JP2003322924A - Heat-developable photosensitive material obtained by using solid dispersion and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a heat-developable photosensitive material including a production process in which a solid dispersion of an organic compound is stably produced in a shortened production time while preventing creaming of a dispersion liquid due to entrained air. <P>SOLUTION: In the method for producing a heat-developable photosensitive material comprising a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder on at least one face of a support and containing a solid dispersion of an organic compound in at least one of the constituent layers, the solid dispersion is produced through a defoaming step in predispersion before dispersion. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention contains a solid dispersion.
The present invention relates to a photothermographic material and a production method thereof.
The [0002] [0002] In recent years, in the medical field, environmental conservation,
From the viewpoint of pace, a reduction in the amount of processing waste liquid is strongly desired.
So, laser imagesetter or laser
It can be exposed efficiently by the imager, and high
Create sharp black images with resolution and sharpness
Photosensitive heat for medical diagnostic and photographic technology applications
There is a need for techniques relating to developed photographic materials. these
For photosensitive photothermographic materials, use of solution processing chemicals
Easier heat development processing system that does not damage the environment
System can be supplied to customers. Similar demands are made in the field of general image forming materials.
However, medical images are sharp because they require fine depiction.
In addition to high image quality and excellent granularity, diagnosis is required.
From the viewpoint of easiness, a cool black image is preferred. Present
Inkjet printers, electrophotographic pigments and dyes
Various image-forming hard copy systems
Although it is distributed as a system, it is a medical image output system.
There is no satisfactory system. On the other hand, a thermal image forming system using an organic silver salt
For example, U.S. Pat. Nos. 3,152,904 and 345.
7075 and B.B. According to Shely
"Thermal Processed Silver System (Thermally Proce
ssed Silver Systems) ”(Imaging Process
Imaging Processes and Mat
erials) Neblette 8th edition, Sturge, V. Wow
Edited by Walworth, A. Shepp, 2nd
Page 1996). Especially photothermographic
The material is generally a catalytically active amount of photocatalyst (eg, halogenated).
Silver), reducing agent, reducible silver salt (eg, organic silver salt), required
To control the color tone of the silver
It has a photosensitive layer dispersed in the lix. Thermal development feeling
Optical materials are exposed to high temperatures (eg, 80 ° C or higher) after image exposure.
Heated, silver halide or reducible silver salt (with oxidizing agent and
The redox reaction between the reducing agent and
A black silver image is formed. Redox reaction occurs upon exposure
Accelerated by the catalytic action of the latent image of the silver halide.
Therefore, a black silver image is formed in the exposure area. Rice
Many, including national patent No. 2910377 and Japanese Patent Publication No. 43-4924
And for medical use by photothermographic material
Fuji Medical Dry Image as an image forming system
FM-DPL was released. Reducing agents, toning agents or
As a method for introducing an additive such as an antifoggant,
There are various methods such as liquids, emulsions, and solid dispersions.
Reproducible and stable in the manufacturing process
It is required to be. Especially emulsions and solid dispersions
In the case of dispersion of dispersion time due to foam mixing during production,
Instability of repeatability such as dispersion of diameter distribution
Increased filtration pressure, filter clogging, and aggregation over time
When there is a problem of concentration abnormalities due to collection, creaming, etc.
There is. In response to such a problem, the coarse dispersion is aged.
However, depending on the state of the compound and the coarse dispersion,
Can take more than 24 hours, so increase the manufacturing time
It is just a thing. Therefore, sufficient manufacturing stability
There is a need to provide a solid dispersion etc. having
The [0006] Accordingly, it is an object of the present invention.
By defoaming before dispersion,
Stable manufacturing process that prevents creaming due to air contamination
And a method for producing a dispersion with reduced production time
Is to provide. In addition, manufactured in this way
Improved dispersion of the coated surface
An object of the present invention is to provide an image-sensitive material and a manufacturing method thereof. [0007] The object of the present invention is to:
Achieved by means. (1) Photosensitive halogenate on at least one side of the support
Silver halide, non-photosensitive organic silver salt, reducing agent and binder
And at least one of the constituent layers has a solid organic compound.
In a method for producing a photothermographic material containing a body dispersion
The defoaming step is performed at the time of pre-dispersion before the solid dispersion is dispersed.
Production of photothermographic material characterized by being manufactured through
Method. (2) A method for dispersing a solid dispersion of the organic compound is a method.
The thermal current according to (1), characterized in that it is a deer dispersion method
A method for producing an image-sensitive material. (3) The defoaming step includes centrifugal defoaming, vacuum defoaming, and heat treatment.
It is at least one of the physical defoaming methods
(1) The method for producing a photothermographic material according to (2). (4) The organic compound is a photographically useful compound
Thermal development feeling as described in (1), (2) or (3)
Manufacturing method of optical material. (5) The photographically useful compound is a reducing agent, a development accelerator, water
Either an element binding compound, an antifoggant or a colorant
(4) The photothermographic material according to (4)
Method. (6) The photographically useful compound is a polyhalogen compound, bi
Sphenol compound or the bisphenol compound and water
Any of the hydrogen-bonding compounds that can be bonded together.
Production of photothermographic material of (4) or (5) characterized
Method. (7) The binder is an aqueous latex and has
The silver salt content layer is coated with an aqueous coating solution.
(1), (2), (3), (4), (5) or
(6) The method for producing a photothermographic material according to (6). (8) This is manufactured in any one of (1) to (7)
The heat present according to any one of (1) to (7),
Image sensitive material. [0008] BEST MODE FOR CARRYING OUT THE INVENTION The production of the solid dispersion of the present invention will be described below.
Details of manufacturing method, solid dispersion, and photothermographic material
Explain in detail. As a method for producing the solid dispersion of the present invention,
Media-type disperser that grinds with media, large shear
High-speed stirring disperser with high strength, high-intensity ultrasonic energy
For example, a ball mill,
Lloyd mill, sand mill, homogenizer, capillary milk
Device, liquid siren, electrostrictive ultrasonic generator, pole
An emulsifying device with a man whistle can be mentioned.
It is preferable to use a disperser, and an aqueous media disperser
More preferably, it is used. As a method of media distribution, there is a dispersive compounding.
The mixture of the product and dispersant solution is sent to the disperser as a preliminary dispersion.
It is common practice to do so, but prior to distributed operations
Water called dispersoid powder or wet cake
Organic compounds moistened with organic solvents can be pre-treated with dispersant solutions and solvents.
Disperse. Well-known means (e.g., pre-dispersion means)
For example, mixing with propeller blades or anchor blades,
High-speed mixer, homogenizer, high-speed impact mill, bamba
(Rea mixer, homo mixer, kneader, etc.)
be able to. In addition to mechanical dispersion,
Fine particles may be obtained by changing the pH in the presence of an auxiliary agent.
At this time, an organic solvent is used as a solvent for coarse dispersion.
Ordinarily, the organic solvent is removed after the formation of the fine particles.
In the present invention, a dispersoid is gradually added to a dispersion medium solution to prepare a process.
Preference is given to the method of mixing with a blade or anchor blade.
Good. In the present invention, the preliminary dispersion is added to
The defoaming step is performed before dispersing with the known pulverizer (disperser)
Do. The method of the defoaming step is a centrifugal defoaming method (for example,
Drop the liquid mixed with bubbles on the rotating disk to form a thin film.
The ratio of liquid to foam (air) using a centrifuge
Method of removing bubbles using the difference in weight), vacuum defoaming method (Tato
For example, vacuum continuous removal made by Colma / Unosawagumi Co., Ltd.
Ki device, Matsubara Ebara de Amil, Ashiza
Wafer bubble buster), heat treatment defoaming method (for example, foam
Method of removing bubbles by heating mixed liquid), ultrasonic defoaming
Method (for example, ultrasonic vacuum defoaming by Ginsen Co., Ltd.)
), Other methods (eg, OPUS system)
Swirl flow type bubble removing device manufactured by Yokota Manufacturing Co., Ltd.
There are various methods such as defoaming pump), but centrifugal defoaming method, depressurization
Defoaming method and heat treatment defoaming method are preferable, heat treatment defoaming method, reduced pressure
The defoaming method is most preferred. Also, combine the above defoaming method
In that case, especially in the heat treatment defoaming method,
A combination of vacuum degassing methods is preferred. Pre-dispersion by providing a defoaming step
Remove the air in the liquid, cream the dispersion,
Delays, filtration, and other problems can be eliminated, ensuring manufacturing stability.
In addition to being maintained, the physical properties such as product quality and viscosity
Qualitative improvement is also achieved, leading to the prevention of troubles during the production of photosensitive materials. The temperature processed in the heat treatment defoaming method is as follows:
Thermal stability of the dispersed compound,
It depends on the size, shape, dispersion concentration and composition.
Although it cannot be generally said, it is preferably 10 ° C or higher and 90 ° C or lower.
Or 20 ° C to 80 ° C, more preferably 30 ° C to 70 ° C.
It is below ℃. In addition, in the heat treatment defoaming method,
Time to be dispersed, the thermal stability of the compound to be dispersed,
Depending on the size and shape of the compound powder, the concentration and composition of the dispersion
Because it is different, I can not say unconditionally, but in 10 minutes to 48 hours
Yes, preferably 30 minutes or more and 12 hours or less, more preferably
It is preferably 1 hour or more and 6 hours or less. In the heat treatment defoaming method, what has been defoamed
Judgment can be made by visual observation and specific gravity measurement of the preliminary dispersion.
The That is, visual observation means visual observation of the preliminary dispersion.
However, the pre-dispersed liquid is creamy and has little fluidity
If so, it is assumed that bubbles are mixed, and the preliminary dispersion is smooth.
If the liquid is fluid, it can be said that bubbles are not necessary. Ma
The specific gravity measurement of the preliminary dispersion is a constant volume (for example, 10
0ml), and the mass divided by the volume
Is the specific gravity of the preliminary dispersion and the dispersion medium (dispersion)
Smaller than the specific gravity of the agent solution)
If it is larger than the dispersion medium (specific gravity of the dispersant solution)
Suppose that The preliminary dispersion thus prepared is publicly known.
Crushers such as ball mills, colloid mills, jets
Mill, roller mill, tron mill, high speed stone mill,
Vibration ball mill, vertical sand mill, pin mill, coball
Mill, caddy mill, vertical sand mill, horizontal sand mill
Or an attritor
Teal balls, ceramic balls, glass beads, al
Mina beads, zirconia silicate beads, zirconia
By mechanical force in the presence of beads, Ottawa sand, etc.)
A method of pulverizing and dispersing is mentioned. Of these,
Roll mill, colloid mill, vertical sand mill, horizontal sand mill
It is preferable to use a mill, vertical sand mill, horizontal type
More preferred. There are various types of vertical sand mills.
For example, Sand Grinder Mill (SGM;
Cus Co., Ltd.), Vertical Mighty Mill (Inoue Seisakusho)
Manufactured by Co., Ltd.), Pearl Mill STS (manufactured by Ajisawa Co., Ltd.), etc.
Can be given. Of these, sand grinder mill
(SGM; manufactured by Imex Corporation) is preferable. Horizontal sun
There are various types of domills.
Viscomill (UVM; manufactured by Imex Co., Ltd.), Agitate
Tamil LMK (manufactured by Ajisawa), Dynomill (Shinma)
Le Enterprise Co., Ltd.). this
Among them, Ultra Viscomill (UVM; Imex Co., Ltd.)
Product). Steel as the dispersion medium (beads)
Ball, ceramic ball, glass bead, alumina bead
, Zirconia silicate beads, zirconia beads
, Ottawa Sand, etc.
, Alumina beads, zirconia silicate beads, di
Luconia beads are preferred, zirconia silicate bees
More preferred are zirconia beads. Distributed media
There are various sizes, but the average diameter
0.3 mm to 5 mm is preferable, and more preferably 0.3 mm
mm to 3 mm, and even more preferably 0.3 mm
~ 2mm. Of these, most preferably used
Those are 0.3mm, 0.5mm, 1.0mm or
2.0 mm beads. These distributed media are simply
You can use it alone, or mix and match types and sizes
Also good. In this case, mix different sized beads of the same species.
It is preferable to combine them in terms of improving the dispersion efficiency. mixture
When using as a mixture, the mixing ratio can be set arbitrarily.
You can. In the above dispersers, the above zirconia-based bee
Elution from these beads when dispersed using
Zirconia and the like may be mixed in the dispersion. Min
Although it depends on the dispersion conditions, it is usually in the range of 1 ppm to 1000 ppm.
If the Zr content in the photosensitive material is 0.5 mg or less per gram of silver
If practical, there is no problem. In the method for producing a solid dispersion of the present invention,
For example, if the preliminary dispersion prepared in the stock tank was used
For example, let it pass through the horizontal sand mill and vertical sand mill.
Transfer to another stock tank. This is called a path.
The defoaming treatment in the method for producing a solid dispersion according to the present invention comprises
It is preferable to carry out in the state of the preliminary dispersion before being dispersed with a dispersing machine.
However, during the pass, that is, with one stock tank
You may perform a defoaming process continuously between a disperser. Transfer
The dispersed liquid is again passed through this disperser, and the target
Repeat this operation several times (several passes) until the diameter is reached
To create a target dispersion (pass method). Also predict
After passing the prepared dispersion through one pass, add the dispersion to the original tank.
Return and pass the dispersion liquid to the disperser in one tank
You may disperse | distribute by the method (one tank system). In addition, a stock tank is used as described above.
First, pre-dispersion is performed directly in the dispersion mill, and the main dispersion continues.
And distribute until the target median diameter is reached.
It is also possible to create a dispersion by dispersing in a batch method. The present invention
In the method, a pass method or a one-tank method is preferable. In the method for producing a solid dispersion of the present invention,
Distributing means the target media from the first pass after preliminary distribution
This is the process of dispersion up to the final pass.
During this dispersion process, Japanese Patent Application Laid-Open No. 2000-55405, Japanese Patent Application 2001-38310
The heat treatment described in 8 may be performed. The solid dispersion prepared by the method of the present invention is:
Store with stirring to prevent sedimentation of particles during storage
Or more viscous due to hydrophilic colloids (for example,
Stored in gelatin in a jelly-like state)
Can. In addition, the solid dispersion of the present invention is
Keep at room temperature for storage or transport until use
It can also be placed in a light room or in a dark room
However, if necessary, store in a dark room in the refrigerator until use after production.
May be. In addition, refrigeration means 1 ℃-20 ℃, room temperature
Means that the temperature is not regulated and that
Say. The process for producing the solid dispersion of the present invention and the process of the present invention
In the solid dispersion, the dispersed organic acid silver, halo
Organic compounds excluding silver halide, especially useful for photography
It is a compound. Here, photographic useful compounds are photographic performance.
(For example, sensitivity, fog, gradation, color tone, density, etc.)
A compound that can be controlled arbitrarily by the amount of addition, etc.
For example, dye image forming coupler, dye image donating redox
Compound, stain inhibitor, antifoggant, UV absorber,
Anti-fading agent, anti-color mixing agent, nucleating agent, silver halide solvent,
Bleach accelerator, developer, oxidizing agent, reducing agent, filter color
Elements and their precursors, dyes, pigments, sensitizers, dura
Agent, whitening agent, desensitizer, antistatic agent, antioxidant, developer
Scavenger, mordant, matting agent, development accelerator, development
Inhibitors, hydrogen bonding compounds, thermal solvents, color modifiers, etc.
Say. The photographically useful compound of the present invention satisfies the above definition.
As long as it is not particularly limited, the reducing agent and development promotion described below.
Using accelerators, hydrogen bonding compounds, antifoggants, and colorants
A reducing agent (bisphenol compound),
Antifogging agent (polyhalogen compound) or bisphenol
Uses hydrogen-bonding compounds that can form hydrogen bonds with nor compounds
More preferably. Usually, for water-based solid dispersions, water or dispersion
It is preferable to use an insoluble compound in the agent solution.
The physical stability of the present invention is often obtained.
