3,666,480, 3,672,898,
No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
No. 7, British Patent No. 1,344,281, No. 1,50
7,803, Japanese Examined Sho 43-4936, 53-12
No. 375, JP-A 52-110618, 52-10
No. 9925. Spectral sensitization by itself with sensitizing dye
Dyes that do not absorb or that do not substantially absorb visible light
May contain in the emulsion a material that is high in quality and exhibits supersensitization.
Yes. The timing for adding the sensitizing dye to the emulsion is as follows.
Any stage of emulsion preparation known to be useful until
It may be. Most commonly after chemical sensitization is completed
Although it is performed before the cloth, U.S. Pat. No. 3,62
Described in 8,969 and 4,225,666
Spectral sensitization added at the same time as chemical sensitizers
Can be carried out simultaneously with chemical sensitization.
Perform prior to chemical sensitization as described in 28
Before the completion of silver halide grain precipitation.
Spectral sensitization can be started by addition. Furthermore, the United States
As taught in US Pat. No. 4,225,666.
Adding these compounds separately, i.e., these
Part of the compound is added prior to chemical sensitization and the rest is chemically
It can also be added after sensitization, U.S. Pat.
183,756 and the method disclosed in
Any time during the formation of silver halide grains may be used. The amount added was 4 × per mole of silver halide.
10^-6~ 8x10^-3Can be used in moles,
More preferable silver halide grain size of 0.2 to 1.2 μm
About 5 × 10^-5~ 2x10^-3Mole is effective. The silver halide emulsion used in the present invention is a table.
It may be a surface latent image type emulsion or an internal latent image type emulsion.
Yes. The internal latent image type emulsion is combined with a nucleating agent and optical fogging.
Directly used as a reversal emulsion. In addition, the inside of the particle and the particle
It is a so-called core-shell emulsion with different phases on the child surface layer.
The composition may vary depending on the epitaxial junction.
The silver halide which becomes may be joined. Halogenated
The silver emulsion may be monodispersed or polydispersed.
As described in 7,743 and 4-223,463,
The method of mixing dispersed emulsion and adjusting the gradation is preferably used
It is done. Particle size is 0.1-2 μm, especially 0.2-
1.5 μm is preferred. Crystal habit of silver halide grains is cubic
With regular crystals such as body, octahedron, and tetrahedron
Of irregular shape like a flat plate with a spherical shape and high aspect ratio
Having crystal system, crystal defects such as twin planes
Or any of those composite systems.
Specifically, US Pat. No. 4,500,626 No. 50
Column, 4,628,021, Research Disclosure
Jar magazine (hereinafter abbreviated as RD) No. 17,029 (1
978), No. 17,643 (December 1978)
22-23, No. 18,716 (November 1979)
648 pages, No. 307, 105 (November 1989)
Pp. 863-865, JP-A 62-253,159
No. 64-13546, JP-A-2-23654
No. 6, No. 3-110,555 and Grafkide
True physics and chemistry ", published by Paul Monte (P. Glafkides, C
hemie etPhisquePhotographique, Paul Montel, 196
7), "Photographic emulsion chemistry" by Duffin, Focal Press
(G.F.Duffin, Photographic Emulsion Chemistry, F
ocalPress, 1966), "Manufacture of photographic emulsions" by Zerikman et al.
And coating ", published by Focal Press (V.L.Zelikman et a
l., Making and Coating Photographic Emalusion, Foc
al Press, 1964) etc.
Any of the silver halide emulsions used can be used. Preparation of the photosensitive silver halide emulsion of the present invention
So-called desalting to remove excess salt in the process
Is preferred. Gelling gelatin as a means for this
Nudelle washing method,
Inorganic salts composed of nion (for example, sodium sulfate), a
Nonionic surfactants, anionic polymers (eg poly
Sodium styrenesulfonate) or gelatin
Conductors (eg aliphatic acylated gelatin, aromatic acylation)
Gelatin, aromatic carbamoylated gelatin, etc.)
The settling method may be used. The sedimentation method is preferably used
The Photosensitive silver halide emulsion used in the present invention
For various purposes, iridium, lodge, platinum, cadmium
Heavy gold such as um, zinc, thallium, lead, iron, osmium
A genus may be included. These compounds are used alone
It may also be used in combination of two or more. Attendant
The amount depends on the intended use, but in general, halogenated
10 per mole of silver^-9-10^-3It is about a mole. Also including
When it is present, the particles may be placed uniformly or
It may be localized inside or on the surface of the child. Specifically, JP
Hei 2-236,542, 1-116,637,
The emulsion described in 5-181,264 etc. is preferably used.
It is. Grain shape of the photosensitive silver halide emulsion of the present invention
In the formation stage, rhodan salts, silver
Ammonia, tetra-substituted thiourea compounds and Japanese Patent Publication No. 47-11
Organic thioether derivatives described in No. 386 or JP-A-5
Sulfur-containing compounds described in 3-144,319, etc.
Can be used. For other conditions, the above graph key is used.
De Writer "Physics and Chemistry of Photography", published by Paul Monte (P.Glaf)
kides, Chemie et Phisique Photographique, Paul Mon
tel, 1967), "Photoemulsion Chemistry" by Duffin, Focal
Press (G.F.Duffin, Photographic Emulsion Chem
istry, Focal Press, 1966)
Manufacturing and application ", published by Focal Press (V.L.Zelikm
an et al., Making and Coating Photographic Emalusi
on, Focal Press, 1964). You
In other words, any of acid method, neutral method and ammonia method can be used.
In addition, a form in which a soluble silver salt reacts with a soluble halogen salt
Formulas include one-side mixing method, simultaneous mixing method, and combinations thereof
Any of these may be used. To obtain a monodisperse emulsion
The simultaneous mixing method is preferably used. Particles with silver ions
It is also possible to use a backmixing method that forms under excess.
Yes. Silver halide production as a form of simultaneous mixing.
So-called control that keeps pAg in the liquid phase constant.
A rolled double jet method can also be used. Further, it is added in order to accelerate the grain growth.
Addition concentration, addition amount, and addition speed of silver salt and halogen salt
It may be raised (Japanese Patent Laid-Open No. 55-142,329).
55-158,124, US Pat. No. 3,650,75
7). Furthermore, the method of stirring the reaction solution is a known method.
A stirring method may be used. Reaction during the formation of silver halide grains
The temperature and pH of the liquid can be set according to the purpose.
Yes. The preferred pH range is 2.2 to 7.0, more preferably
Is 2.5 to 6.0. In the present invention, photosensitive silver halide and
In both cases, an organic metal salt can be used as an oxidizing agent.
The Among such organometallic salts, organic silver salts are particularly preferred.
It is used well. To form the above organic silver salt oxidizing agent
Examples of organic compounds that can be used in US Pat.
Benzotriazo as described in columns 0-626, columns 52-53, etc.
And other compounds. US Patent No.
Acetylene silver described in No. 4,775,613 is also useful.
The Two or more organic silver salts may be used in combination. More than
Organic silver salt is 0.01 ~ per mole of photosensitive silver halide.
Use together 10 mol, preferably 0.01-1 mol.
Can do. Total coating amount of photosensitive silver halide and organic silver salt
Is 0.05 to 10 g / m in terms of silver², Preferably 0.1
4g / m²Is appropriate. The binder of the constituent layer of the photosensitive material is hydrophilic.
Are preferably used. For example
Search Disclosure and JP-A-64-13
And those described on pages (71) to (75) of No. 546
The Specifically, a transparent or translucent hydrophilic binder is preferred.
For example, proteins such as gelatin and gelatin derivatives
Or cellulose derivative, starch, gum arabic, dextst
Polyvinyl chloride and natural compounds such as orchid, pullulan and other polysaccharides
Neil alcohol, polyvinylpyrrolidone, acrylic
Synthetic polymer compounds such as imide polymers are exemplified. Also,
U.S. Pat. No. 4,960,681, JP-A 62-24
Superabsorbent polymer described in No. 5,260, ie, −
COOM or -SO_Three M (M is a hydrogen atom or an
Homopolymers of vinyl monomers having
With other vinyl monomers or with other vinyl monomers
Copolymer (eg sodium methacrylate, methacryl
Ammonium acid, Sumikagel L-5 manufactured by Sumitomo Chemical Co., Ltd.
H) is also used. Two or more of these binders are combined
They can also be used together. Especially gelatin and the above
A combination of binders is preferable, and gelatin has various
Depending on the purpose of the lime-processed gelatin, acid-processed gelatin,
So-called demineralized gelatin with reduced content of Lucium
It is good to use it in combination.
Yes. In the present invention, the amount of binder applied is 1 m.²Per
1 g or more and 20 g or less are preferable, especially 2 g or more and 10 g or less.
It is appropriate to set it down. The dye-donating coupler that can be used in the present invention is:
A 4-equivalent coupler or a 2-equivalent coupler may be used. Also,
The diffusion resistant group may form a polymer chain. coupler
A specific example is T.H.James "The Theory of the Photogra
phic Process "4th edition, pages 291-334, and 354
361 pages, JP-A-58-123533, 58-1
49046, 58-149047, 59-11
1148, 59-124399, 59-174
835, 59-231539, 59-2315
No. 40, No. 60-2950, No. 60-2951, No.
60-14242, 60-23474, 60-
No. 66249, Japanese Patent Application Nos. 6-270700 and 6-30
7049, 6-31380, etc.
ing. In addition, the following couplers should be used.
Is preferred. Yellow coupler: Formula of EP502,424A
Couplers represented by (I) and (II): EP513, 4
A coupler represented by the formulas (1) and (2) of No. 96A,
It is represented by the general formula (I) of claim 1 of No. 5-307,248
Coupler: Column 1, US 5,066,576
Couplers represented by general formula D on lines 45 and 55,
Represented by general formula D in paragraph 0008 of Hei 4-274425
Coupler: EP 498, 38A1, page 40
Coupler described in Lame 1, EP447,969A1
A coupler represented by the formula (Y) on page 4,
6,219, column 7, lines 36 and 58, formulas (I) to (I
A coupler represented by V). Magenta coupler: JP-A-3-39737
No., No. 6-43611, No. 5-204106, No. 4
The coupler described in No. 3626. Cyan coupler: JP-A-4-204843, JP-A-4
-43345. Polymer coupler: JP-A-2-443
No. 45. As couplers in which the coloring dye has an appropriate diffusibility, U
S4,366,237, GB2,125,570,
Described in EP 96,570, DE 3,234,533
Are preferred. Further, this photosensitive material has the following functions.
A functional coupler may be contained. Unnecessary absorption of coloring dye
The coupler for correcting the noise is EP456,257A1
The yellow colored cyan coupler described in No.
Yellow color magenta coupler as described, US 4,8
Magenta colored cyan coupler described in No. 33,069
-, US 4,837,136 (2), WO 92/11
575 colorless cell represented by formula (A) of claim 1
King couplers (especially exemplary compounds on pages 36-45). Present
Reacts with oxidants of the imaging agent to release photographic useful compound residues
The following compounds (including couplers)
Is mentioned. Development inhibitor releasing compound: EP378,2
It is represented by the formulas (I) to (IV) described on page 11 of 36A1
Described on page 7 of EP 436,938A2
A compound represented by the formula (I): JP-A-5-30724
Compound represented by formula (1) of No. 8, EP440,195
It is represented by the formula (I) (II) (III) described on pages 5 and 6 of A2.
A compound of formula (I) in claim 1 of JP-A-6-594
Compounds represented-ligand releasing compounds, US 4,55
Expressed by LIG-X described in claim 1 of 5,478
Compound. In the present invention, as the content of the coupler
Is 0.01 g / m²-10g / m²Is preferred, 0.1 g
/ M²~ 2g / m²Is more preferable. In the light-sensitive material of the present invention, the development time is shortened.
For purposes such as improving sensitivity and image density, silver development can be used.
The resulting oxidant is coupled with the coupler
A mode in which a color developing agent capable of forming a dye is incorporated
Is preferred. In this case, U.S. Pat. No. 3,531,256
P-phenylenediamine developing agent and phenol
Or active methylene coupler, 3,761,270
P-aminophenol developing agent and active methylene
Coupler combinations can be used. US Patent No.
4,021,240, JP-A-60-128438, etc.
And sulfonamidophenol as described in 4
Equivalent coupler combinations are not suitable for use in light sensitive materials.
It is excellent in storage and is a preferable combination. Color developer
If the drug is to be incorporated, use a color developing agent precursor.
May be. For example, as described in US Pat. No. 3,342,597
Indoaniline compounds, US 3,342,599,
Research Disclosure No. 14,850 and the same
Schiff base type compounds described in Nos. 15 and 159, 1
Aldol compound according to 3,924, US 3,719,
No. 492, a metal salt complex, JP-A-53-135628
The urethane-type compound of No. description can be mentioned. Also, as described in JP-A-9-15,806
Sulfonamidophenol based drug, 8-286,34
Hydrazine-based active ingredients described in No. 0 and 8-234388
A combination of a coupler and a coupler is also used in the light-sensitive material of the present invention.
Is preferred. When using a diffusion-resistant developing agent,
Electricity between the diffusion resistant developing agent and the developable silver halide.
If necessary, an electron transfer agent and
And / or an electron transfer agent precursor.
You can. Particularly preferably, said US Pat. No. 5,13.
No. 9,919, described in European Patent Publication No. 418,743
Things are used. JP-A-2-230,143,
Stable introduction into the layer as described in No. 2-235,044
Is preferably used. Electron transfer agent or its
The precursor is the above-mentioned developing agent or its precursor.
You can choose from sir. Electron transfer agent or its
The precursor is a diffusion-resistant developing agent (electron
Desirably larger than the donor). Particularly useful electronic transmission
Agents are 1-phenyl-3-pyrazolidones or aminophenes
Enols. JP-A-3-160,443
Electron donor precursors such as those listed are also preferably used
The In addition, preventing color mixing and improving color reproduction in the intermediate layer and protective layer
Various reducing agents can be used for various purposes. Concrete
Specifically, European Patent Publication Nos. 524,649 and 357,
040, JP-A-4-249,245, 2-46,
No. 450, and reducing agents described in JP-A 63-186,240
Is preferably used. Japanese Patent Publication 3-63,733
, JP-A-1-150,135, 2-46,450
No. 2-64,634, No. 3-43,735, Europe
Development inhibitors such as those described in US Patent Publication No. 451,833
Release reducing agent compounds are also used. In addition, when a photothermographic material is used,
An embodiment in which an image active agent is incorporated is particularly preferable. In that case, use
Is known in the field of photothermographic materials.
Can be used. Also, it returns itself
Not original, but due to the action of nucleophiles and heat during the development process
It is also possible to use a developing agent precursor that exhibits reducing properties.
it can. In addition, even if the following reducing agent is built into the photosensitive material
good. Examples of reducing agents used in the present invention include US
No. 4,500,626, columns 49-50, 4,8
39,272, 4,330,617, 4,59
0,152, 5,017,454, 5,13
No. 9,919, No. 17 of JP-A-60-140,335
To (18), 57-40, 245, 56-138,
736, 59-178,458, 59-53,
No.831, 59-182,449, 59-18
2,450, 60-119,555, 60-1
28,436, 60-128,439, 60-
198,540, 60-181,742, 61
-259,253, 62-244,044, 6
2-131,253, 62-131,256,
No. 64-13,546, pages (40)-(57), JP-A-1-1-1
No. 20,553, European Patent No. 220,746 A2
The reducing agent or reducing agent precursor described on pages 78 to 96, etc.
is there. Also disclosed in US Pat. No. 3,039,869.
Combinations of various reducing agents, such as
You can. When using a photothermographic material, the developing agent
Alternatively, the reducing agent may be incorporated in a processing sheet described later.
However, it may be incorporated in the photosensitive material. In the present invention, development
The total amount of the active ingredient and the reducing agent is 0.
01 to 20 mol, particularly preferably 0.1 to 10 mol
The Couplers, developing agents, diffusion-resistant reducing agents, etc.
Hydrophobic additives described in US Pat. No. 2,322,027
It is introduced into the layer of the photosensitive material by a known method such as
Can. In this case, U.S. Pat. No. 4,55.
5,470, 4,536,466, 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
High boiling point organic solvents such as those described in No. 2,256 are required.
Combined with low boiling point organic solvents with boiling points of 50 ° C to 160 ° C as required
Can be used. Also, these dye donating
Two or more compounds, diffusion-resistant reducing agents, high-boiling organic solvents, etc.
Can be used together. The amount of high boiling organic solvent used
10 g or less with respect to 1 g of the hydrophobic additive, preferably 5
g or less, more preferably 1 g to 0.1 g. Also,
1cc or less, more than 0.5cc per 1g of binder
Below, especially 0.3 cc or less is suitable. Shoko 51-3
No. 9,853, described in JP-A-51-59,943
And a dispersion method using a polymer, or JP-A-62-30242
Of adding a fine particle dispersion described in No.
Can also be used. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles are dispersed in the binder.
Can be made. Divide hydrophobic compounds into hydrophilic colloids
When dispersing, various surfactants can be used.
The For example, JP-A-59-157,636, Nos. (37) to (3
8) Interface, described in Research Disclosure above
Those listed as activators can be used. Also special
Kaihei 7-56267, 7-228589, West German
Phosphate ester described in Japanese Patent No. 1,932,299A
Type surfactants can also be used. In the present invention, the photosensitive material
In addition, a compound that stabilizes the image simultaneously with development activation is used.
Can be. Specific compounds that are preferably used
Nos. 51-5 of U.S. Pat. No. 4,500,626.
It is described in the second column. The light-sensitive material of the present invention comprises at least one layer.
A preferred embodiment of the present invention is to have a silver halide emulsion layer.
As a matter of course, the spectral sensitivity and the hue of the coloring dye are different from each other.
Examples include those containing at least three photosensitive layers. It
Each photosensitive layer has substantially the same color sensitivity but sensitivity.
Even if it is divided into multiple silver halide emulsion layers
good. The three photosensitive layers are preferably blue light, green
This layer is sensitive to either colored light or red light. this
The order of arrangement is generally the red photosensitive layer in order from the support side,
The order is the green photosensitive layer and the blue photosensitive layer. However, the purpose
Depending on the case, a different arrangement may be used. For example, JP
As described in column 162 of Hei 7-152129
A simple arrangement is also acceptable. In the present invention, silver halide and color
The elemental donor coupler and developing agent are contained in the same layer.
It is okay, but if it can be reacted, it is added in separate layers.
You can also For example, a layer containing a developing agent and a halogen
When the silver-containing layer is separated from the layer, the raw shelf life of the light-sensitive material is improved.
Peeled off. The relationship between the spectral sensitivity of each layer and the hue of the coupler
Optionally, a red coupler with a cyan coupler and green
A magenta coupler is used for the light-sensitive layer, and a yellow ink is used for the blue-sensitive layer.
When using the puller, it is projected directly onto conventional color paper.