The method dissolves to some extent in water or dispersant solution
A compound may be used. In this case, its solubility range
Depends on the type and amount of dispersant and dispersion aid used.
Since it is different, it cannot be generally stated, but the dispersant dissolves at 25 ° C.
What dissolves 0.01mg or more in 100g of liquid is good, preferably
0.01mg-100mg dissolved in 100g dispersant solution at 25 ° C
More preferably dispersed at 25 ° C.
25 mg to 50 mg dissolved in 100 g of the agent solution, 25
Dissolve 1 mg to 10 mg in 100 g of dispersant solution at ℃
Is most preferred. Method for measuring solubility of photographically useful compounds
Use HPLC method, absorbance method, mass
There are various methods such as the above-mentioned methods. HPLC method
Is a pre-dispersion of useful photographic compounds at 25 ° C for more than 16 hours
Remove the sample after aging with the supernatant in an ultracentrifuge at 25 ° C.
Useful for photographs that have been separated into precipitates and dissolved in the supernatant by HPLC
A method for quantifying a compound. Method using absorbance and
The photograph is dissolved by measuring the absorbance of the supernatant.
Is a method for quantifying chemical compounds, and is a method using mass
Measured dry solid content of the above supernatant and dissolved
This is a method for quantitatively determining the compound for use. In the present invention, HPLC is used.
The most popular method is to measure the solubility of photographic useful compounds.
Is also preferable. The dispersion medium of the solid dispersion used in the present invention and
Water or organic solvents (methanol, ethanol,
Isopropanol, methyl cersolob, ethyl cellosol
Dimethylformamide, ethyl acetate, etc.)
Examples thereof include a mixture thereof. In the present invention, 30% by mass or less
Water containing the following organic solvents or water containing no organic solvents
It is preferable to contain 10% by mass or less of an organic solvent.
Water that does not contain any organic or organic solvents.
In addition, water or an organic solvent containing 1% by mass or less of an organic solvent
Most preferred is water that does not contain any water. For media dispersion, a surfactant may be used.
Good. Surfactants include nonionic, ionic (a)
Any of (Nion, Cation, Betaine) can be used.
Nonionic surfactants include polyoxyethylene,
Polyoxypropylene, polyoxybutylene, polyglycol
Surface activity with nonionic hydrophilic group of sidyl or sorbitan
Mention may be made of sex agents. Specifically, polyoxye
Tylene alkyl ether, polyoxyethylene alkyl
Phenyl ether, polyoxyethylene-polyoxy
Propylene glycol, polyhydric alcohol fatty acid partial es
Tellurium, polyoxyethylene polyhydric alcohol fatty acid partial ester
Steal, polyoxyethylene fatty acid ester, polyglyceride
Serine fatty acid ester, fatty acid diethanolamide,
Mentioning reethanolamine fatty acid partial esters
it can. As anionic surfactants, carvone
Examples of acid salts, sulfate salts, sulfonate salts, and phosphate ester salts
Typical examples include fatty acid salts, alkyls
Rubenzene sulfonate, alkyl naphthalene sulfone
Acid salt, alkyl sulfonate, α-olefin sulfone
Acid salt, dialkylsulfosuccinate, α-sulfonated fat
Fatty acid salt, N-methyl-N-oleyl taurine, petroleum sulfate
Honates, alkyl sulfates, sulfated fats and oils, polyoxye
Tylene alkyl ether sulfate, polyoxyethylene
Rukiruphenyl ether sulfate, polyoxyethylene
Styrenated phenyl ether sulfate, alkyl phosphoric acid
Salt, polyoxyethylene alkyl ether phosphate, sodium
Phthalene sulfonate formaldehyde condensate
I can make it. As the cationic surfactant, an amine salt,
Examples include quaternary ammonium salts and pyridium salts.
1st to 3rd fatty amine salt, quaternary ammonium salt
(Tetraalkylammonium salts, trialkylbenzines
Ruammonium salt, alkylpyridium salt, alkyli
And midazolium salts). Betaine
Carboxybetaine, sulfobeta as surfactants
And N-trialkyl-N-
Carboxymethylammonium betaine, N-trial
Kill-N-sulfoalkylene ammonium betaine, etc.
Can be mentioned. These surfactants are “interfaces”
Application of activators "(Sachishobo, Kario Takao, September 1980)
Issued on the 1st). Preferred in the present invention
An anionic surfactant having a sulfonic acid group. Specific examples of the surfactant will be described below.
Surfactants that can be used in light are limited to these
(Where -C₆H_Four-Is a phenylene group
Represents). WA-1: Sodium dodecylbenzenesulfonate WA-2: Tri (isopropyl) naphthalene sulfone
Acid sodium WA-3: Tri (isobutyl) naphthalenesulfonic acid
sodium WA-4: Sodium dodecyl sulfate WA-5: α-sulfa succinic acid di (2-ethylhexyl)
Sil) ester sodium salt WA-6: C₈H₁₇-C₆H_Four-(CH₂CH₂O)_Three(CH₂)₂SO_ThreeK WA-7: Cetyltrimethylammonium chloride
Do WA-8: C₁₁H_{twenty three}CONHCH₂CH₂N⁺ (CH_Three)₂-CH₂COO^- WA-9: sodium dodecyl diphenyl ether disulfonate
thorium In the dispersion operation, an aqueous solvent-soluble dispersant (retaining agent)
It is preferable to disperse the dispersoid in the presence of the protective colloid)
Yes. As the dispersant, hydrophilic colloid can be used.
Yes. For example, poly-N-vinylpyrrolidone, polyacyl
Rilic acid, polymethacrylic acid, polyacrylamide, poly
Vinyl imidazole, maleic acid copolymer, maleic acid
Monoester copolymer, acrylomethylpropane sulfone
Acid copolymer, polyvinylpyrazole, polyethylene glycol
Single or recall, polypropylene glycol, etc
Is a variety of synthetic hydrophilic polymer materials such as copolymers, carbo
Xymethyl starch, carboxymethyl cellulose, etc.
Semi-synthetic anionic polymers such as alginic acid and pectic acid
Which anionic polymer is disclosed in JP-A-7-350753
Compounds, gelatin derivatives, gelatin and other
Such as graft polymers with molecules, albumin, casein, etc.
Protein, hydroxyethyl cellulose, carboxymethyl
Cells such as cellulose and cellulose sulfates
Sugars such as loin derivatives, sodium alginate, starch derivatives
Derivatives, polyvinyl alcohol, polyvinyl alcohol
Polyvinyl alcohols such as partial acetals, or
Appropriately use naturally occurring polymer compounds such as gelatin
It can be selected and used. These dispersants alone
You may use it, or 2 or more types may be mixed and used. Of these dispersants, the present invention employs polyester.
Tylene glycol, polypropylene glycol, polyvinyl chloride
Nyl alcohols, water-soluble cellulose derivatives are used
Of these, polyvinyl alcohols are particularly preferred.
Good. As polyvinyl alcohol (PVA)
Can include the following compounds. With complete saponification
PVA-105 [polyvinyl alcohol (PV
A) Content ratio 94.0% by mass or more, degree of saponification 98.5 ±
0.5 mol%, sodium acetate content 1.5 mass% or less
Lower, volatile matter 5.0 mass% or less, viscosity (4 mass%, 20
° C) 5.6 ± 0.4 Pas], PVA-110 [PVA
Content 94.0% by mass, saponification degree 98.5 ± 0.5 mol
%, Sodium acetate content 1.5% by mass, volatile matter 5.0
Mass%, viscosity (4 mass%, 20 ° C.) 11.0 ± 0.8 Pa
  s], PVA-117 [PVA content 94.0 mass
%, Degree of saponification 98.5 ± 0.5 mol%, sodium acetate
Content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 quality)
%, 20 ° C.) 28.0 ± 3.0 Pa s], PVA-1
17H [PVA content 93.5% by mass, saponification degree 99.
6 ± 0.3 mol%, sodium acetate content 1.85 mass
%, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 2
9.0 ± 3.0 Pa s], PVA-120 [PVA contained
The rate is 94.0% by mass, the degree of saponification is 98.5 ± 0.5 mol%,
Sodium acetate content 1.0 mass%, volatile matter 5.0 mass
%, Viscosity (4% by mass, 20 ° C.) 39.5 ± 4.5 Pa
s], PVA-124 [PVA content 94.0% by mass,
Saponification degree 98.5 ± 0.5 mol%, containing sodium acetate
1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass
%, 20 ° C.) 60.0 ± 6.0 Pas], PVA-12
4H [PVA content 93.5% by mass, saponification degree 99.6
± 0.3 mol%, sodium acetate content 1.85 mass
%, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 6
1.0 ± 6.0 Pas], PVA-CS [PVA content
94.0 mass%, degree of saponification 97.5 ± 0.5 mol%, vinegar
Sodium acid content 1.0 mass%, volatile matter 5.0 mass
%, Viscosity (4 mass%, 20 ° C.) 27.5 ± 3.0 Pa
s], PVA-CST [PVA content 94.0% by mass,
Degree of saponification 96.0 ± 0.5 mol%, containing sodium acetate
1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass
%, 20 ° C.) 27.0 ± 3.0 Pas], PVA-HC
[PVA content 90.0 mass%, saponification degree 99.85
% Or more, sodium acetate content 2.5% by mass, volatile content
8.5% by mass, viscosity (4% by mass, 20 ° C.) 25.0 ±
3.5 Pa s] (All of the above are products made by Kuraray Co., Ltd.
Name). Partially saponified products include PVA-203.
[PVA content 94.0% by mass, saponification degree 88.0 ±
1.5 mol%, sodium acetate content 1.0% by mass, volatilization
5.0% by mass, viscosity (4% by mass, 20 ° C.) 3.4 ±
0.2 Pas], PVA-204 [PVA content 9
4.0 mass%, degree of saponification 88.0 ± 1.5 mol%, acetic acid
Sodium content 1.0% by mass, volatile matter 5.0% by mass,
Viscosity (4 mass%, 20 ° C.) 3.9 ± 0.3 Pa s],
PVA-205 [PVA content 94.0% by mass, saponification
Degree 88.0 ± 1.5 mol%, sodium acetate content 1.
0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20%
° C) 5.0 ± 0.4 Pas], PVA-210 [PV
A content 94.0% by mass, saponification degree 88.0 ± 1.0
%, Sodium acetate content 1.0 mass%, volatile content 5.
0% by mass, viscosity (4% by mass, 20 ° C.) 9.0 ± 1.0 P
a]], PVA-217 [PVA content 94.0 mass
%, Degree of saponification 88.0 ± 1.0 mol%, sodium acetate
Content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 quality)
%, 20 ° C.) 22.5 ± 2.0 Pas], PVA-
220 [PVA content 94.0% by mass, saponification degree 88.
0 ± 1.0 mol%, sodium acetate content 1.0 mass
%, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 3
0.0 ± 3.0 Pas], PVA-224 [including PVA]
Proportion 94.0% by mass, degree of saponification 88.0 ± 1.5 mol
%, Sodium acetate content 1.0% by mass, volatile matter 5.0
Mass%, viscosity (4 mass%, 20 ° C.) 44.0 ± 4.0 P
as], PVA-228 [PVA content 94.0 mass
%, Degree of saponification 88.0 ± 1.5 mol%, sodium acetate
Content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 quality)
%, 20 ° C.) 65.0 ± 5.0 Pa s], PVA-
235 [PVA content 94.0% by mass, saponification degree 88.
0 ± 1.5 mol%, sodium acetate content 1.0 mass
%, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 9
5.0 ± 15.0 Pa s], PVA-217EE [P
VA content 94.0% by mass, degree of saponification 88.0 ± 1.0
Mol%, sodium acetate content 1.0% by mass, volatile matter
5.0% by mass, viscosity (4% by mass, 20 ° C.) 23.0 ±
3.0 Pas], PVA-217E [PVA content 9
4.0 mass%, degree of saponification 88.0 ± 1.0 mol%, acetic acid
Sodium content 1.0% by mass, volatile matter 5.0% by mass,
Viscosity (4% by mass, 20 ° C.) 23.0 ± 3.0 Pa
s], PVA-220E [PVA content 94.0 mass
%, Degree of saponification 88.0 ± 1.0 mol%, sodium acetate
Content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 quality)
%, 20 ° C.) 31.0 ± 4.0 Pas], PVA-
224E [PVA content 94.0% by mass, saponification degree 8
8.0 ± 1.0 mol%, sodium acetate content 1.0 quality
% By volume, volatile matter 5.0% by weight, viscosity (4% by weight, 20 ° C.)
45.0 ± 5.0 Pas], PVA-403 [PVA
Content 94.0% by mass, degree of saponification 80.0 ± 1.5 mol
%, Sodium acetate content 1.0% by mass, volatile matter 5.0
Mass%, viscosity (4 mass%, 20 ° C.) 3.1 ± 0.3 Pa
  s], PVA-405 [PVA content 94.0 mass
%, Degree of saponification 81.5 ± 1.5 mol%, sodium acetate
Content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 quality)
%, 20 ° C.) 4.8 ± 0.4 Pa s], PVA-4
20 [PVA content 94.0% by mass, saponification degree 79.5
± 1.5 mol%, sodium acetate content 1.0 mass%,
Volatile matter 5.0 mass%], PVA-613 [PVA content
94.0 mass%, degree of saponification 93.5 ± 1.0 mol%, vinegar
Sodium acid content 1.0 mass%, volatile matter 5.0 mass
%, Viscosity (4 mass%, 20 ° C.) 16.5 ± 2.0 Pa
s], L-8 [PVA content 96.0 mass%, saponification degree
71.0 ± 1.5 mol%, sodium acetate content 1.0
Mass% (ash content), volatile content 3.0 mass%, viscosity (4 mass
%, 20 ° C.) 5.4 ± 0.4 Pas] (all above
Kuraray Co., Ltd. product name). Note that the above measurement
The constant value was obtained according to JISK-6726-1977.
It is. For modified polyvinyl alcohol, see “Polypropyl alcohol”.
"Bar", published by Koichi Nagano et al.
Is used. Cation, anion, -SH compound, a
There is modification with rualkylthio compounds and silanols. this
As such modified polyvinyl alcohol (modified PVA)
Are C-118, C-318, C-3 as C polymers
18-2A, C-506 (all of which are Kuraray Co., Ltd.)
Product name), HL-12E as HL polymer, HL
-1203 (all of the above are manufactured by Kuraray Co., Ltd.)
Name), HM-03, HM-N-03 as HM polymer
(All of the above are trade names made by Kuraray Co., Ltd.), K polymer
-KL-118, KL-318, KL-506,
KM-118T, KM-618 (all of which are Kuraray
Product name), M-115 (M
MP-1 as an MP polymer.
02, MP-202, MP-203 (all
R-113, trade name), R-113 as R polymer
0, R-2105, R-2130 (all
V-2250 as V polymer
(Trade name made by Kuraray Co., Ltd.). Of these polyvinyl alcohols, parts
Saponified polyvinyl alcohol, K polymer, MP poly
Are preferred, and MP polymers are particularly preferred. these
It is preferable to use a dispersant in combination with the surfactant.
Yes. For example, Sodium dodecylbenzenesulfonate / PVA-203 Sodium dodecylbenzenesulfonate / PVA-205 Sodium dodecylbenzenesulfonate / PVA-217 Sodium dodecylbenzenesulfonate / MP-203 Sodium dodecylbenzenesulfonate / KM-618 Sodium tri (isopropyl) naphthalenesulfonate
/ PVA-203 Sodium tri (isopropyl) naphthalenesulfonate
/ PVA-205 Sodium tri (isopropyl) naphthalenesulfonate
/ PVA-217 Sodium tri (isopropyl) naphthalenesulfonate
/ MP-203 Sodium tri (isopropyl) naphthalenesulfonate
/ MP-103 And out of these Sodium dodecylbenzenesulfonate / PVA-205 Sodium tri (isopropyl) naphthalenesulfonate
/ PVA-217 Sodium tri (isopropyl) naphthalenesulfonate
/ MP-203 Is particularly preferred. In the process for producing the solid dispersion of the present invention,
Further heating after dispersion of media described in Japanese Patent Application No. 2000-240658
May be processed. The aqueous solid dispersion of the present invention contains a dispersion or
An antifoaming agent may be added for the purpose of facilitating handling.