Can be exposed. For the light-sensitive material, the above silver halide emulsion layer
Protective layer, subbing layer, middle layer
Interlayer, yellow filter layer, antihalation layer, etc.
Various non-photosensitive layers may be provided on the opposite side of the support.
Various auxiliary layers such as a back layer can be provided. Ingredients
Specifically, the layer structure as described in the above patent, US Patent No.
Undercoat layer as described in US Pat. No. 5,051,335,
-167,838, JP-A 61-20,943
An intermediate layer having a solid pigment such as JP-A-1-120,
No. 553, No. 5-34,884, No. 2-64,634
An intermediate layer having a reducing agent or DIR compound as described in No. 1,
U.S. Pat. Nos. 5,017,454 and 5,139,91
No. 9 and electronic transmission as described in JP-A-2-235044.
Intermediate layer having an extender, described in JP-A-4-249,245
A protective layer having a reducing agent such as
A layer or the like can be provided. Yellow filter layer, antihalation layer
The dyes that can be used in
Or those that elute and do not contribute to the concentration after treatment.
Yes. Yellow filter layer, antihalation layer dye
Discolored or removed during development means that it remains after processing
The amount of the dye is 1/3 or less, preferably 1 /
10 or less, and the component of the dye is the photosensitive material during development.
May be eluted or transferred into processing material, or developed
Sometimes it reacts and turns into a colorless compound. As a dye that can be used in the light-sensitive material of the present invention
For example, known dyes can be used. For example, development
Dyes that dissolve in the alkali of the solution, components in the developer, sulfurous acid
A type that reacts with acid ions, main agents, and alkalis to discolor
Dyes can also be used. Specifically, European patent publication
The dyes described in EP549,489A and JP-A-7-15
No. 2129 ExF2-6 dye. JP
Solid dispersion as described in 8-10487
It is also possible to use dyes that have been prepared. This dye is a photosensitive material
Can also be used when developed with processing solutions.
However, the photosensitive material is thermally developed using a processing sheet described later.
Particularly preferred in some cases. In addition, mordants and dyes in binders
Can be mordanted. In this case mordant and dye
Can be those known in the photographic field, US 4,
50,626, columns 58-59 and JP-A-61-882.
56-32-41, JP-A-62-244043, Special
Raising the mordant described in Kaisho 62-244036 etc.
You can. Also reacts with reducing agents to release diffusible dyes
Using a reducing compound and a reducing agent, it is mobile with alkali during development.
Dye is released and eluted in the processing solution or on the processing sheet
It can also be removed by transcription. Specifically, US Patent No.
4,559,290, 4,783,396, Europe
Patent No. 220,746 A2, published technical report 87-6119
In addition, it is described in JP-A-8-101487.
No. 0080 to 0081. It is also possible to use a leuco dye that decolorizes.
Specifically, organic acid gold is disclosed in JP-A-1-150,132.
Leuco developed in advance with a salt developer
A silver halide light-sensitive material containing a dye is disclosed. B
The ico-dye and developer complex react with heat or alkaline agent.
In the present invention, the photosensitive material is subjected to thermal development.
In this case, this combination of leuco dye and developer is preferred.
Good. As leuco dyes, known ones can be used, such as Moriga,
Yoshida "Dyes and Chemicals", pages 9, 84 (Chemicals Industry Association)
"New Edition Dye Handbook", p.242 (Maruzen, 1970), R.Garn
er "Reports on the Progress of Appl. Chem" 56, 1
99 pages (1971), "dyes and chemicals" pages 19, 230
(Chemicals Products Industry Association, 1974), “Coloring Materials” 62, 288
Page (1989), “Dyeing Industry” 32, 208, etc.
is there. As the developer, acidic clay developer, phenol
In addition to formaldehyde resin, metal salts of organic acids are preferred.
Used frequently. Examples of metal salts of organic acids include salicylic acids
Metal salt, phenol-salicylic acid-formaldehyde
Metal salts of gin, rhodan salts, metal salts of xanthates, etc.
Zinc is particularly preferable as the metal. the above
Of oil soluble zinc salicylic acid
Are disclosed in U.S. Pat. Nos. 3,864,146 and 4,046.
No. 941 specification, Japanese Patent Publication No. 52-1327, etc.
Can be used. In the present invention
Of dyes, especially those that are decolorized or removed during development processing
The amount used is 1 mg / m so that the optical density is about 1.²-10
g / m²Is preferred, 10 mg / m²~ 1g / m²Is more preferred
Yes. The light-sensitive material of the present invention is hardened with a hardener.
It is preferable. Examples of hardeners include U.S. Pat. No. 4,
No. 678,739, column 41, No. 4,791,042,
JP-A-59-116,655, 62-245,26
No. 1, No. 61-18,942, JP-A-4-218,0
Hardeners described in No. 44 and the like can be mentioned. More specifically
Are aldehyde hardeners (formaldehyde, etc.),
Dilysine hardener, epoxy hardener, vinyl sulfone
Type hardener (N, N'-ethylene-bis (vinylsulfone
Luacetamide) ethane), N-methylol hardener
(Such as dimethylol urea), boric acid, metaboric acid or
Is a polymer hardener (see JP-A-62-234,157, etc.)
Described compounds). These hardeners are hydrophilic
0.001 to 1 g per 1 g of binder, preferably
0.005 to 0.5 g is used. The photosensitive material includes various antifoggants or
Using photographic stabilizers and their precursors
Can do. Specific examples include the research disc.
Closure, US Pat. No. 5,089,378
4,500,627, 4,614,702, JP
Sho 64-13564 (7) to (9), (57) to (71)
And (81)-(97), U.S. Pat.No. 4,775,610,
No. 4,626,500, No. 4,983,494, Special
Kaisho 62-174,747, 62-239,148
JP-A-1-150,135, 2-110,55.
No. 7, No. 2-178,650, RD 17,643
(1978) compounds described on pages (24) to (25), etc.
The These compounds are 5 × 10 5 per mole of silver.^-6~ 1
× 10^-1Moles are preferred, further 1 × 10^-5~ 1x1
0^-2Mole is preferably used. A method of developing the light-sensitive material of the present invention after exposure
As a method, heat development and a developing agent are incorporated in a photosensitive material, and
Activator method and development with Lucari processing solution
There is a method of developing with a processing solution containing an active ingredient / base. The present invention
In this case, after the color image is formed by development processing,
It is not necessary to remove the existing silver halide and developed silver. This
Silver halide and developed silver remaining after color image formation
Is not removed after the development process.
Steps for removing silver halide and developed silver (for example, bleaching step,
A fixing process and a bleach-fixing process). The heat treatment of the photosensitive material is well known in the art.
As for the photothermographic material and its process,
For example, the foundation of photographic engineering (published by Corona in 1979)
Pp. 553 to 555, April 1978 Video Information 4
Page 0, Nebulets Handbook of Photography and Reprogra
3 of phy 7th Ed. (Van Nostrand and Reinhold Company)
2-33, U.S. Pat. No. 3,152,904, ibid.
3,301,678, 3,392,020,
No. 3,457,075, British Patent No. 1,131,10
8, No. 1,167,777 and Research D
Closure Magazine, June 1978, 9-15 (RD-
17029). Activator processing refers to color developing agent.
Do not include a color developing agent in the photosensitive material.
This refers to a processing method in which development processing is performed with a large processing solution. this
In this case, the processing solution is contained in the usual development processing solution components.
It contains no color developing agent and other ingredients (eg
May contain alkali, auxiliary developing agent, etc.)
Yes. For activator processing, European Patent 545,
491A1, No. 565, 165A1, etc.
Illustrated in the offering. Developing with a processing solution containing a developing agent / base
The method is described in RD. No. 17643, pp. 28-29, No. 1
No. 30710 of 651 left column to right column of 8716, and the same.
5, pages 880-881. Photosensitivity of the present invention
The color developer used for the development of the material is preferably aromatic.
Alkali mainly composed of aromatic primary amine color developer
Aqueous solution. As this color developing agent, amino
Enol compounds are also useful, but p-phenylenedia
Minine compounds are preferably used, and typical examples and preferred ones thereof.
A new example is EP556700A, page 28, 43-52.
The compounds described in the line are listed. These compounds are
Depending on the situation, two or more kinds can be used in combination. Color developer
Is an alkali metal carbonate, borate or phosphate
PH buffering agents such as chloride salts, bromide salts, iodide salts,
Benzimidazoles, benzothiazoles or
Development inhibitors or antifoggants such as rucapto compounds
Etc. are generally included. If necessary,
Roxylamine, diethylhydroxylamine, sulfurous acid
Salts such as N, N-biscarboxymethylhydrazine
Dorazines, phenylsemicarbazides, trimethano
Various preservatives such as ruamine and catechol sulfonic acids,
Yes, such as ethylene glycol and diethylene glycol
Organic solvent, benzyl alcohol, polyethylene glycol
Accelerate development such as ruthenium, quaternary ammonium salts, amines
Agent, dye-forming coupler, competitive coupler, 1-phenyl-
An auxiliary developing agent such as 3-pyrazolidone, a thickener,
Aminopolycarboxylic acid, aminopolyphosphonic acid, alkyl
Such as phosphonic acid and phosphonocarboxylic acid
Various chelating agents such as ethylenediaminetetraacetic acid, nitric acid
Trilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane
Xanthandiaminetetraacetic acid, hydroxyethyliminodivinegar
Acid, 1-hydroxyethylidene-1,1-diphosphone
Acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N, N-tetramethylene
Sulfonic acid, ethylenediamine-di (o-hydroxyphen
Nyl acetic acid) and salts thereof. P of color developer
H is generally 9-12. Also these
The amount of developer replenishment depends on the color photographic material being processed.
Generally, 3 liters per square meter of photosensitive material
And reduce the bromide ion concentration in the replenisher
It is possible to make it 500ml or less. Replenishment
When reducing the volume, reduce the contact area with the air in the treatment tank.
To prevent liquid evaporation and air oxidation
preferable. By contact of photographic processing solution and air in processing tank
The treatment effect is the aperture ratio (= [contact area between treatment liquid and air cm
²] ÷ [Capacity of treatment liquid cm^Three ]) Can be evaluated
The This aperture ratio is preferably 0.1 or less,
More preferably, it is 0.001-0.05. Opening ratio
As a method of reducing, it floats on the photographic processing liquid level in the processing tank.
In addition to providing a cover such as a lid, JP-A-1-82032
For providing a movable lid described in JP-A-63-216
Name the slit development method described in No. 050
You can. The aperture ratio is determined by both color development and black-and-white development.
As well as subsequent processes such as bleaching, bleach-fixing,
Reduce in all processes such as fixing, washing and stabilization
It is preferable. Also, accumulation of bromide ions in the developer
Reduce the replenishment amount by using measures to suppress
You can also. The color development time is usually between 2 and 5 minutes.
Set to high temperature, high pH, and color developing agent
By using it at a high concentration, the processing time is further reduced.
You can also. Next, in the present invention, the activator treatment is performed.
Details of processing materials and processing methods used in cases
Explained. In the present invention, the photosensitive material is developed (silver developed).
/ Cross oxidation of built-in color developing agent) and washing or
Stabilized. After washing with water or stabilizing treatment,
Sometimes processing for color enhancement such as potashing is also applied.
is there. The photosensitive material of the present invention is converted into an activator processing solution.
As a silver halide developing agent when developing with
And / or developing agent oxidation that occurs in silver development
The color developing agent built into the photosensitive material is cross acid.
To use a compound (auxiliary developing agent)
And are preferred. Preferably pyrazolidones and dihydroxy
Cybenzenes, reductones and aminophenols
And particularly preferably pyrazolidones are used.
The These compounds may be added to the developer.
It is preferable to be built in. As the pyrazolidones, 1-phenyl-3 is used.
-Pyrazolidones are preferred, 1-phenyl-3-pyra
Zolidon, 1-phenyl-4,4-dimethyl-3-pyra
Zolidon, 1-phenyl-4-methyl-4-hydroxy
Methyl-3-pyrazolidone, 1-phenyl-4,4-di
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-thio
Enyl-3-pyrazolidone, 1-p-tolyl-4-methyl
4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl
-3-pyrazolidone, 1-phenyl-2-hydroxyme
Til-4,4-dimethyl-3-pyrazolidone, 1-fe
Nyl-2-acetyl-3-pyrazolidone, 1-phenyl
2-hydroxymethyl-5-phenyl-3-pyrazoli
Don, 1- (2-chlorophenyl) -4-hydroxyme
Til-4-methyl-3-pyrazolidone and the like. Dihydroxybenzenes include hydrides.
Loquinone, chlorohydroquinone, bromhydroquino
, Isopropyl hydroquinone, methyl hydroquino
2,3-dichlorohydroquinone, 2,5-dichloro
Lohydroquinone, 2,5-dimethylhydroquinone,
Examples include potassium hydroquinone monosulfonate. As reductones, N-methyl-p-
Aminophenol, N- (β-hydroxyethyl) -p
-Aminophenol, N- (4-hydroxyphenyl)
Glycine, 2-methyl-p-aminophenol, etc.
The These compounds are usually used alone but are developed.
And in combination of two or more to increase cross-oxidation activity
It is also preferable to use it. Use of these compounds in developers
The dose is 2.5 x 10^-FourMol / liter to 0.2 mol / liter
Tuttle, preferably 0.0025 mol / liter to 0.00.
1 mol / liter, more preferably 0.001 mol / liter
Liter to 0.05 mol / liter. As a preservative used in the developer of the present invention
Are sodium sulfite, potassium sulfite, and lithium sulfite.
, Formaldehyde sodium bisulfite, hydroxy
There are ruamine and sulfate, and the amount used is 0.1 mol /
Liters or less, preferably 0.001 to 0.02 mol /
Sometimes used in the liter range. High to photosensitive material
When a silver chloride emulsion is used, the above compound is 0.00
1 mol / liter or less, preferably not contained at all
Sometimes not. In the present invention, the hydroxylamine and the sublimation are used.
It is preferable to contain organic preservatives instead of sulfate ions.
Yes. Here, the organic preservative is added by adding to the developer.
It refers to all organic compounds that reduce the deterioration rate of developing agents.
That is, a machine that prevents oxidation of developing agent by air
Is an organic compound that has
Amine derivatives (excluding hydroxylamine), hydroxyl
Samic acids, hydrazines, phenols, α-hydroxy
Cyketones, α-amino ketones, sugars, monoamines
, Diamines, polyamines, quaternary ammoniums,
Nitroxy radicals, alcohols, oximes, di
Amide compounds and condensed amines are particularly effective for organic preservation.
It is a constant agent. These are disclosed in JP-A-63-4235 and 63.
No. 5341, No. 63-30845, No. 63-216
47, 63-43655, 63-46454
No. 63-53551, No. 63-43140, No.
63-56654, 63-58346, 63-
43138, 63-146041, 63-44
No. 657, No. 63-44656, US Pat. No. 3,61
No. 5,503, No. 2,494,903, JP 48
-30496. Other preservatives
JP-A-57-44148 and 57-537
Various metals described in No. 49, JP-A-59-180588
Of salicylic acid described in JP-A No. 54-3532
Alkanolamines, described in JP-A-56-94349
Polyethyleneimines, US Pat. No. 3,746,54
Aromatic polyhydroxy compounds described in No. 4 etc. are required
Depending on the content, it may be contained. In particular, JP-A-4-97355
Alkanolamines described on pages 631 to 632 and
And dialkylhydro compounds described on pages 627 to 630
It is preferable to contain xylamine. In addition, Zia
Rukyl hydroxylamines and / or hydrazine
Use derivatives and alkanolamine in combination.
Or as described in European Patent No. 530,921A1.
Α represented by alkylhydroxylamine and glycine
It is also preferable to use an amino acid in combination. The amount of these compounds used is 1 liter of developer.
Preferably 1 x 10 per torr^-3~ 5x10^-1Mole,
More preferably 1 × 10^-2~ 2x10^-1Is a mole. In the present invention, chlorine ions and odors are contained in the developer.
Contains halogen ions such as elementary and iodine ions
It is. Especially when using high silver chloride emulsions,
3.5 × 10^-3~ 3.0 × 10^-1Contains mol / liter
Preferably 1 × 10^-2~ 2
× 10^-1Mol / liter and / or bromine
ON 0.5 × 10^-Five~ 1.0 × 10^-3Mol / liter
It is preferable to contain, more preferably 3.0 × 10
^-Five~ 5x10^-FourMol / liter. Halide here
May be added directly to the developer and exposed to light during the development process.
It may be eluted from the material into the developer. When added to a developer, as a feed material
Each sodium salt, potassium salt, ammonium
Salt, lithium salt, and magnesium salt are mentioned. In the case of elution from the light-sensitive material, halogenated mainly.
Supplied from silver halide emulsion, but supplied from other than emulsion
Also good. The developer used in the present invention is preferably
The pH is 8 to 13, more preferably 9 to 12. P above
In order to retain H, it is preferable to use various buffers.
Yes. Buffers include carbonate, phosphate, borate, quaternary
Borate, hydroxybenzoate, glycine salt, N, N
-Dimethylglycine salt, leucine salt, norleucine salt,
Guanine salt, 3,4-dihydroxyphenylalanine
Salt, alanine salt, aminobutyrate, 2-amino-2-methyl
1,3-propanediol salt, valine salt, proline
Salt, trishydroxylamine methane salt, lysine salt, etc.
Can be used. Especially carbonates, phosphates, tetraboric acid
Salt and hydroxybenzoic acid are soluble and have a pH of 9.0 or higher.
Excellent buffering capacity in H region, and photographic performance even when added to developer
It is preferable to use these buffers without adversely affecting the surface.
That's right. Specific examples of these buffering agents include carbonic acid carbonate.
Tium, sodium carbonate, potassium carbonate, potassium bicarbonate
, Tripotassium phosphate, trisodium phosphate, diphosphate
Potassium, disodium phosphate, potassium borate, boron
Sodium phosphate, sodium tetraborate, potassium tetraborate
Sodium o-hydroxybenzoate (sodium salicylate)
Thorium), potassium 5-sulfo-2-hydroxybenzoate
Um (potassium 5-sulfosalicylate)
And come. The amount of the buffer added to the developer is 0.05 mol.
Is preferably at least 0.1 mol / liter.
It is particularly preferred that the amount be from ˜0.4 mol / liter. In addition, calcium and magnesia are included in the developer.
As an anti-precipitation agent for sium or for developer stability
Various chelating agents can be used for the above. Example
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-trimethylenediamine
Sphonic acid, ethylenediamine-N, N, N ', N'-te
Tramethylene sulfonic acid, 1,2-diaminopropane tetra
Acetic acid, glycol ether diamine tetraacetic acid, ethylene di
Amine orthohydroxyphenylacetic acid, 2-phosphonobu
Tan-1,2,4-tricarboxylic acid, 1-hydroxy ester
Tylidene-1,1-diphosphonic acid, 1,2-dihydroxy
Cybenzene-4,6-disulfonic acids and their al
A potash metal salt is mentioned. These chelating agents are needed
Two or more types may be used in combination. Of these chelating agents
The amount added is sufficient to conceal metal ions in the developer.