Defoamers include higher alcohols, fatty acid esters, phosphorus
Acid ester, polypropylene glycol, silicone oil
Emulsions are often used. These antifoam tools
Examples include Pionein (Takemoto Oil), Nissan D
Shome (Japanese fats and oils), NUC silicone (Nippon Unica)
-), Shin-Etsu Chemical KM series (Shin-Etsu Chemical), Pluronic
Series (Pluronic), surfynol series (Air
Products). Also methanol or ethanol
A small amount of organic solvent such as may be used. These compounds
Are readily available as commercial products.
Of these, Pluronic series, surfynol series,
Methanol is preferred, and surfynol104E is more preferred
Yes. The amount of antifoam added was 1 kg of the dispersion.
0.1g to 10g, preferably 0.5g
5g, and more preferably 0.5g to 3g
is there. The solid dispersion of the organic compound of the present invention contains
Add preservatives to prevent the growth of various germs
It is preferable. Specific examples of the preservative include the following general formula (I
There are compounds represented by I), (III), or (IV). Ahead
First, the compound represented by formula (II) will be described. [0043] [Chemical 1] Where R¹², R¹³Are each independently a hydrogen atom,
Alkyl group, aryl group, cyano group, heterocyclic group, alkyl
A ruthio group, an arylthio group, an alkylsulfoxy group or
Represents an alkylsulfonyl group, R¹²And R¹³Are connected to each other
Thus, an aromatic ring may be formed. R¹¹Is a hydrogen atom, an alkyl
Group, alkenyl group, aralkyl group, aryl group, complex
Ring group or [0045] [Chemical 2] (Wherein R¹⁴And R¹⁵Are water independently
Represents an elementary atom, an alkyl group, an aryl group or an aralkyl group
The ). The compound represented by the general formula (II) is HC
l, bonded with salt such as NaCl, ammonium chloride
It may be a monium salt. Representative represented by general formula (II)
Specific compounds are shown below, but are not limited to these.
There is no. [0047] [Chemical Formula 3] [0048] [Formula 4]Next, the compound represented by the general formula (III)
explain about. [0050] [Chemical formula 5] Where R¹⁶Is a hydrogen atom or lower alkyl
Represents a group. R¹⁷Is a hydrogen atom, a lower alkyl group, or a hydride
Represents a loxymethyl group. Representative represented by general formula (III)
Specific compounds are shown below, but are not limited to these.
There is no. [0052] [Chemical 6] Next, the compounds represented by the general formula (IV)
I will explain. [0054] [Chemical 7] Where R¹⁸, R¹⁹And R²⁰Are independent
A hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxylic acid or
Its ester, halogen atom, lower acyl group or allyl
Represents a group, which may be the same or different. General formula
Representative compounds represented by (IV) are shown below.
It is not limited to that. [0056] [Chemical 8] All of these compounds are commercially available.
It can be easily obtained. As addition amount of preservative,
0.1 to 5000 mg per kg of dispersion
Preferably from 1 mg to 1000 mg, and
Preferably it is 10 mg to 200 mg. These
Of the compounds, benzoisothiazolinone sodium salt is preferred.
Good. Next, thermal development containing the solid dispersion of the present invention
The photosensitive material will be described. Such a photothermographic material
A photosensitive halo on at least one side of the support.
Silver halide, non-photosensitive organic silver salt, reducing agent and binder
And at least one of the constituent layers contains an organic compound.
A photothermographic material containing a solid dispersion is used. (Explanation of organic silver salt)
The non-photosensitive organic silver salt that can be produced is relatively stable to light.
Existence of exposed photosensitive silver halide and reducing agent
Silver ions when heated to 80 ° C or higher
Silver salt that functions as a supplier and forms a silver image.
The Organic silver salts provide silver ions that can be reduced by a reducing agent.
It can be any organic substance that can be supplied. Such insensitivity
For the light-sensitive organic silver salt, paragraph number of JP-A-10-62899
Nos. 0048 to 0049, European Patent Publication No. 0803684A1
Page 18, line 24 to page 19, line 37, European special
No. 0962812A1, JP 11-349591, JP 2000-7
683, 2000-72711, etc. Organic acid
Silver salts, especially (with a carbon number of 10-30, preferably 15-28)
A silver salt of a chain aliphatic carboxylic acid is preferred. Preferred fatty acid silver salt
Examples include lignoceric acid, silver behenate, ara
Silver quinate, silver stearate, silver oleate, laurin
Silver acid, silver caproate, silver myristate, palmitic acid
Including silver, erucic acid and mixtures thereof. The present invention
Contains silver behenate, among these fatty acid silver
The rate is preferably 50 mol% or more, more preferably 85 mol%.
% Of fatty acid silver, more preferably 95 mol% or more of fatty acid silver
Is preferably used. Forms of organic silver salts that can be used in the present invention
There are no particular restrictions on the shape, such as needles, rods, plates, phosphorus
Any one piece may be sufficient. In the present invention, scaly organic
Silver salts are preferred. Also, the ratio of the length of the long axis to the single axis is 5 or less
Short needle, rectangular parallelepiped, cube or potato-like irregular shape
Particles are also preferably used. These organic silver particles have a long axis
And heat development compared to long needle-like particles with a uniaxial length ratio of 5 or more
It has the feature that there is little fogging of time. Especially long
Particles with a shaft to uniaxial ratio of 3 or less have a mechanical stability of the coating film
Improved and preferable. In the present specification, scaly organic silver
The salt is defined as follows. Electron microscopy of organic acid silver salt
Observe with a micro-mirror and approximate the shape of organic acid silver salt particles to a rectangular parallelepiped
The sides of this cuboid are a, b, c from the shortest side.
(C may be the same as b.)
Calculation is performed using the values a and b, and x is obtained as follows. x = b / a In this way, about 200 particles
x is calculated and the average value x (average) is obtained.
The one satisfying the relation of (average) ≧ 1.5 shall be scaly. Like
Or 30 ≧ x (average) ≧ 1.5, more preferably 20 ≧ x
(Average) ≧ 2.0. By the way, needle shape is 1 ≦ x (average)
<1.5. In flake shaped particles, a is b and c are sides.
The thickness of the tabular grain with the surface to be
Yes. The average of a is preferably 0.01μ or more and 0.23μm, preferably 0.1μ
m to 0.20 μm is more preferable. c / b average is good
Preferably from 1 to 6, more preferably from 1.05 to 4
Below, more preferably 1.1 or more and 3 or less, particularly preferably
1.1 or more and 2 or less. The particle size distribution of the organic silver salt is monodispersed.
It is preferable. Monodispersion is the length of the short axis and long axis
100 percent of the standard deviation of the value divided by the short axis and long axis
Is preferably 100% or less, more preferably 80% or less,
Preferably it is 50% or less. Measuring method of organic silver salt shape
Is obtained from a transmission electron microscope image of an organic silver salt dispersion.
Can. As another way to measure monodispersity,
There is a method to calculate the standard deviation of the volume weighted average diameter of organic silver salt.
Yes, a percentage of the value divided by the volume weighted average diameter (variation factor
Number) is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. An example of a measurement method
If the organic silver salt dispersed in the liquid is irradiated with laser light,
Obtaining autocorrelation function for fluctuation of scattered light over time
Particle size (volume weighted average diameter)
Can be obtained. Production of organic acid silver used in the present invention and
As the dispersion method, a known method or the like can be applied. Example
For example, the above-mentioned JP-A-10-62899, European Patent Publication No. 0803673A
1, European Patent Publication No. 0962812A1, JP-A-11-349591,
JP 2000-7683, 2000-72711, Japanese Patent Application No. 11-348228
No. 30, No. 11-203413, No. 2000-90093, No. 2000-1956
No. 21, 2000-191226, 2000-213813, 2000-214
155, 2000-191226 etc. can be referred to. It should be noted that when the organic silver salt is dispersed, the photosensitive silver salt is added.
When coexisting, fog increases and sensitivity decreases significantly.
Therefore, it may contain substantially no photosensitive silver salt during dispersion.
More preferred. In the present invention, in the aqueous dispersion to be dispersed
The amount of photosensitive silver salt is 1m per 1mol of organic acid silver salt in the solution.
It is preferably ol% or less, more preferably 0.1 mol%
The following is preferable, and more preferable is the active photosensitive silver salt.
No addition is performed. In the present invention, organic silver salt aqueous dispersion and photosensitivity are used.
Photosensitive materials can be manufactured by mixing silver salt water dispersions.
However, the mixing ratio of organic silver salt and photosensitive silver salt depends on the purpose.
The ratio of photosensitive silver salt to organic silver salt is 1
In the range of ~ 30 mol%, more preferably 2 to 20 mol%, especially 3 to
A range of 15 mol% is preferred. 2 or more organics when mixing
Mix silver salt water dispersion and two or more photosensitive silver salt water dispersions.
Is preferably used for adjustment of photographic properties
Is the method. The organic silver salt of the present invention can be used in a desired amount.
However, the total applied silver amount including silver halide is 0.1-5.0 g /
m²Is more preferable, more preferably 0.3 to 3.0 g / m²Even better
Preferably 0.5 ~ 2.0g / m²It is. In particular, improved image storage
In order to achieve this, the total amount of silver applied is 1.8 g / m²Less preferred
Or 1.6g / m²It is preferable that Preferred of the present invention
Even if such a low amount of silver is used,
It is possible to obtain a sufficient image density. (Description of Reducing Agent) Photothermographic material of the present invention
Contains a thermal developer which is a reducing agent for organic silver salts
Is preferred. Reducing agent for organic silver salt gold ion silver
Any substance (preferably an organic substance) that reduces to genus silver
It may be. Examples of such reducing agents are disclosed in JP-A-11-65021.
Paragraph numbers 0043 to 0045 and European Patent Publication No. 0803
764A1 page 7 line 34 to page 18 line 12
It is described in. In the present invention, the reducing agent is fluorinated.
So-called having a substituent at the ortho position of the enolic hydroxyl group
Hindered phenol reducing agent or bisphenol
A compound represented by the following general formula (R):
More preferred. Formula (R) [0069] [Chemical 9] (In the general formula (R), R¹ And R¹'
Each independently represents an alkyl group having 1 to 20 carbon atoms. R² Oh
And R²'Is independently substituted with a hydrogen atom or benzene ring
Represents a possible substituent. L is a -S- group or -CHR^Three-List groups
The R^Three Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
Represent. X¹And X¹Each independently represents a hydrogen atom or ben.
This represents a group that can be substituted on the zen ring. ) The general formula (R) will be described in detail. R
¹ And R¹'Is independently substituted or unsubstituted carbon number 1
~ 20 alkyl groups, and the substituents of the alkyl group are particularly limited.
Preferably, aryl group, hydride
Roxy group, alkoxy group, aryloxy group, alkyl
Thio group, arylthio group, acylamino group, sulfone
Mid group, sulfonyl group, phosphoryl group, acyl group, cal
Vamoyl group, ester group, ureido group, urethane group,
For example, a rogen atom. R² And R²'Is independently a hydrogen atom or
Is a substituent that can be substituted on the benzene ring, and X¹and
X¹'Can also be independently substituted with hydrogen atom or benzene ring
Represents a radical. As a group that can be substituted on the benzene ring,
Is preferably an alkyl group, an aryl group, or a halogen atom.
Child, alkoxy group, and acylamino group. L is a -S- group or -CHR.^Three -Group
The R^Three Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
And the alkyl group may have a substituent. R^Three
Specific examples of the unsubstituted alkyl group are methyl group, ethyl group,
Propyl, butyl, heptyl, undecyl,
Sopropyl group, 1-ethylpentyl group, 2,4,4-to
Examples thereof include a limethylpentyl group. Placement of alkyl group
An example of a substituent is R¹ And the same groups as those described above. R¹ And R¹Preferably as 3 carbon atoms
~ 15 secondary or tertiary alkyl groups, specifically
Are isopropyl, isobutyl, t-butyl, t-
Amyl group, t-octyl group, cyclohexyl group, cyclo
Pentyl group, 1-methylcyclohexyl group, 1-methyl
And cyclopropyl group. R¹ And R¹'When
And more preferably a tertiary alkyl group having 4 to 12 carbon atoms.
Among them, among them, t-butyl group, t-amyl group, 1-methyl
A rucyclohexyl group is more preferred, and a t-butyl group is most preferred.
Is also preferable. R² And R²Preferably as 1 carbon
~ 20 alkyl groups, specifically methyl group, ethyl
Group, propyl group, butyl group, isopropyl group, t-butyl
Group, t-amyl group, cyclohexyl group, 1-methyl
Chlohexyl group, benzyl group, methoxymethyl group, metho
Examples thereof include a xylethyl group. More preferably methyl
Group, ethyl group, propyl group, isopropyl group, t-butyl
Group. X¹ And X¹'Is preferably a hydrogen atom,
A halogen atom or an alkyl group, more preferably a hydrogen atom
It is. L is preferably -CHR.^Three-The group. R^Three
Preferably a hydrogen atom or an alkyl having 1 to 15 carbon atoms
It is a kill group, and as an alkyl group, a methyl group, ethyl
Group, propyl group, isopropyl group, 2,4,4-trime
A tilpentyl group is preferred. R¹³Particularly preferred as
Is a hydrogen atom, methyl group, ethyl group, propyl group or
Sopropyl group. R^Three R is a hydrogen atom, R² And R
²'Is preferably an alkyl group having 2 to 5 carbon atoms,
More preferred are ethyl group and propyl group.
That's right. R^Three Is a primary or secondary alkyl having 1 to 8 carbon atoms
R is a group² And R ²'Is preferably a methyl group.
R^Three A primary or secondary alkyl group having 1 to 8 carbon atoms
Methyl group, ethyl group, propyl group, isopropyl group
Is more preferred, and methyl, ethyl, and propyl groups are more
Is preferred. R¹ , R¹', R² And R²'
In the case of a til group, R^Three Is a secondary alkyl group
It is preferable. In this case R^Three As a secondary alkyl group
Is isopropyl, isobutyl, 1-ethylpentyl
Group is preferred, and isopropyl group is more preferred. Above
The base agent is R¹ , R¹', R² , R²'and^R3 Combination
Depending on the heat developability, developed silver tone, and the like. 2 or more types
These can be adjusted by combining reducing agents
Can be used in combination of two or more depending on the purpose.
It is preferable to use. The compounds represented by the general formula (R) of the present invention are as follows:
Although the specific example of the reducing agent of this invention including a compound is shown,
The present invention is not limited to these. [0079] Embedded image[0080] Embedded image[0081] Embedded imageIn the present invention, the reducing agent is added in an amount of 0.1 to 3.0.
g / m²And more preferably 0.2 to 1.5.
g / m²And more preferably 0.3 to 1.0 g / m²It is. Picture
5 to 50% mol is contained per 1 mol of silver on the surface having the image forming layer.
Preferably, it is 8 to 30 mol%.
More preferably, it is contained at 10 to 20 mol%. Return
The base agent is preferably contained in the image forming layer. The reducing agent is in the form of a solution, emulsified dispersion, solid fine
It can be included in the coating solution in any way, such as in the form of a particle dispersion.
Therefore, it may be contained in the photosensitive material. Well-known milk
As the chemical dispersion method, dibutyl phthalate, tricresyl
Phosphate, glyceryl triacetate or di
Oils such as ethyl phthalate, ethyl acetate and cyclohexane
Dissolve using an auxiliary solvent such as xanone and mechanically emulsify
A method for producing a dispersion is mentioned. Further, as the solid fine particle dispersion method, a reducing agent is used.
Ball mill, colloidal powder in a suitable solvent such as water.
, Vibration ball mill, sand mill, jet mill, low
Disperse by ramil or ultrasonic wave, solid dispersion
The method of making is mentioned. In this case, protective colloid
(E.g., polyvinyl alcohol), surfactant (e.g.
If sodium triisopropyl naphthalene sulfonate
(Mixing of three isopropyl groups with different substitution positions
Anionic surfactants such as Up
In mills, beads such as zirconia are used as a dispersion medium.
Z, which usually elutes from these beads
r and the like may be mixed in the dispersion. Depending on the dispersion condition
However, it is usually in the range of 1 ppm to 1000 ppm. Zr in sensitive material
If the content of silver is 0.5mg or less per gram of silver, it is practically
I do not support. Aqueous dispersions may contain preservatives (eg benzoisothia
Zolinone sodium salt) is preferably contained.
In the present invention, the reducing agent is used as a solid dispersion.
And are preferred. (Description of Development Accelerator) Photothermographic photosensitive material of the present invention
In the material, as a development accelerator, JP-A-2000-267222
And general formula (A) described in JP-A-2000-330234, etc.
Sulfonamidophenol compounds represented by
Hinder Dof represented by the general formula (II) described in 2001-92075
Enol compounds, such as JP-A-10-62895 and JP-A-10-62895.
General formula (I), Japanese Patent Application No. 2001-0
Hydra represented by the general formula (1) described in the specification of No. 74278
Gin-based compounds described in Japanese Patent Application No. 2000-76240
Phenolic or naphtho represented by the general formula (2)
A group-based compound is preferably used. These development prompts
The accelerator is used in the range of 0.1 to 20 mol% with respect to the reducing agent.
Preferably in the range of 0.5 to 10 mol%, more preferably
Preferably it is the range of 1-5 mol%. Introduction method to photosensitive material
Is the same method as the reducing agent, but in particular solid dispersions.
Or it is preferable to add as an emulsified dispersion. Emulsified part
High boiling point solvent that is solid at room temperature when added as a dust
And an emulsified dispersion dispersed using a low boiling point auxiliary solvent.
So-called organic solvents that do not use high-boiling solvents.
It is preferable to add it as an irless emulsified dispersion. Book
In the invention, among the above development accelerators, Japanese Patent Application No. 2001-074
Hydrazi represented by the general formula (1) described in No. 278
Compounds described in Japanese Patent Application No. 2000-76240
Phenol or naphtha represented by the general formula (2)
Toll compounds are particularly preferred. Hereinafter, development of the present invention
Preferable specific examples of the accelerator are given below. The present invention is not limited to these.
It is not specified. [0086] Embedded image (Explanation of Hydrogen Bonding Compound) In the present invention
When the reducing agent has an aromatic hydroxyl group (—OH),
Especially in the case of the aforementioned bisphenols, these groups and
Non-reducing with groups capable of forming hydrogen bonds
It is preferable to use a compound in combination. Hydroxyl or amino
Examples of groups that form hydrogen bonds with groups include phosphoryl groups and
Ruxoxide group, sulfonyl group, carbonyl group, amide
Group, ester group, urethane group, ureido group, tertiary amino
Group, nitrogen-containing aromatic group and the like. Preferred among them
Are phosphoryl group, sulfoxide group, amide group (however,
> N—H group, and> N—Ra (Ra is other than H
Blocked). ), Urethane group
(However,> N—H group does not exist,> N—Ra (Ra is other than H
As a substituent). ), Ureid
Group (provided that it has no> N—H group,> N—Ra (Ra is H or less)
Outside substituents). )
A compound. In the present invention, particularly preferred hydrogen bonding
The compound is a compound represented by the following general formula (D). Formula (D) [0088] Embedded image In the general formula (D), R³¹Or R³³Each
Each independently an alkyl group, aryl group, alkoxy group,
Represents an oxy group, amino group or heterocyclic group
These groups may be unsubstituted or may have a substituent.
R³¹Or R³³As the substituent when is substituted,
Halogen atom, alkyl group, aryl group, alkoxy
Group, amino group, acyl group, acylamino group, alkylthio group
O group, arylthio group, sulfonamido group, acyloxy group
Si group, oxycarbonyl group, carbamoyl group, sulfa
Moyl group, sulfonyl group, phosphoryl group, etc.
Preferred as a substituent is an alkyl group or aryl
Such as methyl, ethyl, isopropyl,
t-butyl group, t-octyl group, phenyl group, 4-al
Coxiphenyl group, 4-acyloxyphenyl group, etc.
can give. R³¹Or R³³Specific examples of alkyl groups
Are methyl, ethyl, butyl, octyl,
Decyl group, isopropyl group, t-butyl group, t-amyl
Group, t-octyl group, cyclohexyl group, 1-methyl
Chlohexyl group, benzyl group, phenethyl group, 2-phen
And a nonoxypropyl group. As an aryl group
Are phenyl, cresyl, xylyl, naphthyl,
4-t-butylphenyl group, 4-t-octylphenyl group
Group, 4-anisidyl group, 3,5-dichlorophenyl group, etc.
And so on. Alkoxy groups include methoxy and eth
Toxi group, butoxy group, octyloxy group, 2-ethyl
Hexyloxy group, 3,5,5-trimethylhexylo
Xy group, dodecyloxy group, cyclohexyloxy group,
4-methylcyclohexyloxy group, benzyloxy group
Etc. Phenoxy as an aryloxy group
Group, cresyloxy group, isopropylphenoxy group, 4
-T-Butylphenoxy group, naphthoxy group, biphenyl
An oxy group etc. are mentioned. As an amino group, dimethyla
Mino group, diethylamino group, dibutylamino group, dioctyl
Tilamino group, N-methyl-N-hexylamino group, di-
Cyclohexylamino group, diphenylamino group, N-methyl
And a til-N-phenylamino group. R³¹Or R³³As an alkyl group,
A group of aryl, alkoxy and aryloxy are preferred.
In terms of the effect of the present invention, R³¹Or R³³At least
Preferably one or more are alkyl or aryl groups.
Preferably, two or more are alkyl groups or aryl groups
It is more preferable. Also, it can be obtained at a low price
In terms of R³¹Or R³³Are preferably the same group
Good. The compound of the general formula (D) in the present invention is shown below.
Specific examples of hydrogen bonding compounds such as
Akira is not limited to these. [0091] Embedded image[0092] Embedded imageSpecific examples of the hydrogen bonding compound include those other than those described above.
State Patent No. 1096310, Japanese Patent Application No. 2000-270498, 2001-1
Those described in No. 24796 can be mentioned. General formula of the present invention
The compound (D) is in the form of a solution, emulsified and dispersed as with the reducing agent.
In the form of a solid dispersion fine particle dispersion
Can be used in photosensitive materials, but solid dispersions
It is preferable to use as. The compounds of the present invention
Compound having phenolic hydroxyl group and amino group in liquid state
A hydrogen-bonding complex with the reducing agent of the present invention.
Depending on the combination with the compound of general formula (D)
And can be isolated in the crystalline state. In this way
Use isolated crystal powder as solid dispersion fine particle dispersion
It is particularly preferable to obtain stable performance. Also,
Mixing reducing agent and compound of general formula (D) of the present invention in powder
Using a suitable dispersant, sand grinder mill, etc.
It is also preferable to use the method of complex formation at the time of dispersion with
Yes. The compound of the general formula (D) of the present invention is
And preferably used in the range of 1 to 200 mol%.
More preferably, it is in the range of 10 to 150 mol%.
Preferably it is the range of 20-100 mol%. (Description of silver halide) Used in the present invention
The photosensitive silver halide is particularly limited as a halogen composition.
No, silver chloride, silver chlorobromide, silver bromide, silver iodobromide, iodine
Silver chlorobromide and silver iodide can be used. Among them
Silver bromide and silver iodobromide are preferred. C in the particle
The distribution of the rogen composition may be uniform and the halogen composition
May be stepped or continuously
It may be changed. Also has a core / shell structure
Silver halide grains can be preferably used. Structure
The preferred structure is a 2-5 layer structure, which is more preferred
Alternatively, core / shell particles with 2-4 layers can be used.
The Odor on the surface of silver chloride, silver bromide or silver chlorobromide grains
Use technology to localize silver iodide and silver iodide
Can do. A method for forming photosensitive silver halide is known in the art.
Are well known, for example, research disclosure
No. 17029, June 1978, and U.S. Pat.No. 3,700,45
The method described in No. 8 can be used.
Physically, silver in gelatin or other polymer solution
Sensitive by adding compounds and halogen-providing compounds
Prepare light-sensitive silver halide, then mix with organic silver salt
Method is used. Also, paragraphs of JP-A-11-119374
No. 0217 to 0224, the method disclosed in
11-352627 (Japanese Patent Application No. 11-98708), JP-A 2000-347335
The listed method is also preferable. The grain size of the photosensitive silver halide is determined by the image
Small is preferable for the purpose of keeping the cloudiness after formation low.
More specifically, 0.20 μm or less, more preferably 0.01 μm
m to 0.15 μm, more preferably 0.02 μm to 0.12
μm or less is preferable. The particle size here is halogen
Projected area of silver halide grains (in the case of tabular grains, the projected plane of the main plane
Product) and the diameter when converted to a circular image of the same area. The shape of the silver halide grains is cubic.
Octahedron, tabular grain, spherical grain, rod-like grain, potato
In the present invention.
In particular, cubic particles are preferred. Corner of silver halide grains
Particles with rounded corners can also be preferably used. Photosensitivity
The surface index (Miller index) of the outer surface of silver halide grains
There is no particular limitation, but when the spectral sensitizing dye is adsorbed
The proportion of the [100] plane with high spectral sensitization efficiency is high.
And are preferred. The ratio is preferably 50% or more, 6
5% or more is more preferable, and 80% or more is more preferable. mirror
-Ratio of index [100] plane is [111] in adsorption of sensitizing dye
T.Tani; J.Imagin using the adsorption dependence of the [100] plane
g Sci., 29, 165 (1985)
You can. In the present invention, the hexacyano metal complex is granulated.
Silver halide grains present on the outermost surface of the child are preferred. Six
Cyano metal complexes include [Fe (CN)₆]^Four-, [Fe (CN)₆]^3-,
[Ru (CN)₆]^Four-, [Os (CN)₆]^Four-, [Co (CN)₆]^3-, [Rh (C
N)₆]^3-, [Ir (CN)₆]^3-, [Cr (CN)₆]^{Three -}, [Re (CN)₆]^3-Such
Is mentioned. In the present invention, hexacyano Fe complex is preferred.
That's right. The hexacyano metal complex is an ionic compound in aqueous solution.
The counter cation is not important because it exists in a form, but it is mixed with water.
Easy to soften and suitable for silver halide emulsion precipitation operations
Sodium ion, potassium ion, rubidium ion
Alkali, cesium ions and lithium ions
Metal ion, ammonium ion, alkylammonium
Ions (eg, tetramethylammonium ion,
Traethylammonium ion, tetrapropylammo
Nium ion, tetra (n-butyl) ammonium ion
Are preferred. The hexacyano metal complex is miscible with water in addition to water.
Suitable organic solvents (eg alcohols, ethers)
, Glycols, ketones, esters, amides
Etc.) and mixed with gelatin or gelatin
it can. The amount of hexacyano metal complex added is about 1 mol of silver.
Per 1 × 10^-FiveMore than mole 1 × 10^-2Molar or less is preferable,
More preferably 1 × 10^-FourMore than mole 1 × 10^-3Below the mole
is there. The hexacyano metal complex is converted to the outermost surface of silver halide grains.
To make it exist on the surface, a hexacyano metal complex is used to form particles.
After the addition of the aqueous silver nitrate solution to be used, sulfur sensitization,
Len sensitization and tellurium sensitization chalcogen sensitization and gold sensitization, etc.
At the end of the preparation process before the chemical sensitization process for sensitizing noble metals
Before completion, during washing process, during dispersion process, or before chemical sensitization process
Add directly to. Don't grow silver halide grains
For this purpose, the hexacyano metal complex should be added immediately after the grain formation.
It is preferable to add it before the end of the preparation process.
Good. Incidentally, the addition of the hexacyano metal complex causes the formation of particles.
96% by mass of the total amount of silver nitrate to be added
May be started after the addition of 98% by mass
It is more preferable to start, especially after adding 99% by mass.
Is preferred. Completion of particle formation with these hexacyano metal complexes
If added after adding the aqueous silver nitrate solution just before
It can be adsorbed on the outermost surface of silver halide grains.
Most of them form a sparingly soluble salt with silver ions on the surface of the particles. This
The silver salt of hexacyano iron (II) is less soluble than AgI
Because it can prevent re-dissolution by fine particles,
It is possible to produce small silver halide grains
It became Noh. The photosensitive silver halide grain of the present invention has a periodicity.
Metals of Groups 8 to 10 of the chart (showing Groups 1 to 18)
Or a metal complex can be contained. On the periodic table
Preferred as the central metal of Group 8 to Group 10 metals or metal complexes
Preferred are rhodium, ruthenium and iridium.
One kind of these metal complexes may be used.
Two or more metal complexes may be used in combination. Preferred content
Is 1 x 10 per mole of silver^-9From mole to 1 × 10^-3The molar range is
preferable. These heavy metals and metal complexes and their addition
Regarding the method, paragraphs of JP-A-7-225449 and JP-A-11-65021
Nos. 0018 to 0024, Japanese Patent Laid-Open No. 11-119374, paragraph numbers 0227 to 024
0. Further, silver halide grains used in the present invention
Metal atoms that can be contained in the child (eg [Fe (CN)₆]
^Four- ), Regarding desalting and chemical sensitization of silver halide emulsions
JP-A-11-84574, paragraph numbers 0046 to 0050, JP-A-11-6
No. 5021, paragraph numbers 0025 to 0031, JP-A-11-119374, paragraph number
No. 0242-0250. In the photosensitive silver halide emulsion used in the present invention,
Various gelatins are used as the contained gelatin.
Can. Organic silver salt content of photosensitive silver halide emulsion
It is necessary to maintain a good dispersion state in the coating liquid.
Yes, using gelatin with molecular weight of 10,000-1,000,000
It is preferable to do. In addition, gelatin substituents
It is also preferable to perform the treatment. These gelatins are in particle form
It may be used at the time of dispersion or after desalting,
It is preferable to use it at the time of grain formation. As a sensitizing dye applicable to the present invention, halo is used.
When adsorbed on silver halide grains, halogen in the desired wavelength region
Spectral sensitization of silver halide grains, spectral characteristics of exposure light source
Sensitizing dyes with spectral sensitivity suitable for
You can. For sensitizing dyes and addition methods, see JP-A-11
No. -65021, paragraph numbers 0103 to 0109, JP-A-10-186572
Compounds represented by general formula (II), as disclosed in JP-A-11-119374
Dye represented by formula (I) and paragraph number 0106, U.S. Pat.
No. 510,236, No. 3,871,887 Example 5
Colors disclosed in Kaihei 2-96131 and JP-A-59-48753
Elementary, European Patent Publication No. 0808374A1, page 19, line 38 ~
Page 20, line 35, JP-A-2001-272747 (Japanese Patent Application 2000-86865)
No., Japanese Patent Application No. 2001-290238 (Japanese Patent Application No. 2000-102560), Japanese Patent Application No. 2000-2
It is described in 05399 etc. These sensitizing dyes alone
Or may be used in combination of two or more. Main departure
When adding sensitizing dyes to silver halide emulsions in the light
The period is preferably the period from the desalting step to the application, more preferably
More preferably, after desalting and before the end of chemical ripening
is there. In the present invention, the amount of the sensitizing dye added depends on the sensitivity and fog.
The desired amount can be adjusted to match the performance of the
10 per mole of silver halide in the light-sensitive layer^-6~ 1 mole is preferred
More preferably 10^-Four~Ten^-1Is a mole. In the present invention, in order to improve the spectral sensitization efficiency,
A supersensitizer can be used. Super color used in the present invention
As sensitizers, European Patent Publication No. 587,338, US Patent
No. 3,877,943, No. 4,873,184, JP-A-5-341432,
Examples include compounds described in JP-A-11-109547, JP-A-10-111543, etc.