The amount is sufficient, for example, 0.1 g to 10 g per liter
It is about g. In the present invention, an arbitrary card is used as necessary.
An anti-blur agent can be added. Anti-fogging agents include chloride
Such as sodium, potassium bromide, potassium iodide
Lucari metal halide and nitrogen-containing heterocyclic compounds
Used. As the nitrogen-containing heterocyclic compound, for example,
Benzotriazole, 5-nitrobenzotriazole,
5-methylbenzotriazole, 5-nitrobenzimi
Dazole, 5-nitroindazole, 2-thiazolylbe
Imidazole, indazole, hydroxyazaine
Dridine, adenine, 1-phenyl-5-mercaptote
Give a representative example of tolazole or its derivatives
Can do. The amount of nitrogen-containing heterocycle added is 1 × 10^-Five~ 1
× 10^-2Mol / liter, preferably 2.5 × 10^-Five~
1 × 10 ^-3Mol / liter. In the developer, an optional development accelerator is used if necessary.
Can be added. As a development accelerator, JP-B-37-16
088, 37-5987, 38-7826,
44-12380, 45-9019 and the United States
Thioethers represented in Japanese Patent No. 3,813,247
Compounds, JP-A 52-49829 and 50-1
P-Phenylenediamine compound represented by No. 5554
, JP-A-50-137726, JP-B 44-300
74, JP-A-56-156826 and 52-4.
Quaternary ammonium salt represented by No. 3429, US patent
Nos. 2,494,903, 3,123,182,
4,230,796, 3,253,919, special public
Sho 41-11431, U.S. Pat. No. 2,482,546
Nos. 2,596,926 and 3,582,34
Amine compounds described in No. 6, etc., JP-B 37-1608
No. 8, No. 42-25201, US Pat. No. 3,532,
Polyalkylene oxides and imi represented by No. 501 etc.
Dazoles can be added as needed. The developer may contain a fluorescent brightening agent.
preferable. Especially 4,4-diamino-2,2'-disulfo
It is preferable to use a stilbene compound. Specifically
Are commercially available optical brighteners such as “Dyeing Note 19th Edition”
Compounds described on pages 165 to 168, and JP-A-4-24
No. 2943, pages 3 to 7 can be used.
it can. Addition amount is 0.1g-10g / liter, preferable
Or 0.5 g to 5 g / liter. The processing temperature of the developer applied to the present invention is 2
It is 0-50 degreeC, Preferably it is 30-45 degreeC. processing time
Is from 5 seconds to 2 minutes, preferably from 10 seconds to 1 minute. Replenishment amount
Is preferably less, but 15 to 6 per 1 m @ 2 of photosensitive material.
00ml, preferably 25-200ml, more preferably
35-100 ml. The light-sensitive material of the present invention is washed with water after development processing.
And / or a stabilization process. The amount of water washed in the washing process
Is a characteristic of the photosensitive material (for example, depending on the material used such as a coupler).
), Use, and also the temperature of the washing water, the number of washing tanks (stage
Number), countercurrent, forward flow, etc., and other various conditions
Can be set in a wide range. Of these, the multistage countercurrent method
The relationship between the number of flush tanks and the volume of water
iety of Motion Picture and Television Engineers
Volume 64, pages 248-253 (May 1955)
It can be obtained by this method. Multi-stage orientation described in this document
According to the flow method, the amount of water to be washed can be greatly reduced.
Increased water residence time in the
Problems such as adhering floating material generated and propagated to photosensitive material
Occurs. As a solution to this problem, Japanese Patent Laid-Open No. 62-288,8
Calcium ions and magnesium ions described in No. 38
The method of reducing the is very effective. In addition, JP-A-5
7-8,542 isothiazolone compounds and
Abendazoles, chlorinated sodium isocyanurate
Chlorinated fungicides such as benzotriazoles, Horiguchi
Hiroshi, “Chemistry of Antibacterial and Antifungal Agents” (1986) Sankyo Publishing, Mamoru
“Technology for Sterilization, Sterilization, and Antifungal” of Biotechnology Society (198)
2 years) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal
The fungicides described in “Ten” (1986) can also be used.
The The pH of the washing water in the processing of the photosensitive material of the present invention is 4
~ 9, preferably 5-8. Washing water temperature, water washing
The time can also be set according to the characteristics and application of the photosensitive material.
Generally, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably 25
A range of 30 seconds to 5 minutes at -40 ° C is selected. In addition, book
The light-sensitive material of the invention uses a direct stabilizing solution instead of the above water washing.
Can also be processed. Such stabilization process
JP-A-57-8543, 58-14834.
And known methods described in JP-A-60-220345 are applied.
it can. Further, following the water washing treatment, further stabilization treatment
As an example of this, it is necessary to
Contains dye stabilizer and surfactant used as final bath
And a stable bath. As a dye stabilizer
Aldehydes such as formalin and glutaraldehyde
, N-methylol compounds, hexamethylenetetrami
Or aldehyde sulfite adduct
The Various chelating agents and antifungal agents can be added to this stabilizing bath.
You can also. Next, in the present invention, in the case of heat development processing
Processing materials and processing methods used in the process are described in detail
To do. The light-sensitive material of the present invention contains silver development and dye formation.
Use a base or base precursor to accelerate the reaction
It is preferable. As a base precursor, heat
Organic acid and base salts to be decarboxylated, intramolecular nucleophilic substitution reaction,
Release of amines by the Rosen or Beckmann transition
There are compounds to be released. Specific examples are given in U.S. Pat.
4,514,493, 4,657,848 and
Known Technology No. 5 (March 22, 1991, with Aztec)
Page 55 to page 86, etc.
In addition, European Patent Publication No. 210,660, which will be described later,
Water as described in permit 4,740,445
-Soluble basic metal compound and the basic metal compound
Complex formation reaction using metal ions and water as a medium
Base is generated by a combination of compounds (referred to as complex-forming compounds)
It is also possible to make it. Use of base or base precursor
The amount is 0.1-20g / m², Preferably 1-10 g / m²so
is there. The light-sensitive material of the present invention accelerates heat development.
A hot solvent may be added for the purpose. For example, the United States
Patent Nos. 3,347,675 and 3,667,9
Organic compounds having polarity as described in No. 59
Is mentioned. Specifically, amide derivatives (benzamide
Etc.), urea derivatives (methyl urea, ethylene urea, etc.),
Ruhonamide derivatives (Japanese Patent Publication No. 1-40974 and
Compounds described in No. 4-13701, etc.)
Riol compounds sorbitols) and polyethylene
And glycols. When the hot solvent is insoluble in water
Is preferably used as a solid dispersion. Added
Depending on the purpose, the layer can be either a photosensitive layer or a non-photosensitive layer.
Yes. The amount of the hot solvent added is 10% of the binder of the layer to be added.
% By mass to 500% by mass, preferably 20% by mass to 300%
% By mass. The heating temperature in the heat development step is from about 50 ° C. to 2 ° C.
50 ° C, but 60 ° C to 150 ° C is particularly useful
The In the heat development process, air is blown during heat development.
Block or prevent volatilization of the material from the sensitive material
Supply to the photosensitive material or no longer required after development
Materials in photosensitive materials (YF dye, AH dye, etc.) or current
In order to remove unnecessary components generated during imaging,
Overlay the material other than the material on the photosensitive surface of the photosensitive material and heat it.
Also good. Treatment sheet support and vine used in this case
The same material as the photosensitive material can be used.
The The treatment sheet has the above-mentioned dye removal and other purposes.
Then, a mordant may be added. Mordants are known in the photographic field
Can be used, US4,500,626
Columns 58-59 and JP-A-61-88256, 32-4
1 page, JP-A-62-244043, JP-A-62-224
The mordant described in No. 4036 can be used. Ma
In addition, high dye acceptability described in US Pat. No. 4,463,079
A child compound may be used. When using a treated sheet, a base or salt
The base precursor should be contained in a separate sheet.
It is preferable in terms of enhancing the raw storage stability. Also, use a hot solvent.
Depending on the purpose, either photosensitive material or processing sheet
You can put it in both. In the case of heat development using a processing sheet,
Promotion of development or transfer of processing materials, expansion of unnecessary materials
A solvent may be used for the purpose of promoting dispersion. Specifically, rice
National Patent Nos. 4,704,245 and 4,470,445
And JP-A 61-238056.
In this method, the heating temperature is lower than the boiling point of the solvent used.
Below is preferred. For example, when the solvent is water, 50 ° C. to 10 ° C.
0 ° C. is preferred. Development and / or processing materials
Examples of solvents used for diffusion transfer of water include water and inorganic
Basic aqueous solution containing alkali metal salt or organic base
These bases are those described in the section on image formation accelerators.
Low boiling solvent or low boiling solvent and water
Or a mixed solution with the basic aqueous solution. Also
Complex formation with surfactants, antifoggants and sparingly soluble metal salts
A compound, an antifungal agent, or an antibacterial agent may be included in the solvent. this
Water is the preferred solvent used in these thermal development processes.
However, water that is commonly used can be used.
Anything can be used. Specifically, distilled water, tap water, wells
Water, mineral water, etc. can be used. Also
In a heat development apparatus using the photosensitive material and the image receiving element of the present invention
In most cases, you can use up all the water, or circulate it repeatedly.