It is done. Photosensitive silver halide grains in the present invention
For sulfur sensitization, selenium sensitization or tellurium sensitization
It is preferably chemically sensitized. Sulfur sensitization,
Compounds preferably used in the Ren sensitization method and Tellurium sensitization method
As a known compound, for example, JP-A-7-128768
The described compounds and the like can be used. Especially in the present invention
In this case, tellurium sensitization is preferable.
Compound described in literature described in No. 0030, JP-A-5-31
Compounds represented by general formulas (II), (III) and (IV) in 3284
More preferred. Photosensitive silver halide grains in the present invention
In combination with the above chalcogen sensitization or alone
And preferably chemically sensitized by a gold sensitization method. Money
As the sensitizer, gold valence of +1 or +3 is preferred.
As gold sensitizers, commonly used gold compounds are preferred.
Yes. Typical examples are chloroauric acid, bromoauric acid, potassium
Chloroaurate, potassium bromoaurate, auri
Trichloride, potassium auric thiocyanate
, Potassium iodoaurate, tetracyanoourito
Quasiside, ammonium aurothiocyanate, pyridi
Rutrichlorogold is preferred. US patents
No. 5858637 and Japanese Patent Application No. 2001-79450
The listed gold sensitizers are also preferably used. In the present invention, chemical sensitization is performed after grain formation.
Can be used at any time before application
After (1) Before spectral sensitization, (2) Simultaneous with spectral sensitization, (3) Spectral sensitization
After the sensation, there may be (4) just before application. Used in the present invention
Use amount of sulfur, selenium and tellurium sensitizers
Depending on silver halide grains, chemical ripening conditions, etc.
10 per mole of silver halide^-8-10^-2Mol, preferred
10^-7-10^-3Use moles. Addition of gold sensitizer
The amount varies depending on various conditions, but as a guide, halogen
10 per mole of silver halide^-7From mole 10^-3Mole, more preferred
10^-6Mol ~ 5 × 10^-FourIs a mole. Chemistry in the present invention
The sensitization conditions are not particularly limited, but the pH is 5
~ 8, 6 ~ 11 as pAg, 40 ~ 9 as temperature
It is about 5 ° C. In the silver halide emulsion used in the present invention
In accordance with the method shown in European Patent Publication No. 293,917.
In other words, a thiosulfonic acid compound may be added. Photosensitive silver halide grains in the present invention
It is preferable to use a reduction sensitizer. Reduction sensitization
Specific compounds include ascorbic acid and thiourine dioxide
In addition, stannous chloride, aminoiminome
Tansulfinic acid, hydrazine derivatives, borane compounds,
It is preferable to use silane compounds, polyamine compounds, etc.
That's right. The addition of the reduction sensitizer is performed immediately after the crystal growth and before the application.
Any process in the photosensitive emulsion production process up to the production process may be performed. Ma
In addition, the pH of the emulsion is kept at 7 or more or the pAg is kept at 8.3 or less.
It is preferable to reduce sensitization by holding and aging
Single addition part of silver ion during grain formation
It is also preferable to carry out reduction sensitization by introducing. Photosensitive silver halide emulsion in the present invention
Increases FED as a compound that generates two electrons with one photon
Sensitizer (Fragmentable electrode)
containing onizing sensitizer)
It is preferable. As an FED sensitizer, US Pat.
No. 747235, No. 5747236, No. 6054260
No., 5999451, Japanese Patent Application No. 2001-86161
Are preferred. Work to add FED sensitizer
The process is sensitive from crystal growth to preparation process just before coating.
Any step in the emulsion production process is preferred. As addition amount
Depends on various conditions, but as a guide, halogen
10 per mole of silver halide^-7From mole 10^-1Mole, more preferred
10^-6Mol ~ 5 × 10^-2Is a mole. The photosensitive layer in the photosensitive material used in the present invention.
One type of silver halide emulsion may be used, or two or more types (examples)
For example, those with different average particle sizes and different halogen compositions
, Different crystal habits, different chemical sensitization conditions
Thing) You may use together. Photosensitive halogenation with different sensitivities
The gradation can be adjusted by using a plurality of types of silver.
As technologies related to these, JP-A-57-119341, 53-
106125, 47-3929, 48-55730, 46-5187,
Examples include 50-73627 and 57-150841. sensitivity
The difference is that each emulsion has a difference of 0.2 logE or more.
It is preferable. The amount of photosensitive silver halide added was 1 m of photosensitive material.
²Indicated by the amount of silver applied per unit, 0.03 to 0.6 g / m²Be
Is preferred, 0.07 to 0.4 g / m²More preferred to be
0.05-0.3g / m²Most preferably, organic silver
For 1 mol of salt, the photosensitive silver halide is 0.01 mol or less.
0.5 mol or less is preferable, more preferably 0.02 mol or less
0.3 mol or less, more preferably 0.03 mol or more and 0.2 mol
It is as follows. Separately prepared photosensitive silver halide and organic
For silver salt mixing method and mixing conditions, prepare each
The finished silver halide grains and organic silver salt are
Roll mill, sand mill, colloid mill, vibration mill, homo
Method of mixing with a generator, etc., or preparation of organic silver salt
A photosensitive halo that has been prepared at any time during production
There is a method to prepare organic silver salt by mixing silver halide
However, as long as the effects of the present invention are fully manifested,
There is no limit. Also, two or more organic silver salt moisture when mixing
Mixing the dispersion with two or more photosensitive silver salt water dispersions
Is a preferred method for adjusting photographic properties. The silver halide image forming layer coating solution of the present invention
The preferred timing of addition to the inside is from 180 minutes before application.
Before, preferably from 60 minutes to 10 seconds ago.
And mixing conditions as long as the effects of the present invention are sufficiently exhibited.
There is no particular limitation in the case. As a specific mixing method
Average residence time calculated from the flow rate of addition and the amount of liquid delivered to the coater
Mixing in a tank with a desired time interval
Law, N.Harnby, M.F.Edwards, A.W.Nienow, Koji Takahashi
Translated “Liquid Mixing Technology” (published by Nikkan Kogyo Shimbun, 1989)
Use the static mixer described in Chapter 8 etc.
There is a way to do it. (Explanation of Binder) Including organic silver salt of the present invention
Any polymer can be used for the layered binder.
Suitable binders are transparent or translucent and generally colorless
Natural resins, polymers and copolymers, synthetic resins
And polymers and copolymers, and other films
Medium such as gelatin, rubber, poly (vinyl alcohol)
Coal), hydroxyethylcelluloses, cellulose
Suacetates, cellulose acetate butyrate,
Poly (vinyl pyrrolidone), casein, starch, po
Li (acrylic acid), poly (methyl methacrylic acid),
Poly (vinyl chloride), poly (methacrylic acid), steel
Lene-maleic anhydride copolymers, styrene-acrylo
Nitrile copolymers, styrene-butadiene copolymers
, Poly (vinyl acetal) s (for example, poly (vinyl
Leformal) and poly (vinyl butyral)), poly
(Ester), poly (urethane), phenoxy tree
Fat, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonates), poly (vinyl acetate) s,
Poly (olefins), cellulose esters, poly
There are (amides). The binder can be water or an organic solvent or
May be coated from an emulsion. In the present invention, it is used in combination with a layer containing an organic silver salt.
The glass transition temperature of the binder that can be made is 10 ° C to 80 ° C.
The following (hereinafter, sometimes referred to as a high Tg binder)
Preferably, it is 15 to 70 ° C.
Furthermore, it is more preferable that the temperature is 20 ° C or higher and 65 ° C or lower.
Yes. In this specification, Tg is calculated by the following formula.
I calculated. 1 / Tg = Σ (Xi / Tgi) Here, the polymer is n monomers from i = 1 to n
Assume that the components are copolymerized. Xi is the i-th monomer
Mass fraction (ΣXi = 1), Tgi is the homopolymerization of the i-th monomer
It is the glass transition temperature (absolute temperature) of the body. Where Σ is i =
Take the sum from 1 to n. Each monomer homopolymer
The glass transition temperature value (Tgi) is the Polymer Handbook (3rd Ed
ition) (by J. Brandrup, E.H. Immergut (Wiley-Interscien
ce, 1989)) was adopted. [0122] If necessary, two or more binders may be used in combination.
You may do it. Also, glass transition temperature of 20 ° C or higher
Used in combination with a glass transition temperature of less than 20 ° C
May be. Blend of two or more polymers with different Tg
The mass average Tg is in the above range.
It is preferable to enter. In the present invention, the organic silver salt-containing layer is a solvent.
Apply and dry with an aqueous coating solution in which 30% by mass or more of water is water.
It is preferable to dry to form a film. In the present invention
In the organic silver salt-containing layer, 30% by mass or more of the solvent is water.
When it is formed using a coating solution and dried,
In addition, the binder of the organic silver salt-containing layer is an aqueous solvent (aqueous solvent)
Especially when soluble or dispersible at 25 ° C, 60% RH
Latex of polymer having an equilibrium moisture content of 2% by mass or less
The performance is improved when it consists of The most preferred form is
Prepared so that the ionic conductivity is 2.5 mS / cm or less.
As such a preparation method, separation after polymer synthesis
A purification method using a functional membrane can be mentioned. The polymer mentioned here is soluble or dispersed.
A possible aqueous solvent is water or 70% by weight or less in water.
It is a mixture of water-miscible organic solvents. Water miscible
Examples of the organic solvent include methyl alcohol and ethyl.
Alcohols such as alcohol and propyl alcohol,
Chircellosolve, ethylcellosolve, butylcellosolve
Cellosolve such as ethyl acetate, dimethylformamide
And so on. It should be noted that the polymer is dissolved thermodynamically.
In the case of a system that exists in a so-called dispersed state,
Here, the term aqueous solvent is used. “Equilibrium moisture content at 25 ° C. and 60% RH”
Is a polymer in a humidity-controlled equilibrium at 25 ° C and 60% RH
ー mass W₁And the mass W of the polymer in an absolutely dry state at 25 ° C₀The
It can be expressed as follows. Equilibrium moisture content at 25 ℃ 60% RH = [(W₁-W₀) / W₀] X 100 (mass
%) For the definition and measurement method of the moisture content, for example,
Polymer Engineering Lecture 14, Polymer Material Testing Method (Polymer Society)
Jinjinshokan) can be consulted. The binder polymer of the present invention at 25 ° C. and 60% R
The equilibrium moisture content in H is preferably 2% by mass or less.
More preferably, it is 0.01% by mass or more and 1.5% by mass or less.
Lower, more preferably 0.02% to 1% by weight
Good. In the present invention, a polymer dispersible in an aqueous solvent is used.
Limers are particularly preferred. Examples of dispersed states are water insoluble
Latex in which fine particles of hydrophobic polymer are dispersed
Polymer molecules disperse in a molecular state or form micelles
It can be anything, but latex distributed
Particles are more preferred. The average particle size of the dispersed particles is 1-50000n
m, preferably in the range of 5 to 1000 nm, more preferably 10
In the range of ~ 500nm, more preferably in the range of 50 ~ 200nm.
The There is no particular limitation on the particle size distribution of the dispersed particles.
Have a monodispersed particle size distribution
But you can. Mix two or more types with monodisperse particle size distribution
To control the physical properties of the coating solution.
Usage. In the present invention, polydispersible in an aqueous solvent is used.
Preferred embodiments of the polymer include acrylic polymers and polymers.
Re (esters), rubbers (eg SBR resin), poly
(Urethane), poly (vinyl chloride), poly (vinyl acetate)
Nyl), poly (vinylidene chloride), poly (Olephy)
Hydrophobic polymers such as
The These polymers can be straight-chain polymers or branched.
It may be a crosslinked polymer or a crosslinked polymer
A so-called homopolymer in which a single monomer is polymerized.
Or a copolymer of two or more monomers
But you can. In the case of a copolymer, a random copolymer
Or a block copolymer. The fraction of these polymers
The molecular weight is 5,000 to 100,000, preferably 10,000 in terms of number average molecular weight.
~ 200000 is good. If the molecular weight is too small, the power of the emulsion layer
Academic strength is inadequate.
It is not preferable. Crosslinkable polymer latex
Are preferably used. (Specific Examples of Latex) Preferred Polymer
Specific examples of latex include the following:
it can. The following are expressed using raw material monomers, and are in parentheses.
A numerical value is mass% and a molecular weight is a number average molecular weight. Multifunctional
When a monomer is used, the molecular weight is approximated to form a crosslinked structure.
Since it is not applicable, write it as crosslinkable and write the molecular weight.
Omitted. Tg represents the glass transition temperature. Latec of P-1; -MMA (70) -EA (27) -MAA (3)-
(Molecular weight 37000, Tg61 ℃) P-2; -MMA (70) -2EHA (20) -St (5) -AA (5)-latex (min
(Quantity 40,000, Tg 59 ° C) P-3; -St (50) -Bu (47) -MAA (3)-latex (crosslinkable, Tg-
(17 ℃) Latex of P-4; -St (68) -Bu (29) -AA (3)-(crosslinkability, Tg17
℃) P-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg24
℃) Latex of P-6; -St (70) -Bu (27) -IA (3)-(crosslinkability) P-7; -St (75) -Bu (24) -AA (1)-latex (crosslinkable, Tg29
℃) Latex of P-8; -St (60) -Bu (35) -DVB (3) -MAA (2)-
sex) Latex of P-9; -St (70) -Bu (25) -DVB (2) -AA (3)-
sex) Latec of P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-
(Molecular weight 80000) P-11; -VDC (85) -MMA (5) -EA (5) -MAA (5)-latex (min
(Quantity 67000) Latex of P-12; -Et (90) -MAA (10)-(molecular weight 12000) P-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130
000, Tg43 ℃) P-14; -MMA (63) -EA (35)-AA (2) latex (molecular weight 330
00, Tg47 ℃) P-15; -St (70.5) -Bu (26.5) -AA (3)-latex (crosslinkable,
(Tg23 ℃) P-16; -St (69.5) -Bu (27.5) -AA (3)-latex (crosslinkable,
(Tg20.5 ℃) The abbreviations for the above structures represent the following monomers.
MMA; methyl methacrylate, EA; ethyl acrylate
, MAA; methacrylic acid, 2EHA; 2-ethylhexyl aqua
Relate, St; Styrene, Bu; Butadiene, AA; Acry
Luric acid, DVB; Divinylbenzene, VC; Vinyl chloride, AN;
Acrylonitrile, VDC; Vinylidene chloride, Et; Ethylene
IA; Itaconic acid. The polymer latexes described above are commercially available.
The following polymers can be used. A
Examples of cryl polymers include Sebian A-4635, 471
8, 4601 (above made by Daicel Chemical Industries), Nipol Lx8
11, 814, 821, 820, 857 (above ZEON CORPORATION)
As an example of poly (ester) such as
ES650, 611, 675, 850 (above Dainippon Ink Chemical Co., Ltd.)
), WD-size, WMS (Eastman Chemical)
However, as an example of poly (urethane), HYDRAN AP10, 2
Rubber such as 0, 30, 40 (above Dainippon Ink & Chemicals)
Examples of classes include LACSTAR 7310K, 3307B, 4700H, 71
32C (above Dainippon Ink and Chemicals), NipolLx416, 41
Poly, such as 0, 438C, 2507 (manufactured by Nippon Zeon Co., Ltd.)
Examples of (vinyl chloride) are G351, G576 (Japan)
Examples of poly (vinylidene chloride) such as ZEON Co., Ltd.
As L502, L513 (made by Asahi Kasei Kogyo Co., Ltd.)
As an example of poly (olefin) s, Chemipearl S1
20, SA100 (Mitsui Petrochemical Co., Ltd.)
You can. These polymer latexes are used alone.
Or you can blend two or more as needed
Yes. (Preferred Latex) Used in the present invention
As the polymer latex, styrene-butadiene
Latex of ene copolymer is preferred. Styrene-pig
Styrene monomer units and pigs in diene copolymers.
The mass ratio of diene to monomer units is 40:60 to 95: 5
It is preferable. Also, styrene monomer unit and pig
The proportion of diene in the copolymer with monomer units is 60 to
It is preferable that it is 99 mass%. The polymer of the present invention
-Latex uses acrylic or methacrylic acid
1 to 6% by mass based on the sum of styrene and butadiene
Is preferable, and more preferably 2 to 5% by mass. Book
The polymer latex of the invention contains acrylic acid
Is preferred. Styrene preferably used in the present invention
As the latex of butadiene acid copolymer, the P-
3 to P-8, 15, commercially available LACSTAR-3307B, 7132C, Ni
polLx416 etc. are mentioned. The organic silver salt-containing layer of the light-sensitive material of the present invention is essential.
Gelatin, polyvinyl alcohol, methyl
Roulose, hydroxypropylcellulose, carboxy
Hydrophilic polymers such as methylcellulose may be added
Yes. The amount of these hydrophilic polymers added is the organic silver salt-containing layer
30% by weight or less of the total binder, more preferably 20% by weight
% Or less is preferable. The organic silver salt-containing layer of the present invention (ie, image formation)
Layer) is formed using polymer latex
preferable. The amount of binder in the organic silver salt-containing layer is
The mass ratio of the binder / organic silver salt is 1/110 to 10/1, more preferably
Is in the range of 1 / 3-5 / 1, more preferably in the range of 1 / 1-3 / 1
is there. Also, such an organic silver salt-containing layer is not
Usually contained photosensitive silver halide, which is a photosensitive silver salt
It is also the photosensitive layer (emulsion layer).
Inder / silver halide mass ratio of 400-5, more preferred
Or in the range of 200-10. The total amount of binder in the image forming layer of the present invention is good.
Preferably 0.2-30g / m², More preferably 1-15 g / m²And more
Preferably 2-10 g / m²Range. Image shape of the present invention
Cross-linking agent for cross-linking, interface for improving coating properties
An activator or the like may be added. (Preferable solution of coating solution
Medium) In the present invention, the organic silver salt-containing layer of the light-sensitive material
Solvent for coating solution (For simplicity, remove solvent and dispersion medium.
Also referred to as solvent. ) Is an aqueous solution containing 30% by mass or more of water.
A medium is preferred. As a component other than water, methyl alcohol
, Ethyl alcohol, isopropyl alcohol, methyl
Lucerosolve, ethylcellosolve, dimethylformami
Use any water-miscible organic solvent such as ethyl acetate
Yes. The water content of the solvent of the coating solution is more than 50% by mass, more preferred
It is preferably 70% by mass or more. Examples of preferred solvent compositions
For example, in addition to water, water / methyl alcohol = 90/10, water /
Methyl alcohol = 70/30, water / methyl alcohol / dime
Tylformamide = 80/15/5, water / methyl alcohol / ethyl
Lucerosolve = 85/10/5, water / methyl alcohol / isopropyl
Pill alcohol = 85/10/5
%). (Description of antifogging agent)
Antifoggants, stabilizers and stabilizer precursors that can be
Japanese Patent Laid-Open No. 10-62899, paragraph 0070, European Patent Publication No.
0803764A1 page 20 line 57 to page 21 line 7
Permitted, compounds described in JP-A-9-281637 and 9-329864
Product, U.S. Patent No. 6,083,681, No. 6,083,681, European Patent No. 10
Examples include the compounds described in No. 48975. Also, in the present invention
Antifoggants preferably used are organic halides.
Yes, these are paragraph numbers of JP-A-11-65021
Examples disclosed in the patents described in 0111 to 0112
It is. In particular, organic compounds represented by the formula (P) in JP-A-2000-284399
Rogen compound, represented by general formula (II) of JP-A-10-339934
Organic polyhalogen compounds, JP-A-2001-31644 and
Organic polyhalogen compounds described in JP-A-2001-33911 are preferred.
Good. (Description of polyhalogen compound)
Specific examples of clear and preferred organic polyhalogen compounds
explain. Preferred polyhalogen compounds of the present invention are:
It is a compound represented by general formula (H). General formula (H) Q- (Y) n-C (Z₁) (Z₂) X In general formula (H), Q is an alkyl group, aryl group or
Represents a heterocyclic group, Y represents a divalent linking group, and n represents
Represents 0 or 1, Z₁And Z₂Represents a halogen atom
X represents a hydrogen atom or an electron-withdrawing group. General formula
In (H), Q is preferably an aryl group or hetero
It is a cyclic group. In general formula (H), Q is a heterocyclic group
In some cases, a nitrogenous heterogene containing 1 or 2 nitrogen atoms
A cyclic group is preferred, and a 2-pyridyl group and a 2-quinolyl group are particularly
Is preferred. In the general formula (H), Q is an aryl group
In some cases, Q is preferably Hammett's substituent constant σp
A phenyl group substituted with a positive electron-withdrawing group is represented.
The For Hammett's substituent constants, see Journal of Med
See icinal Chemistry, 1973, Vol. 16, No. 11, 1207-1216, etc.
Can be considered. As such an electron-withdrawing group
Is, for example, a halogen atom (fluorine atom (σp value: 0.0
6), chlorine atom (σp value: 0.23), bromine atom (σp
Value: 0.23), iodine atom (σp value: 0.18)),
Trihalomethyl group (tribromomethyl (σp value: 0.2
9), trichloromethyl (σp value: 0.33), trif
Fluoromethyl (σp value: 0.54)), cyano group (σp
Value: 0.66), nitro group (σp value: 0.78), fat
Group aryl or heterocyclic sulfonyl groups (eg,
Tansulfonyl (σp value: 0.72)), aliphatic, ant
Or an acyl group such as acetyl (σp
Value: 0.50), benzoyl (σp value: 0.43)),
Alkynyl group (for example, C≡CH (σp value: 0.2
3)), aliphatic, aryl or heterocyclic oxycarbo
Nyl group (for example, methoxycarbonyl (σp value: 0.4
5), phenoxycarbonyl (σp value: 0.44)),
Carbamoyl group (σp value: 0.36), sulfamoyl
Group (σp value: 0.57), sulfoxide group, heterocyclic ring
Group, phosphoryl group and the like. Preferred as σp value
Or in the range of 0.2 to 2.0, more preferably 0.4.
To 1.0. Especially preferred as an electron withdrawing group
Carbamoyl group, alkoxycarbonyl group,
Alkylsulfonyl group, alkylphosphoryl group,
However, a carbamoyl group is most preferable. X is preferably
Electron withdrawing group, more preferably halogen atom, fat
Aliphatic / aryl or heterocyclic sulfonyl group, aliphatic /
Aryl or heterocyclic acyl group, aliphatic / aryl
Or a heterocyclic oxycarbonyl group, carbamoyl group,
Rufamoyl group, particularly preferably a halogen atom
is there. Among halogen atoms, preferably chlorine atom, odor
An elementary atom, an iodine atom, more preferably a chlorine atom,
A bromine atom, particularly preferably a bromine atom. Y is
Preferably -C (= O)-, -SO- or -SO₂ −
More preferably -C (= O)-, -SO₂ -
Yes, particularly preferably -SO₂ -. n is 0 or
Represents 1 and is preferably 1. In the following, the compounds of the general formula (H) of the present invention are prepared.
An example is shown. [0146] Embedded image [0147] Embedded imageThe compound represented by the general formula (H) of the present invention is
10 per mole of non-photosensitive silver salt in the image forming layer^-Four~ 1 mo
It is preferable to use within the range of more than 1, more preferably 1
0^-3In the range of ~ 0.5 mol, more preferably 1 × 10
^-2It is preferable to use in the range of ~ 0.2 mol. Main departure
To add anti-fogging agent to light sensitive materials
Examples of the method include the method described in the method for containing a reducing agent.
Organic polyhalogen compounds can also be used for solid fine particles.
It is preferable to add as a dust. (Other antifoggants) Other fog
As the inhibitor, mercury (I
I) Salts, benzoic acids of paragraph No. 0114 of the same, JP 2000-20664
No. 2 salicylic acid derivative, in formula (S) of JP-A-2000-221634
Formalin scavenger compounds represented, JP-A-11-3
No. 52624, triazine compound according to claim 9, Japanese Patent Laid-Open No. 6-1
Compound represented by general formula (III) of No. 1791, 4-hydroxy-
Examples include 6-methyl-1,3,3a, 7-tetrazaindene. The photothermographic material of the present invention is antifoggant.
An azolium salt may be contained for the purpose of stopping. Azori
As the um salt, general formula (XI) described in JP-A-59-193447
Compounds represented by JP-B-55-12581,
The compound represented by the general formula (II) described in Kaikai 60-153039 is
Can be mentioned. Azolium salt can be applied to any part of the photosensitive material.
It may be added, but the additive layer has a photosensitive layer
It is preferable to add it to the layer of organic silver salt
More preferably. When azolium salt is added
Therefore, it can be done in any process of preparing the coating solution,
When adding to a silver salt-containing layer
It can be applied at any stage of preparation, but it can be applied after the organic silver salt is prepared.
Immediately before the cloth is preferred. As a method of adding azolium salt, powder
Powder, solution, fine particle dispersion, etc.
Yes. In addition, other additives such as sensitizing dyes, reducing agents, and toning agents
You may add as a mixed solution. In the present invention
Zorium salt can be added in any amount, but silver
1 x 10 per mole^-61 to 2 moles are preferred, 1
× 10^-3More preferably, it is more than mol and less than 0.5 mol. In the present invention, development is suppressed or promoted.
In order to control the image and improve the spectral sensitization efficiency,
Mercapto compounds to improve preservability before and after images
Products, disulfide compounds, and thione compounds.
Paragraph Nos. 0067 to 0069 of JP-A-10-62899,
Compounds represented by general formula (I) of Kaihei 10-186572 and
As specific examples, paragraph numbers 0033 to 0052, European Patent Publication No. 0803
764A1, page 20, lines 36-56
The Among them, JP-A-9-297367, JP-A-9-304875,
JP 2001-100358, Japanese Patent Application 2001-104213, Japanese Patent Application 2001-104
Mercapto-substituted heteroaromatic compounds described in 214 etc.
Things are preferred. (Description of Toning Agent) Photothermographic material of the present invention
Then, it is preferable to add a color toning agent.
No. 10-62899, paragraphs 0054-0055, European Patent Publication No. 08
03764A1 page 21, lines 23-48, JP 2000-356317
And Japanese Patent Application No. 2000-187298.
Radinones (phthalazinone, phthalazinone derivatives or
Is a metal salt; for example 4- (1-naphthyl) phthalazinone, 6-chloro
Lophthalazinone, 5,7-dimethoxyphthalazinone and 2,
3-dihydro-1,4-phthalazinedione); phthalazinones
And phthalic acids (e.g. phthalic acid, 4-methylphthalic acid, 4
-Nitrophthalic acid, diammonium phthalate, phthalic acid
Sodium, potassium phthalate and tetrachloroanhydrous
In combination with phthalic acid; phthalazines (phthalazine, phthalates)
Tarazine derivatives or metal salts; for example 4- (1-naphthyl)
Phthalazine, 6-isopropylphthalazine, 6-t-butylphenol
Latazine, 6-chlorophthalazine, 5,7-dimethoxyphthala
Gin and 2,3-dihydrophthalazine); with phthalazines
A combination with phthalic acids is preferred, especially with phthalazines
A combination of phthalic acids is preferred. Especially preferred among them
The new combination is 6-isopropylphthalazine and phthalic acid
Or a combination with 4-methylphthalic acid. (Other additives) Used for the photosensitive layer of the present invention.
Regarding plasticizers and lubricants that can be used,
11-65021 Paragraph No. 0117, Carbide for forming super high contrast images
For the preparation and its addition method and amount, paragraph number 01 of the same item
18, Japanese Patent Laid-Open No. 11-223898, paragraph numbers 0136 to 0193, Japanese Patent Laid-Open No. 200
Compound of formula (H), formula (1) to (3), formula (A), (B) of 0-284399
Of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652
Compounds (specific compounds: Chemical Formula 21 to Chemical Formula 24), high contrast accelerator
JP-A-11-65021 paragraph number 0102, JP-A-11-223
No. 898, paragraph numbers 0194-0195. Use formic acid or formate as a strong fogging substance
An image forming layer containing photosensitive silver halide.
Less than 5 millimoles per mole of silver,
It is preferable to contain it at a millimol or less. In the photothermographic material of the present invention, a super high contrast agent is used.
The acid formed by hydration of diphosphorus pentoxide or
These salts are preferably used in combination. Diphosphorus pentoxide
Hydrated acid or its salts include metaphosphoric acid
(Salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triri
Acid (salt), tetraphosphoric acid (salt), hexametaphosphoric acid (salt)
And so on. Particularly preferably used
As an acid or salt thereof formed by hydrating diphosphorus oxide,
List of orthophosphoric acid (salt) and hexametaphosphoric acid (salt)
be able to. Specific salt is sodium orthophosphate
Um, sodium dihydrogen orthophosphate, hexametaline
Sodium phosphate, ammonium hexametaphosphate, etc.
The Use of acid or its salt formed by hydration of diphosphorus pentoxide
Dose (photosensitive material 1m²Coating amount) is sensitivity and fog
The desired amount may be selected according to the performance, but 0.1 to 500m
g / m²Is preferred, 0.5-100 mg / m²Is more preferable. (Explanation of layer structure) Thermal development feeling in the present invention
The optical material is a surface protective layer for the purpose of preventing adhesion of the image forming layer.
Can be provided. The surface protective layer may be a single layer,
Multiple layers may be used. Regarding the surface protective layer,
11-65021 No. 0119-0120, Japanese Patent Application No. 2000-171936
Has been described. As a binder for the surface protective layer of the present invention
Gelatin is preferred, but polyvinyl alcohol (PV
It is also preferred to use A) or in combination. Gelati
Inert gelatin (eg Nitta Gelatin 75)
0), phthalated gelatin (eg Nitta Gelatin 801), etc.
Can be used. As PVA, JP 2000-171 A
936 No. paragraphs 0009-0020 are listed,
Fully saponified PVA-105, partially saponified PVA
-205, PVA-335, modified polyvinyl alcohol
MP-203 (trade name, manufactured by Kuraray Co., Ltd.)
Is preferred. Polyvinyl protective layer (per layer)
Nyl alcohol coating amount (support 1m²As a win) is 0.
3 ~ 4.0g / m²Is preferably 0.3 to 2.0 g / m²Is more preferable. Especially for printing applications where dimensional change is a problem.
When using a bright photothermographic material, a surface protective layer or
It is preferable to use a polymer latex for the backing layer.
For such polymer latex, “Synthetic resin
Marujon (edited by Taira Okuda, Hiroshi Inagaki, published by Kobunshi Publishing Co.
(1978)) ”,“ Application of synthetic latex (Takashi Sugimura)
Akira, Katsuo Kataoka, Junichi Suzuki, Keiji Kasahara, polymer publication society
Published (1993)), “Synthetic Latex Chemistry (Muroi)
Written by Soichi, published by Kobunshi Shuppankai (1970))
Specifically, methyl methacrylate (33.5% by mass)
/ Ethyl acrylate (50% by mass) / Methacrylic acid (16.5 quality)
%) Copolymer latex, methyl methacrylate (4
7.5% by mass) / Butadiene (47.5% by mass) / Itaconic acid (5% by mass)
%) Copolymer latex, ethyl acrylate / meta
Latex of copolymer of crylic acid, methyl methacrylate
(58.9% by mass) / 2-ethylhexyl acrylate (2
5.4% by mass) / styrene (8.6% by mass) / 2-hydroxyethyl
Dimethacrylate (5.1% by mass) / acrylic acid (2.0% by mass)
Polymer latex, methyl methacrylate (64.0 quality
%) / Styrene (9.0 mass%) / butyl acrylate (20.0%)
% By mass) / 2-hydroxyethyl methacrylate (5.0% by mass)
%) / Latex of acrylic acid (2.0 mass%) copolymer, etc.