You may use it back. In the latter case, components eluted from the material
Will be used. JP-A-63-14
4,354, 63-144,355, 62-3
8,460, JP-A-3-210,555, etc.
You may use an apparatus and water. These solvents are sensitive materials, processing
Use the method of applying to the physical sheet or both
it can. In this case, it corresponds to the maximum swelling volume of the entire coating film.
It may be less than or equal to the mass of the solvent. As a method of applying this water
Are disclosed in, for example, JP-A-62-253159, page (5),
The method described in Sho 63-85,544 is preferably used.
It is done. Also, the solvent is trapped in the microcapsule
In the form of hydrate, the photosensitive material or processing sheet or
Can also be used in both of them. Give
The temperature of water is described in JP-A 63-85,544.
Thus, what is necessary is just 30 to 60 degreeC. Thermal development in the presence of a small amount of water or solvent
If so, European Patent Publication 210,660, US Patent No.
As described in No. 4,740,445, difficult to water
A soluble basic metal compound and the basic metal compound.
Of complexing reaction using metal ions and water as a medium
A base is generated by a combination of compounds (called complex-forming compounds).
It is effective to adopt this method. In this case, difficult to water
Soluble basic metal compounds are treated with light-sensitive materials, and complex-forming compounds are treated with light-sensitive materials.
It is desirable to add it to the physical sheet from the viewpoint of raw preservation. As a heating method in the development step, heating is used.
Touching a block or plate that has been
Toppressor, heat roller, heat drum, halogen lamp
Contact with heaters, infrared and far-infrared lamp heaters, etc.
Or let it pass through a hot atmosphere.
A method for superimposing a photosensitive material and a processing sheet is disclosed in JP-A-62.
-253,159, JP-A-61-147,244 (2
7) The method described on page is applicable. The processing of the photographic elements of the present invention may involve various heat developments.
Any of the devices can be used. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, JP-A-6-130,509, 6
-95,338, 6-95,267, 8-2
9,955, 8-29,954, etc.
Such a device is preferably used. Also, as a commercially available device
Pictorostat 10 manufactured by Fuji Photo Film Co., Ltd.
0, the same Pictrostat 200, the same Pictrostat 3
00, pictorostat 330, pictorostat
50, pictogram 3000, pictogram
Fee 2000 or the like can be used. Photosensitive material and / or processing sheet of the present invention
Is a conductive heating element layer as a heating means for heat development
The form which has this may be sufficient. In the heating element of this invention
The one described in JP-A-61-145,544 is used.
Can be used. Photosensitive materials include coating aids, releasability improvements, stains.
Various interfaces for purposes such as improved verifiability, antistatic and development promotion
Activators can be used. Specific examples of surfactants
Known Technology No. 5 (March 22, 1991, with Aztec)
136-138 pages of the limited company), JP-A 62-17
3,463, 62-183,457, etc.
ing. For photosensitive materials, slipperiness prevention, antistatic, peeling
Organic fluoro compounds may be included for the purpose of improving
Yes. As a representative example of the organic fluoro compound, JP-B-57
No. 9053, columns 8-17, JP-A 61-20944
And fluorine described in 62-135826
Surfactants or oily fluorine such as fluorine oil
Compound or solid fluoride such as tetrafluoroethylene resin
And hydrophobic fluorine compounds such as elemental compound resins. The light-sensitive material preferably has a slip property. Slip
The agent-containing layer is preferably used on both the photosensitive layer surface and the back surface.
That's right. As a preferable slipping property, the coefficient of dynamic friction is 0.25 or more.
Lower than 0.01. The measurement at this time is a step with a diameter of 5 mm.
Represents the value when transported at 60cm / min for a ballless ball
(25 ° C., 60% RH). In this evaluation,
Even if it is replaced with the photosensitive layer surface, the value is almost the same level. Messenger
Possible slip agents include polyorganosiloxane, high
Grade fatty acid amide, higher fatty acid metal salt, higher fatty acid and higher grade
Alcohol esters, etc., polyorganosiloxa
Examples of polydimethylsiloxane and polydiethylsiloxane
Loxane, polystyrylmethylsiloxane, polymethyl
Phenylsiloxane or the like can be used. With additive layer
Therefore, the outermost layer and the back layer of the emulsion layer are preferable. Especially poly
Esters with dimethylsiloxane or long-chain alkyl groups
Is preferred. In the present invention, an antistatic agent is preferred.
Used. These antistatic agents include carbo
Polymers containing acids and carboxylates and sulfonates;
List thionic polymers and ionic surfactant compounds
You can. The most preferable antistatic agent is Zn.
O, TiO₂, SnO₂, Al₂O_Three , In₂O_Three , SiO₂, MgO, BaO, M
oO_Three, V₂O_FiveAt least one volume resistivity selected from
10⁷ Ω · cm or less, more preferably 10^Five Ω ・ cm or less
Particle size of 0.001 to 1.0 μm Crystalline metal
Oxides or their complex oxides (Sb, P, B, In, S,
Si, C, etc.) fine particles, and also sol-like metal oxides
Or fine particles of these composite oxides. Inclusion in sensitive material
The amount is 5 to 500 mg / m²Is particularly preferred
10 to 350 mg / m²It is. Conductive crystalline oxide or
The mass ratio of the composite oxide to the binder is 1/300 ~
100/1 is preferable, more preferably 1/100 to 1
00/5. Composition of photosensitive material or processing sheet (back
Including layer), dimension stabilization, curl prevention, adhesion prevention,
Improvement of film physical properties such as prevention of film cracking and pressure fluctuation
Various polymer latexes can be included
The Specifically, JP-A-62-245258 and 62
-136648, 62-110066, etc.
Any polymer latex can be used. In particular, Gala
Polymer latex with low transition point (40 ° C or less)
When used in dyed layers, it can prevent cracking of the mordant layer.
And polymer latex with a high glass transition point.
When used in the cover layer, an anti-curl effect can be obtained. The light-sensitive material of the present invention preferably has a matting agent.
That's right. Matting agent can be emulsion side or back side
Although it is good, it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble or insoluble in the processing solution.
Preferably, both are used together. For example, polymethyl
Methacrylate, poly (methyl methacrylate / metac
(Rylic acid = 9/1 or 5/5 (molar ratio)), polystyrene
Particles are preferred. The particle size is 0.8-10μm
Preferably, the particle size distribution is also narrower, the average particle size
90% or more of the total number of particles contained between 0.9 and 1.1 times
It is preferred that Also, to improve matting properties
It is also preferable to add fine particles of 0.8 μm or less at the same time.
For example, polymethylmethacrylate (0.2 μm),
Poly (methyl methacrylate / methacrylic acid = 9/1
(Molar ratio), 0.3 μm)), polystyrene particles (0.25
μm) and colloidal silica (0.03 μm).
The Specifically, it is described in JP-A-61-88256 (page 29).
It is listed. Others, benzoguanamine resin beads,
Special features such as polycarbonate resin beads and AS resin beads
Kaisho 63-274944, 63-274952
There are listed compounds. Other Research Disclosure
The compounds described in the jar can be used. In the present invention, the photosensitive material and the processing sheet are used.
Supports that can withstand the processing temperature
Is used. In general, the Japanese Society for Photography
Basics-Silver Salt Photo Edition ", published by Corona Inc. (Showa 54)
Year) (223) to (240) pages of paper, synthetic polymer (fill
And the like. Specifically, poly
Ethylene terephthalate, polyethylene naphthalate,
Polycarbonate, polyvinyl chloride, polystyrene, polyethylene
Polypropylene, polyimide, celluloses (eg tri
Acetylcellulose) and the like. These are alone
Or synthetic polymers such as polyethylene
Use as a support laminated on one or both sides
You can also. In addition, JP-A-62-25315
9 (29)-(31), JP-A-1-161,236 (14)-
(17), JP-A 63-316,848, JP-A 2-2
No. 2,651, No. 3-56,955, U.S. Pat.
Supports described in 001, 033 etc. can be used
The Especially where heat resistance and curl characteristics are particularly demanding
JP-A-6-41281 as a support for photosensitive material.
No., No. 6-43581, No. 6-51426, No. 6-
51437, 6-51442, JP-A-6-829
61, 6-82960, 6-123937,
6-82959, 6-67346, 6-11
No. 8561, No. 6-266050, No. 6-20227
No. 7, No. 6-175282, No. 6-118561,
In the publications 7-219129 and 7-219144
The described supports can be preferably used. Also main
Styrene polymerization with syndiotactic structure as
A support that is a body can also be preferably used. In addition, the support and the light-sensitive material constituting layer are bonded together.
Therefore, it is preferable to perform a surface treatment. Chemical treatment, mechanical
Treatment, corona discharge treatment, flame treatment, UV treatment, high frequency
Treatment, glow discharge treatment, active plasma treatment, laser treatment
Surface activation treatment such as chemical treatment, mixed acid treatment, ozone oxidation treatment
Is mentioned. Among the surface treatments, ultraviolet rays are preferable.
Irradiation treatment, flame treatment, corona treatment, glow treatment.
Next, the primer method is described.
Also good. As binder for undercoat layer, vinyl chloride, salt
Vinylidene chloride, butadiene, methacrylic acid, acrylic
Selected from acid, itaconic acid, maleic anhydride, etc.
Starting with copolymers starting from monomers,
Tylene imine, epoxy resin, grafted gelatin, ni
Examples include trocellulose and gelatin. Swelling support
And resorcinol and p-chlorophenol
There is. Chromium salt as gelatin hardener for undercoat
(Such as chromium alum), aldehydes (formaldehyde)
, Glutaraldehyde, etc.), isocyanates,
Active halogen compounds (2,4-dichloro-6-hydroxy
C-s-triazine), epichlorohydrin resin,
An active vinyl sulfone compound etc. can be mentioned.