Is mentioned. Furthermore, as a binder for the surface protective layer
The polymer latex set of Japanese Patent Application No. 11-6872
In addition, paragraph numbers 0021 to 0 of Japanese Patent Application No. 11-143058
The technology described in 025, paragraph number 00 of Japanese Patent Application No. 11-6872
The technology described in 27-0028, Japanese Patent Application No. 10-199626
The techniques described in the numbers 0023 to 0041 may be applied. surface
The ratio of polymer latex in the protective layer is 10% of the total binder
It is preferable to be at least 90% by mass, especially at least 20% by mass
80 mass% or less is preferable. Surface protective layer (per layer)
All binders (water-soluble polymers and latex polymers)
Coating amount (including support 1m)²As per) 0.3-5.0
g / m²Is preferably 0.3 to 2.0 g / m²Is more preferable. The preparation temperature of the image forming layer coating solution of the present invention is 30.
℃ ≧ 65 ℃ is better, more preferable temperature is 35 ℃
Less than 60 ° C, more preferable temperature is 35 ° C or more and 55 ° C or less
The Also, the image forming layer coating immediately after the addition of the polymer latex
It is preferable that the temperature of the cloth liquid is maintained between 30 ° C and 65 ° C.
That's right. The image-forming layer of the present invention is a monolayer on the support.
Consists of more layers. Yes, if it consists of one layer
Silver salt, photosensitive silver halide, reducing agent and binder
Tones, coating aids and other aids as needed
Including optional additional materials such as agents. Consists of two or more layers
The first imaging layer (usually adjacent to the support)
Layer) contains an organic silver salt and a photosensitive silver halide, the second
Do not contain some other ingredients in the imaging layer or both layers
I have to. The composition of the multicolor photosensitive photothermographic material is
You may include a combination of these two layers for each color.
As described in U.S. Pat.No. 4,708,928.
All components may be included in one layer. Multi-dye multicolor feeling
In the case of photothermographic materials, each emulsion layer is generally
As described in Patent No. 4,460,681, each photosensitivity
Use functional or non-functional barrier layers between layers
Thus, they are kept distinguished from each other. The photosensitive layer of the present invention has an improved color tone, a laser.
Viewpoints to prevent interference fringes and exposure to radiation during exposure
To various dyes and pigments (for example, C.I.Pigment Blue 60, C.I.
I. Pigment Blue 64, C.I. Pigment Blue 15: 6)
be able to. For these, WO98 / 36322, JP
10-268465, 11-338098, etc.
The In the photothermographic material of the present invention,
Set the thihalation layer farther from the light source than the photosensitive layer.
Can be provided. The photothermographic material is generally added to the photosensitive layer.
And has a non-photosensitive layer. Non-photosensitive layer from its arrangement
(1) Provided on the photosensitive layer (the side farther from the support)
(2) Protection between the photosensitive layers and between the photosensitive layers
An intermediate layer provided between the layers; (3) a photosensitive layer and a support;
(4) on the opposite side of the photosensitive layer
The back layer can be classified. The filter layer
It is provided in the photosensitive material as the layer (1) or (2).
The antihalation layer shall be the layer (3) or (4)
Provided in the photosensitive material. The antihalation layer is disclosed in JP-A-11
No. -65021, paragraph numbers 0123 to 0124, JP-A-11-223898, 9
-230531, 10-36695, 10-104779, 11-23145
No. 7, 11-352625, 11-352626, etc.
The Antihalation layer has absorption at exposure wavelength
Containing antihalation dyes. Exposure wavelength is infrared
If it is in the range, an infrared absorbing dye may be used.
In some cases, a dye having no absorption in the visible region is preferred. Visible
Prevents halation using dyes that absorb in the region
In some cases, the dye color does not substantially remain after image formation.
It is preferable to remove the color by heat of heat development.
It is preferable to use a means, and in particular, heat decolorization in the non-photosensitive layer
Add dye and base precursor to anti-halation
It is preferable to function as an active layer. To these technologies
This is described in JP-A-11-231457. The amount of decoloring dye added depends on the use of the dye.
Determine. In general, light measured at the target wavelength
Use in an amount where the chemical concentration (absorbance) exceeds 0.1. Optical density
The degree is preferably 0.15 to 2, preferably 0.2 to 1.
Are more preferable. Dyeing to obtain such optical density
The amount of charge used is generally 0.001 to 1 g / m²Degree. Note that when the dye is decolored in this way,
The optical density after image can be reduced to 0.1 or less.
The Use two or more types of decoloring dyes, thermal decoloring type recording materials,
You may use together in an image photosensitive material. Similarly, two or more types
The above base precursor may be used in combination. Such an erase
In thermal decolorization using a color dye and a base precursor,
A base precursor as described in JP-A-11-352626
Substances that lower the melting point by 3 ° C (deg) or more when mixed (eg,
For example, diphenyl sulfone, 4-chlorophenyl (pheny
E) Sulfone), 2-naphthylbenzoate, etc.
It is preferable in terms of thermal decoloring properties. In the present invention, silver tone and aging of image are changed.
Coloring with an absorption maximum at 300-450 nm for the purpose of improving
An agent can be added. Such colorants are disclosed in JP
Sho 62-210458, 63-104046, 63-103235, 63-
208846, 63-306436, 63-314535, JP 01-6
1745, JP-A-2001-100363 and the like. This
Colorants like are usually 0.1mg / m²~ 1g / m²In the range of
The layer to be added is provided on the opposite side of the photosensitive layer.
A back layer is preferred. In the present invention, the photothermographic material is a support.
Contains at least one silver halide emulsion on one side of
It has a photosensitive layer and a back layer on the other side.
It is preferably a single-sided photosensitive material. (Description of Matting Agent) In the present invention, the conveying
It is preferable to add a matting agent to improve the
Regarding the adhesive, paragraph numbers 0126 to 01 of JP-A-11-65021
27. Matting agent is photosensitive material 1m²Hit
When expressed in terms of coating amount, preferably 1 to 400 mg / m²More like
Preferably 5 ~ 300mg / m²It is. Matting agent in the present invention
The shape can be either regular or irregular, but preferably
As the mold, a spherical shape is preferably used. The average particle size is 0.5 ~
It is preferably 10 μm, more preferably 1.0 μm.
To 8.0 μm, more preferably 2.0 to 6.0 μm.
It is a range. The size distribution coefficient of variation is 50.
% Or less, more preferably 40% or less
Below, more preferably 30% or less. Fluctuate here
The coefficient is (standard deviation of particle size) / (average value of particle size) × 10
A value represented by 0. A mat with a small coefficient of variation
Use two agents with an average particle size ratio greater than 3
Both are preferable. The matte degree of the emulsion surface is likely to cause stardust failure.
If it doesn't fit, the Beck smoothness is 30 seconds or more.
Upper 2000 seconds or less is preferable, especially 40 seconds or more and 1500 seconds or less is preferable.
Good. Beck smoothness is Japanese Industrial Standard (JIS) P811
9 "How to test the smoothness of paper and paperboard using the Beck tester
Method and TAPPI standard method T479
it can. In the present invention, the matte degree of the back layer
The Beck smoothness is preferably 1200 seconds or less and 10 seconds or more, 800
20 seconds or more is preferable, more preferably 500 seconds or less.
Under 40 seconds or more. In the present invention, the matting agent is the most photosensitive material.
A layer that functions as an outer surface layer or outermost surface layer, or
Is preferably contained in a layer close to the outer surface.
It is preferably contained in a layer that acts as a loose protective layer.
Yes. In the back layer applicable to the present invention
JP-A-11-65021, paragraph numbers 0128 to 0130
It is. The photothermographic material of the present invention is obtained before heat development.
It is preferable that the film surface pH is 7.0 or less,
Preferably it is 6.6 or less. There is no limit to the lower limit.
No, but about 3. The most preferred pH range is 4 to
The range is 6.2. Adjustment of membrane surface pH is phthalic acid derivative
Non-volatile acids such as organic acids and sulfuric acid, and ammonia
Which volatile base is used reduces the membrane surface pH
From the viewpoint of Ammonia is particularly volatile
Can be removed before coating or heat development
From the viewpoint of achieving a low film surface pH. Also hydroxylation
Nonvolatility of sodium, potassium hydroxide, lithium hydroxide, etc.
It is also preferable to use an exogenous base and ammonia together
It is done. The method for measuring the film surface pH is described in Japanese Patent Application No. 11-87297.
It is described in paragraph number 0123 of the specification. Photosensitive layer, protective layer, back layer and the like of the present invention
A hardener may be used for each layer. An example of a hardener is T.
“THE THEORY OF THE PHOTOGRAPHIC PROCESS” by H.James
FOURTH EDITION ”(Macmillan Publishing Co., Inc.
(Published in 1977) There are various methods described on pages 77 to 87.
Rom Alum, 2,4-Dichloro-6-hydroxy-s-tria
Gin sodium salt, N, N-ethylenebis (vinylsulfone
Acetamide), N, N-propylenebis (vinylsulfone)
Acetamide) and other polyvalent metal ions described on page 78, etc.
U.S. Pat.No. 4,281,060, JP-A-6-208193, etc.
Epoxy such as reisocyanates, US Patent 4,791,042
Xylon compounds, vinyl sulfones such as JP-A 62-89048
System compounds are preferably used. The hardener is added as a solution and the solution
The timing of addition to the protective layer coating solution is from 180 minutes before application.
Immediately before, preferably 60 minutes to 10 seconds before, mixing method
And the mixing conditions as long as the effects of the present invention are sufficiently exhibited.
There are no particular restrictions on the location. As a specific mixing method
Is the average residence calculated from the flow rate of addition and the amount of liquid delivered to the coater
Mix in a tank with the desired time
Method and by N.Harnby, M.F.Edwards, A.W.Nienow, Yuki Takahashi
Translation of “Liquid mixing technology” (published by Nikkan Kogyo Shimbun, 1989)
Use the static mixer described in Chapter 8 etc.
There is a way to use. Regarding the surfactants applicable to the present invention,
Japanese Patent Laid-Open No. 11-65021, paragraph number 0132
Drop number 0133, the same paragraph number 0134 for the support, charging
For prevention or conductive layer, paragraph number 0135, color image
For how to obtain an image, refer to paragraph 0136 of the same
JP-A-11-84573, paragraphs 0061 to 0064 and Japanese Patent Application No.
No. 11-106881, paragraph numbers 0049-0062. In the present invention, a conductive layer containing a metal oxide
It is preferable to have. The conductive material of the conductive layer is metal acid
Improves conductivity by introducing oxygen defects and dissimilar metal atoms into the fluoride
The metal oxide obtained is preferably used. Examples of metal oxides
As ZnO, TiO₂ , SnO₂ Is preferred, Zn
O₂ Al, In addition, SnO₂ Against
Addition of Sb, Nb, P, halogen elements, etc., TiO₂ Vs.
Therefore, addition of Nb, Ta or the like is preferable. Add Sb in particular
SnO₂ Is preferred. The added amount of different atoms is 0.01
A range of ˜30 mol% is preferred, 0.1 to 10 mo
A range of 1% is more preferred. Metal oxide shape is spherical,
Either needle-like or plate-like may be used, but in terms of the effect of imparting conductivity
Acicular particles having a long axis / uniaxial ratio of 2.0 or more, preferably 3.0-50
Is good. The amount of metal oxide used is preferably 1 mg / m²~ 100
0mg / m²In the range, more preferably 10 mg / m²~ 500mg / m²of
Range, more preferably 20 mg / m²~ 200mg / m²In the range
The The conductive layer of the present invention is on either the emulsion surface side or the back surface side.
May be installed, but installed between support and back layer
It is preferable. Specific examples of the conductive layer of the present invention are described in JP-A-7-29.
No. 5146 and JP-A-11-223901. The present invention
Use of fluorosurfactants
That's right. Specific examples of fluorosurfactants are disclosed in JP-A-10-197985.
No., JP 2000-19680, JP 2000-214554, etc.
Compounds. Also described in JP-A-9-281636
These polymeric fluorine-based surfactants are also preferably used. Book
In the photothermographic material of the invention, Japanese Patent Application No. 2000-206560,
Japanese Patent Application 2001-203462, Japanese Patent Application 2001-242357 and Japanese Patent Application 2001
-264110 Fluorosurfactant is preferred
Yes. In particular, Japanese Patent Application No. 2001-242357 and Japanese Patent Application No. 2001-264110
The described fluorosurfactants can be coated and manufactured with aqueous coating solutions.
When performing, charge adjustment ability, stability of coated surface, smoothness
In view of this, the fluorine-based boundary described in Japanese Patent Application No. 2001-264110
Surfactants have a high charge control capability and require less usage.
This is the most preferable. In the present invention, fluorine-based surface activity
Sex agent can be used on both emulsion and back side.
It is preferable to use it on both sides. Also mentioned above
Can be used in combination with conductive layers containing metal oxides
Particularly preferred. In this case, fluorine on the surface having the conductive layer
Even if the amount of surfactant used is reduced or removed
Performance is obtained. Preferred amount of fluorosurfactant
Is 0.1 mg / m for each emulsion side and back side²~ 100mg / m²Range of
More preferably 0.3 mg / m²~ 30mg / m²Range, further
Preferably 1 mg / m²~ 10mg / m²Range. Special application 2
Fluorosurfactants described in 001-264110 are highly effective
0.01 ~ 10mg / m²Is preferably in the range of 0.1 to 5 mg / m²Range of
An enclosure is more preferred. The transparent support remains in the film during biaxial stretching.
Heat generated during thermal development processing
130-185 ° C temperature range to eliminate shrinkage strain
Heat treated polyester, especially polyethylene tele
Phthalate is preferably used. Medical photothermographic exposure
In the case of materials, the transparent support is a blue dye (for example,
It may be colored with dye-1) described in Example 240877
However, it may be uncolored. The support is disclosed in JP-A-11-84574.
Water-soluble polyester, styrene butadiene of No. 10-186565
Ene copolymer, Japanese Patent Application Laid-Open No. 2000-39684 and Japanese Patent Application No. 11-106881
Under the vinylidene chloride copolymer etc. of paragraph numbers 0063-0080
It is preferable to apply a coating technique. Also, antistatic layer
Or, as for undercoating, JP-A-56-143430 and JP-A-56-1434
31, No. 58-62646, No. 56-120519, JP-A-11-84573
No. paragraphs 0040-0051, US Pat.
The technology described in paragraph numbers 0078 to 0084 of Kaihei 11-223898
Can be applied. The photothermographic material is a monosheet type (image receiving material).
On photothermographic materials without using other sheets such as
It is preferable that the mold is capable of forming an image. The photothermographic material further includes an antioxidant.
Agent, stabilizer, plasticizer, UV absorber or coating aid
May be added. Various additives are used in the photosensitive layer or
Add to any of the non-photosensitive layers. WO98 about them
/ 36322, EP803764A1, JP-A-10-186567, 10-18
Reference can be made to No. 568. In the present invention, any photothermographic material can be used.
It may be applied by a method. Specifically, Extrusion
Coating, slide coating, curtain coating
Coating, dip coating, knife coating,
Flow coating, or US Pat. No. 2,681,294
Includes extrusion coating with the type of hopper described
Various coating operations are used, Stephen F. Kistl
er, “LIQUID FILM COATING” by Petert M. Schweizer (C
HAPMAN & HALL (1997), pages 399-536.
Crustion coating or slide coating
Are preferably used, particularly preferably a slide cord.
Ting is used. Used for slide coating
An example of the shape of the slide coater is shown on page 427 of the same book.
11b.1. If desired, pages 399 to 536
US Patent No. 2,761,791 and British Patent No. 83
Combine two or more layers by the method described in 7,095.