SiO², TiO², Inorganic fine particles or polymethyl methacrylate
Copolymer fine particles (0.01 to 10 μm) with a matting agent
And may be contained. Also, as a support, for example, Japanese Patent Laid-Open No. 4-1
No. 24645, No. 5-40321, No. 6-35092
And a magnetic recording layer described in JP-A-6-317875.
It is preferable to record photographing information and the like using a holder. With the magnetic recording layer, magnetic particles are bonded to a binder.
Aqueous or organic solvent-based coating solution dispersed in
It is a thing painted on. Magnetic particles are γFe₂O_Three Such as
Ferromagnetic iron oxide, Co-coated γFe₂O_Three , Co-deposited magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic gold
Genus, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite
, Pb ferrite, Ca ferrite, etc. can be used. Co
Duplicated γFe₂O₂ Co-coated ferromagnetic iron oxide such as is preferred. form
The shape is needle, rice grain, sphere, cube, plate, etc.
It may be. S in specific surface area_BET 20m²/ G or more is preferred
30m²/ G or more is particularly preferable. Saturation of ferromagnets
The sum magnetization (σs) is preferably 3.0 × 10 ^Four ~ 3.0
× 10^Five A / m 2, particularly preferably 4.0 × 10^Four~
2.5.times.100@5 A / m. Ferromagnetic particles on silica
And / or surface treatment with alumina or organic materials
May be. Further, the magnetic particles are disclosed in JP-A-6-1610.
Silane coupling on the surface as described in No. 32
It may be treated with an agent or a titanium coupling agent. or
Described in JP-A-4-259911 and 5-81652
Magnetic particles with inorganic or organic coating on the surface can be used.
The The binder used for the magnetic particles is a special one.
Thermoplastic resin and thermosetting described in Kaihei 4-219569
Resin, radiation curable resin, reactive resin, acid, alkali
Or biodegradable polymer, natural product polymer (cellulose-derived
Body, sugar derivatives, etc.) and mixtures thereof
You can. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is 20,000 to 1,000,000. For example
Nyl copolymer, cellulose diacetate, cellulose
Triacetate, cellulose acetate propionate
, Cellulose acetate butyrate, cellulose tri
Cellulose derivatives such as propionate, acrylic tree
Fat, polyvinyl acetal resin,
Latin is also preferred. Cellulose di (tri) acetate
Is preferred. Binder is epoxy, aziridine
Curing by adding an isocyanate or isocyanate crosslinking agent
be able to. Isocyanate-based crosslinking agents include
Lylene diisocyanate, 4,4'-diphenylmethane
Diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate
Reaction of these isocyanates with polyalcohols
Reaction products (eg 3 mol of tolylene diisocyanate and
1 mol trimethylolpropane reaction product), and this
Polyisothesis formed by condensation of these isocyanates
Examples thereof include cyanate. For example, JP-A-6-5935
It is described in No.7. Disperse the above-mentioned magnetic material in the binder.
The method described in JP-A-6-35092
Like kneader, pin type mill, annular type mill
Are preferably used together. JP-A-5-088283
Or other known dispersants can be used.
The The thickness of the magnetic recording layer is preferably 0.1 μm to 10 μm.
Or 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The mass ratio of magnetic particles to binder is preferred
Or 0.5: 100-60: 100
Preferably, it is 1: 100-30: 100. Magnetic particles
The coating amount is 0.005 to 3 g / m², Preferably 0.01
~ 2g / m²More preferably, 0.02 to 0.5 g / m²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferred and 0.03 to 0.20 is more preferred
0.04 to 0.15 is particularly preferable. Magnetic recording layer
Is applied or printed on the back of the photographic support.
Alternatively, they can be provided in stripes. Magnetic recording layer
The application method is air doctor, blade, air
Knives, squeeze, impregnation, reverse roll, transf
Galore, gravure, kiss, cast, spray, di
, Bars, extrusions, etc.
The coating solution described in JP-A-5-341436 is preferable. For the magnetic recording layer, improved lubricity, curl adjustment,
Combines functions such as antistatic, adhesion prevention, and head polishing
Or provide another functional layer for these functions.
And at least one of the particles may be Morse.
Abrasives of non-spherical inorganic particles having a hardness of 5 or more are preferred. Non
The composition of spherical inorganic particles includes aluminum oxide, oxidation
Chrome, silicon dioxide, titanium dioxide, silicon carbide
Oxide such as silicon carbide, carbide such as silicon carbide, titanium carbide, die
A fine powder such as almond is preferred. These abrasives are
Surface of silane coupling agent or titanium coupling
It may be treated with an agent. These particles are added to the magnetic recording layer.
In addition, an overcoat on the magnetic recording layer (example
For example, a protective layer or a lubricant layer may be used. Use at this time
The binders mentioned above can be used, preferably magnetic.
The same binder as the recording layer is preferable. Has a magnetic recording layer
For the sensitive material to be used, US Pat. No. 5,336,589
5,250,404, 5,229,259,
5,215,874 and EP466,130
It is. Preferred for the light-sensitive material having the magnetic recording layer described above.
The polyester support used is described further.
Details including materials, processing, cartridges and examples
Published technical bulletin, public technical number 94-6023 (invention
1994; 3.15). Polyes
Tells diol and aromatic dicarboxylic acid as essential components
2,6-, 1,5 formed as aromatic dicarboxylic acids
-, 1,4- and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, diol
Diethylene glycol, triethylene glycol,
Chlohexanedimethanol, bisphenol A, bisphenol
Enol. As this polymer,
Reethylene terephthalate, polyethylene naphthalate
, Polycyclohexanedimethanol terephthalate, etc.
Can be mentioned. I especially like it
2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 100
Polyester containing mol%. Especially preferred
Is polyethylene 2,6-naphthalate. Average
The range of the mass is about 5,000 to 200,000
The The Tg of the polyester is 50 ° C. or higher, and 9
0 degreeC or more is preferable. Next, the polyester support is provided with a curl.
In order to make it difficult, the heat treatment temperature is 40 ° C. or higher and lower than Tg.
More preferably, heat treatment is performed at Tg−20 ° C. or more and less than Tg.
Yeah. The heat treatment may be performed at a constant temperature within this temperature range.
Alternatively, heat treatment may be performed while cooling. This heat treatment time
Is 0.1 hours to 1500 hours, more preferably
Is 0.5 hours or more and 200 hours or less. Heat treatment of support
The process may be carried out in roll form or conveyed in web form.
However, it may be carried out. Provide irregularities on the surface (for example,
(SnO2 or Sb2O5 etc.) Conductive inorganic fine particles)
The shape may be improved. Also, add knurling to the end
Preventing the cut-out of the core part by slightly raising only the part
It is desirable to devise such as These heat treatments
After forming the support, after surface treatment, after coating the back layer (antistatic
Agent, slip agent, etc.)
Also good. Preferred is after application of the antistatic agent. This
A UV absorber may be incorporated into the reester. Also la
Mitsubishi Chemical's Diaresin, Japan
It is marketed for polyesters such as Kayaset made by Nippon Kayaku.
The purpose is achieved by kneading the dyes or pigments
Is possible. Next, a photosensitive material can be loaded.
I will write about Irum Patrone. The package used in the present invention
The main material of Trone is either metal or synthetic plastic
Yes. Preferred plastic materials are polystyrene and polyethylene.
Tylene, polypropylene, polyphenyl ether, etc.
The Furthermore, the patrone may contain various antistatic agents.
Well carbon black, metal oxide particles, nonions,
Nion, cationic and betaine surfactants or polymers
-Etc. can be preferably used. These antistatic
The patrone is disclosed in JP-A-1-3123737 and 1-
No. 312538. Especially 25 ° C, 25%
The resistance at RH is preferably 1012 Ω or less. Normal plastic
In order to add light shielding,
Made of plastic kneaded with racks and pigments
Made. The size of the cartridge is currently 135.
It is also possible to reduce the size of the camera.
The diameter of the 25 mm cartridge must be 22 mm or less.
Is also effective. The volume of the cartridge case is 30cm3.
In the following, it is preferably 25 cm 3 or less. Pa
Plastic used for trolley and patrol cases
The weight of the pack is preferably 5 to 15 g. Furthermore, the spool is rotated to send out the film.
A patrone is also acceptable. The film tip is also patrone.
The spool shaft is stored in the main body and the film feed direction is
Rotate the film tip of the cartridge
A structure of sending out from the port portion may be used. These are U
Opened on S4,834,306 and 5,226,613
It is shown. Color paper using this color photographing material
As a method of producing prints on photothermographic materials,
JP-A-5-241251, No.5,19364, No.5
The method described in No. 19363 can be used. [0180] The present invention will be described in more detail with reference to the following examples.
Although described, the present invention is not limited to these.
Yes. (Preparation of emulsion) (Preparation of emulsion A (silver iodobromide)) Weight average molecular weight 1500
1.0g of low molecular weight oxidized gelatin of 0 and KBr
Keep 1200 mL of 1.0 g aqueous solution at 35 ° C
Agitate. AgNO ₃30m aqueous solution containing 1.9g
L, KBr 1.5g, weight average molecular weight 15000 low
30 mL of aqueous solution containing 0.7 g of molecular weight oxidized gelatin
Is added over 30 seconds by the double jet method to form nuclei
Went. At this time, keep the excessive concentration of KBr constant.
It was. 6 g of KBr was added and the mixture was aged by raising the temperature to 75 ° C.
After ripening, 35 g of succinated gelatin was added. pH
Was adjusted to 5.5. AgNO₃Aqueous solution 1 containing 30 g
50 mL and KBr aqueous solution for 16 minutes by double jet method
Was added over a period of time. At this time, the silver potential is applied to the saturated calomel electrode.
On the other hand, it was kept at -40 mV. Furthermore, AgNO₃11
An aqueous solution containing 0 g and an aqueous KBr solution
Accelerate the flow rate so that the final flow rate is 1.2 times the initial flow rate.
Added over 15 minutes. At this time, the size is 0.03μ
m AgI fine grain emulsion with a silver iodide content of 3.8%
So that the flow rate is accelerated at the same time and the silver potential is -4
It was kept at 0 mV. AgNO₃Aqueous solution 132 containing 35 g
mL and KBr aqueous solution for 7 minutes by double jet method
Added. Make the potential at the end of addition -20mV
The addition of the aqueous KBr solution was adjusted. The temperature was 40 ° C
Thereafter, 5.6 g of Compound 1 in terms of KI was added, and further 0.1.
64 mL of an 8M aqueous sodium sulfite solution was added. The
In addition, an aqueous NaOH solution was added to raise the pH to 9.0 and 4 minutes.
For a period of time to generate iodide ions rapidly, and then pH
Was returned to 5.5. After returning the temperature to 55 ° C, benzene
Add 1 mg of sodium thiosulfonate and add
13g of lime-processed gelatin with a concentration of 1ppm
Added. After the addition, AgNO₃Aqueous solution 2 containing 70 g
Keep 50 mL and KBr aqueous solution at 60 mV potential
Added over 20 minutes. At this time, yellow blood salt is silver 1
1.0 x 10 per mole^-5Mole was added. Washed with water
Then, lime-processed gelatin with a calcium concentration of 1 ppm was added.
and adjust pH to 5.8 and pAg to 8.7 at 40 ° C.
Arranged. Compound 1 [Chemical 1] [0183] Calcium and magnesium in the above emulsion.
And strontium content in ICP emission spectroscopy
Measured more than 15ppm and 2ppm respectively.
And 1 ppm. Emulsion A is the average equivalent sphere diameter of all grains
Is 0.92 μm, average equivalent circle diameter is 1.2 μm, average particle
Thickness 0.08μm, average aspect ratio 14, equivalent to a circle
The variation coefficient of the diameter distribution is 24%, and the projected area of all particles
70% or more is equivalent circle diameter 1.0μm or more, average particle thickness
Silver iodobromide (including silver iodide) of 0.01 μm to 0.1 μm
4 mol% and silver chloride content 0%). (Preparation of emulsion B (silver chloride))
1740 ml of latin aqueous solution (methionine content is about 40 μm)
Containing 36 g of deionized alkali-treated bone gelatin
PH 4.8) and maintain the temperature at 40 ° C.
NO_Three  6 mL of 1N solution, NaCl-solution (Na in 100 mL)
14 ml of Cl (containing 10 g) is added, and Ag-1 solution (100 ml) is added.
AgNO inside_Three 20g in) and X-1 solution (in 100ml)
6.5 g NaCl, KBr 0. 68ml / min)
At the same time, only 51 ml was added. After stirring for 2 minutes, X
-2 liquid (containing 2.1 g of KBr in 100 ml) 186
Only 62 ml was co-mixed at ml / min. Stir for 1 minute
After that, Ag-1 solution and X-1 solution are the same at 77 ml / min.
When mixed, it was added. Set the pH to 4.8 and raise the temperature to 75 ° C.
Warm up. Aged for 10 minutes. Next, A at silver potential + 120mV
g-3 solution (AgNO in 100 ml)_Three 40g included) and X
-3 solution (containing 15 g of KBr in 100 ml) CD
(Controlled double jet) method was added. At the start of addition
The flow rate is 5 ml / min, and the flow rate is accelerated by 0.1 ml / min per minute.
609 ml of Ag-3 solution was added. After further 5 minutes, Ag-4 at a silver potential of +130 mV.
Liquid (AgNO in 100 ml)_Three 10g inclusive) and X-4 liquid
(Contains 3.6 g NaCl in 100 ml) CDJ (c
ontrolled double jet). The flow rate at the start of addition is
Accelerated addition of 0.1 ml / min per minute at 7 ml / min
Then, 140 ml of Ag-4 solution was added. The obtained emulsion grains were found to have a main plane from a TEM image.
The projected area ratio of tabular grains with {100} faces is about 70%.
Average sphere equivalent diameter 0.87 μm, average circle equivalent diameter 1.91 μm
m, average particle thickness 0.12 μm, variation in equivalent circle diameter distribution
The coefficient was 32%. Also, the annealed particles
From the X-ray diffraction, the total Cl- content is 95 mol%.
It was. (Preparation of sample) The above emulsion, titanium oxide
Emulsion dispersions as shown in Table 1
3. Triacetic acid cells provided with an undercoat layer in Examples 1 to 4
Prepared on a loin film support. [0188] [Table 1] The coated silver amount of each sample was 1.75 g / m.²age
It was. As a hydrophilic binder for each sample, gelatin is used.
The total amount of titanium oxide and gelatin used for each sample
The product is 2mL / m²It applied so that it might become. Only Comparative Example 1 is oxidized
Contains no titanium and other samples contain titanium oxide.
ing. The titanium oxide of Comparative Example 2 is 495 g of steam at room temperature.
Prepare a reaction vessel containing distilled water and stir it vigorously.
Et al. 250 mL titanium tetraisopropoxide and 4
Add a solution containing 0 mL isopropanol from the dropping funnel.
Add at a rate of about 25 mL and add the resulting material to a metal container.
And then 25% water of tetramethyl hydroxide
2 g of solution is added and the mixture is heated to isopropanol.
When the reaction product is evaporated and then reaches 100 ° C.
8.6% aqueous solution of tetramethyl hydroxide in terms of point 38.
2 g are added and the mixture is then added to a triangular flask equipped with a concentrator.
Transfered to Lasco and refluxed for 40 hours to obtain a dispersion. Also ratio
Comparative Example 3 and Examples 1 to 4 use Dispex N- as a dispersion stabilizer.
40 (Allied Colloids Ltd.) or weight average molecular weight 2
25 masses of 5,000 low molecular weight gelatin to titanium oxide
% And using zirconium oxide beads (particle size 0.3
Mm) Parallel 4-cylinder 1 / 8G Sun made by IMEX
Dispersion liquid dispersed with dog grinder TSG-1 / 8-4U for 8 hours
It was used. For the following comparative examples and examples,
Tan's average primary particle size is X-ray diffraction, Anatase is (1,
The strongest interference line on the (0, 1) plane, rutile is the (1, 1, 0) plane
It was determined from the half width of the strongest interference line. Also rutile crystallinity
Is 1: 5 by mass of silicon and titanium oxide to be measured
And then by X-ray diffraction, rutile (1, 1,
0) take the ratio of the peak area of the surface to the peak area of silica,
As a standard sample, MT600B (Taika Co., Ltd. fine particles
Titanium oxide, average primary particle size 50nm, no surface treatment)
Measure this and set it to 100% rutile crystallinity.
The ratio to the fee was calculated. The average particle size of the aqueous dispersion is Horiba
Measurement was performed with LA920 manufactured by Sakusho. Titanium oxide volume%
The sample application area is 1m²Quality of titanium oxide
The value obtained by dividing the amount (g) by the specific gravity 4 is α, the sample application area 1
m²Gelatin weight per gram (g)
The value obtained by dividing by 4 was defined as β, and α / (α + β) was calculated. Ma
Specular transmission density B is Hitachi C-2000 color
-Angular direction at an angle of 3 ° (half angle) measured with an analyzer
The specular transmittance at a wavelength of 550 nm integrated with T
s and B = −logTs. B / A is the value of B
Amount of applied silver A (Unit: g / m²The value divided by. In Comparative Example 2, the titanium oxide aggregated.
Therefore, the coated surface is extremely bad, causing reading errors and reading.
It became impossible to remove. For Comparative Example 3, the titanium oxide
Since the dispersing agent was deposited, the coated surface was bad. Comparative Example 1 and B / A exceeding 0.57
And B / A was less than 0.57.
Scan with LS-4000 scanner manufactured by Con Co., Ltd.
It was. For Comparative Example 1, scanning takes 20 seconds or more
However, the finished print image was also inferior.
1-4 can be read well within 10 seconds.
It was. Comparative Examples 1 to 3 and Examples 1 to 4
Zera containing titanium oxide and excluding silver halide grains
Cellulose triacetate film with an undercoat layer
An attempt was made to form a film on a film support to a thickness of 1 μm.
In Comparative Examples 2 and 3, the surface shape is poor and a uniform film is prepared.
Although it was not possible to manufacture, other comparative examples and examples
It was possible to form a uniform film. Comparative Example 1 and Examples 1-4
About Nippon Denshoku Industries Co., Ltd. VG-1D variable angle gloss meter
The haze value was 10 or less.
It was a highly transparent film.

Claims (1)

What is claimed is: 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
The total silver coating amount (g / m ² ) of the silver halide emulsion contained in the silver halide emulsion layer is A, and the specular transmission density in the state where desilvering is not performed after development processing, which is expressed by the following formula: A silver halide photographic light-sensitive material, wherein the value of B / A is less than 0.57 when the value of B is B. B = −log Ts where Ts is 5 measured by integrating at an angle of 3 ° (half angle).
It represents the specular transmittance at 50 nm.