Sometimes it can be coated. The organic silver salt-containing layer coating solution in the present invention is
A so-called thixotropic fluid is preferred. This
As for the technology of this, refer to JP-A-11-52509.
it can. In the present invention, the organic silver salt-containing layer coating solution is shear rate.
Viscosity at a degree of 0.1S-1 is 400 mPa ・ s or more and 100,000 mPa ・ s
The following is preferable, more preferably 500 mPa · s or more and 20,00
0 mPa · s or less. Also, shear rate 1000S^-1In
Is preferably 1 mPa · s or more and 200 mPa · s or less, more preferably
It is 5 mPa · s or more and 80 mPa · s or less. Since it is used for the photothermographic material of the present invention,
As technologies that can be used, EP803764A1, EP883022A1, WO98
No. / 36322, JP-A 56-62648, 58-62644, JP-A-9-
43766, 9-281637, 9-297367, 9-304869, 9
-311405, 9-329865, 10-10669, 10-62899
10-69023, 10-186568, 10-90823, 1
0-171063, 10-186565, 10-186567, 10-186
569 to 10-186572, 10-197974, 10-197982
No., 10-197983, 10-197985 to 10-197987,
10-207001, 10-207004, 10-221807, 10-
282601, 10-288823, 10-288824, 10-30736
No. 5, No. 10-312038, No. 10-339934, No. 11-7100, No.
11-15105, 11-24200, 11-24201, 11-30832
11-84574, 11-65021, 11-109547, 1
1-125880, 11-129629, 11-133536 to 11-133
539, 11-133542, 11-133543, 11-223898
, 11-352627, 11-305377, 11-305378,
11-305384, 11-305380, 11-316435, 11-
327076, 11-338096, 11-338098, 11-33809
No. 9, No. 11-343420, No. 2000-187298, No. 2000-1022
9, 2000-47345, 2000-206642, 2000-98530
No., 2000-98531, 2000-112059, 2000-112060
, 2000-112104, 2000-112064, 2000-17193
There is also No. 6. (Description of Packaging Material) The photosensitive material of the present invention is a raw material.
To suppress fluctuations in photographic performance during storage or
Oxygen permeability and / or m
Wrapping with a packaging material with low moisture permeability is preferred
Yes. Oxygen permeability is 50ml / atm ・ m at 25 ℃²・ Day (57 × 1
0^-Tenml / Pa · m²S) is preferably
More preferably 10ml / atm · m²・ Day (11.4 × 10^-Tenm
l / Pa · m²S) or less, more preferably 1.0 ml / atm
・ M²・ Day (1.14 × 10^-Tenml / Pa · m²・ S) Below
It is. Moisture permeability is 10g / atm · m²・ Day (11.4 × 1
0^-Teng / Pa · m²S) is preferably
More preferably 5g / atm · m²・ Day (5.7 × 10^-Tenml /
Pa · m²・ S) or less, more preferably 1 g / atm · m²・ Da
y (1.14 × 10^-Tenml / Pa · m²・ S) or less
The Packaging with low oxygen permeability and / or moisture permeability
Specific examples of the material include, for example, JP-A-8-25479.
No.3. It is described in JP 2000-206653 A
Packaging material. (Explanation of heat development) What is the photothermographic material of the present invention?
It may be developed by the method, but it is usually exposed imagewise.
The developed photothermographic material is heated to be developed. Preferred development
As temperature, it is 80-250 degreeC, Preferably it is 100-140
° C, more preferably 110 to 130 ° C. Development time and
Is preferably 1 to 60 seconds, more preferably 3 to 30 seconds.
More preferably, 5 to 25 seconds and 7 to 15 seconds are particularly preferable. As a thermal development system, a drum type heater,
You can use any of the plate heaters,
A heater system is more preferable. Plate heater
What is described in Japanese Patent Application Laid-Open No. 11-133572 is the heat development method by the formula
The photothermographic material on which a latent image is formed is heat developed.
Heat to obtain a visible image by contacting the heating means
A developing device, wherein the heating means is a plate heater
And a plurality along the one surface of the plate heater
A plurality of presser rollers are arranged opposite to each other, and the presser roller and the presser roller
The photothermographic material is passed between the plate heater and the plate heater.
The thermal development apparatus is characterized by performing thermal development. The
Divide the rate heater into 2-6 stages and
It is preferable to lower the temperature by about 10 ° C. For example, independently
Use 4 sets of plate heaters that can control the temperature.
112 ° C, 119 ° C, 121 ° C, 120 ° C
An example of controlling is given. Such a method is disclosed in JP-A-54.
No.-30032, which is contained in the photothermographic material.
Moisture and organic solvents can be excluded from the system,
In addition, the heat developed by the rapid development of the photothermographic material.
It is also possible to suppress changes in the shape of the support of the image photosensitive material. The photosensitive material of the present invention can be exposed by any method.
However, laser light is preferable as the exposure light source.
As the laser beam according to the present invention, a gas laser (Ar⁺,
He-Ne), YAG laser, dye laser, semiconductor laser
Etc. are preferable. Also, semiconductor laser and second harmonic generation
A raw element or the like can also be used. Preferably red to infrared
A light emitting gas or a semiconductor laser. A medical array having an exposure section and a heat development section.
Fuji Medical Dry Laser as the imager
-Imager FM-DPL. F
For M-DP L, Fuji Medical Review No.8, p.
age 39-55, and those techniques are
Apply as a laser imager for photothermographic materials
Needless to say. In addition, the network is adapted to the DICOM standard.
Fuji Medical System as a network system
For the laser imager in the proposed "AD network"
It can also be applied as a photothermographic material. The photothermographic material of the present invention is based on a silver image.
Form black and white images, photothermographic materials for medical diagnosis, industrial
Photothermographic material for photography, Photothermographic material for printing, COM
It is preferably used as a photothermographic material. [0188] The present invention will be more specifically described with reference to the following examples.
Explained. Materials, usage, proportions, shown in the following examples
The processing contents, processing procedures, etc. are not limited as long as they do not depart from the spirit of the present invention.
Can be appropriately changed. Therefore, the scope of the present invention
The enclosure is not limited to the specific examples shown below. Example 1 <Preparation of dispersion of organic polyhalogen compound> Modified polyvinyl chloride
Nyl alcohol (Kuraray Co., Ltd. Poval MP203) 10
20kg of mass% aqueous solution and triisopropyl naphthalene
40kg of 0.4kg of 20 mass% aqueous solution of sodium fonate and 4kg of water
To a solution heated to ℃ and mixed for 3 hours with propeller stirring,
About 20 minutes of 10kg organic polyhalogen compound (Compound Example H-8)
To prepare a preliminary dispersion. This preliminary dispersion
Specific gravity of the liquid (where the specific gravity is the mass of 100 ml of the preliminary dispersion
Hereinafter, specific gravity is measured according to this definition)
Is 1.18, and the preliminary dispersion is free from visual observation.
It was. This pre-dispersion is sent with a diaphragm pump and
Horizontal sand filled with zirconia beads with a uniform diameter of 0.5 mm
Use 2 tanks in the mill (UVM-2: made by Imex Co., Ltd.)
The temperature inside the disperser is 50 ° C, stock tank with the pass method for
Light scattering particle size distribution measurement made by Shimadzu Corporation at a temperature of 50 ° C
Fixed device SALD-2000 (refractive index parameter is 1.70-0.1i
So that the median diameter measured in (4) is 0.45μm or less.
Dispersed. After dispersion is complete, heat the dispersion at 40 ° C for 5 hours.
Then benzoisothiazolinone sodium salt
Add 0.2g and water to 30 organic polyhalogen compounds.
Fuji Photo Film Co., Ltd.
Filter FC-3 (Polypropylene pore size 3.0μm filter
-) To remove foreign substances such as dust and store.
It was. Included in the polyhalogen compound dispersion thus obtained
Organic polyhalogen compound (PH-6) particles are median 0.45
The viscosity at μm, 25 ° C. was 99 cp, and the specific gravity was 1.199. Organic of the above organic polyhalogen compound H-8
In the preparation of polyhalogen solid compound dispersion PH-6,
PH-6 except that the heating temperature and heating time of the preliminary dispersion were changed
Prepare solid dispersions PH-1 to PH-5, PH-7, and PH-8 in the same manner as
(Table 1). << Evaluation of foam in coarse dispersion process >>
In a dispersion method of an aqueous solid dispersion of a halogen compound,
Specific gravity of the dispersion (measurement method is described above) and foam
Observe the state visually, evaluate it according to the following criteria, and allow ○ and ◎
The range. The results are shown in Table 1. [Standard] ◎… Preliminary dispersion is liquid, fluid and smooth
The ○: The pre-dispersion liquid is liquid but has a little fluidity. Δ: The preliminary dispersion is creamy and inferior in fluidity. × ... The pre-dispersion is whipped cream and has almost no fluidity
I'm bobbing. << Repeated reproducibility dispersion experiment >> The solid dispersion pH-1 to pH-7
In exactly the same way to confirm the reproducibility of the preparation of
Adjust pH-11 to pH17 and median as well as pH-1 to pH-7
The number of passes until the diameter became 0.45 μm or less was comparatively evaluated.
The reproducibility of the number of passes is ± 1 for pH-1 to pH-7.
The allowable range is up to The results are shown in Table 2. [0191] [Table 1] [0192] [Table 2] As shown in Tables 1 and 2, the organic compounds of the present invention
The solid dispersion manufacturing method of the present invention can efficiently remove bubbles.
The pre-dispersion process time is short and the dispersion process is repeated
It can be seen that the production stability is excellent. On the other hand, book
Under pre-dispersion conditions outside the scope of the invention, the fluidity of the dispersion is obtained.
Distribution path until the same median diameter
The number is reduced, and repeatability is not obtained.
It was. Example 2 《Preparation of solid dispersion of reducing agent (bisphenol compound)
Modified polyvinyl alcohol (Kuraray Co., Ltd., Pova
10 kg of water is added to 16 kg of 10 wt% aqueous solution of
Then, the reducing agent R-4 (6,6'-
di-t-butyl-4,4'-dimethyl-2,2'-butylidene diphe
Knoll) 10kg gradually added and stirred well for 3 hours
Was used as a preliminary dispersion. This predispersion is used as a diaphragm
And filled with zirconia beads with an average diameter of 0.5 mm.
Filled horizontal sand mill (UVM-2: Imex Co., Ltd.)
, Distributed by the path method using two tanks, manufactured by Shimadzu Corporation
Light scattering particle size distribution analyzer SALD-2000 (refractive index parameter)
The meter median diameter is 1.70-0.1i)
It was dispersed so as to fall within the range of 0.45 μm to 0.51 μm. dispersion
After completion, add 0.2 g of sodium benzoisothiazolinone and water
In addition, adjust the concentration of the reducing agent to 25% by mass and return it.
A base agent dispersion (PR-6) was obtained. The reducing agent dispersion thus obtained
Reducing agent particles contained in the median diameter 0.46μm, the largest particles
The diameter was 1.5 μm or less. The resulting reducing agent dispersion has a pore size of 3.
Filter with a 0 μm polypropylene filter
Foreign matter such as mist was removed and stored. Preparation of the solid dispersion PR-6 of the above reducing agent R-4
The same as PR-6 except that the pre-dispersion condition was changed.
In the same manner, solid dispersions PR-1 to PR-5 were prepared. The reducing agent R-
Change to a different reducing agent represented by general formula (R) instead of 4.
Prepare solid dispersions PR-7 to PR-8 prepared in the same manner as above.
did. The evaluation method of the preliminary dispersion is the organic polymer of Example 1.
It carried out like the solid dispersion of the rogen compound. Table 3 shows the results.
Shown in [0196] [Table 3] As shown in Table 3, the organic compound of the present invention is solidified.
The method for producing a body dispersion is effective because the foam can be removed efficiently.
The dispersion process time is short and the repeatability of the dispersion process is repeatable.
It can be seen that the production stability is excellent. Example 3 《Hydrogen bondability capable of hydrogen bonding with bisphenol compounds》
Preparation of solid dispersion of compound >> modified polyvinyl alcohol
10% aqueous solution (Poval MP203, manufactured by Kuraray Co., Ltd.) 1
Add 6Kg to 10Kg water and keep at 60 ° C for hydrogen bonding
Compound D-7 (tri (4-t-butylphenyl) phosphite
) 10Kg is added gradually and mixed well for 3 hours.
A preliminary dispersion was obtained. This pre-dispersion is used as a diaphragm pump.
And then filled with zirconia beads with an average diameter of 0.5 mm
Horizontal sand mill (UVM-2: made by Imex Co., Ltd.)
The temperature in the disperser is 38 ° C using a two-tank pass method.
The light scattering particle size distribution measurement made by Shimadzu Corporation
Fixed device SALD-2000 (refractive index parameter is 1.70-0.1i
So that the median diameter measured in step 4) is 0.40 μm or less.
Dispersed. Here, the temperature in the disperser is discharged from the disperser.
The temperature of the dispersion immediately after being taken out was measured. After the distribution ends
The dispersion was heat treated at 60 ° C. for 24 hours to obtain benzoisothiazolino
Concentration of reducing agent is 25 mass by adding 0.2g sodium salt and water
% To prepare a hydrogen bonding compound dispersion (PD-
5) got. Reduction contained in the reducing agent dispersion thus obtained
The agent particles have a median diameter of 0.38 μm and a maximum particle diameter of 1.5 μm or less.
there were. The resulting hydrogen bonding compound dispersion has a pore size of 3.0 μm.
Filtered with a polypropylene filter of trash, etc.
The foreign matter was removed and stored. Solid dispersion of the above hydrogen bonding compound D-7
In the preparation of PD-5, disperser heating conditions and stock
Solid as in PD-5, except for changing the tank heating conditions
Dispersions PD-1 to PD-4 were prepared. In addition, hydrogen bonding compounds
Another hydrogen bond represented by general formula (D) instead of D-7
Solid dispersion PD-6 prepared in the same manner as above except that the compound was changed
~ PD-7 was prepared (Table 4). Evaluation method of solid dispersion
Is a solid dispersion of the organic polyhalogen compound of Example 1 and
The same was done. The results are shown in Table 4. [0199] [Table 4] As shown in Table 4, the organic compound of the present invention is solidified.
The method for producing a body dispersion is effective because the foam can be removed efficiently.
The dispersion process time is short and the repeatability of the dispersion process is repeatable.
It can be seen that the production stability is excellent. Example 4 Creating a solid dispersion <Preparation of dispersion of photographically useful compound> Modified polyvinyl alcohol
10% water by weight of coal (Kuraray Co., Ltd. Poval MP203)
20 kg of solution and sodium triisopropylnaphthalenesulfonate
Add 0.4kg of 20% by weight aqueous solution of thorium and 4kg of water at room temperature.
Add the organic polyhalogen compound to the solution
10 kg of Compound-2 (Compound Example H-8) was added over about 20 minutes,
A preliminary dispersion was prepared. Those who show this preliminary dispersion in Table 5
After defoaming by the method, liquid is sent with a diaphragm pump and averaged
Horizontal sand mill filled with 0.5 mm zirconia beads
(UVM-2: made by Imex Co., Ltd.)
It was. After that, the temperature during dispersion is reduced to 3 using a 2-tank pass method.
5 ℃, Shimadzu Corporation Co., Ltd. Light scattering particle size
Cloth measuring device SALD-2000 (refractive index parameter is 1.70-0.1i
The median diameter measured in step 2) is 0.50μm or less.
Dispersed. Here, the temperature inside the disperser is
The temperature of the dispersion immediately after being discharged was measured. After dispersion,
Nsoisothiazolinone sodium salt 0.2g and water
Adjust the concentration of the polyhalogen compound to 30% by mass.
Manufactured by Fuji Photo Film Co., Ltd. Filter FC-3
Filtered with a polypropylene resin pore size 3.0μm filter)
Foreign matter such as dust was removed and stored. The above organic polyhalogen compound is represented by the general formula
Organic polyhalogenation represented by (R) and general formula (D)
Compound, bisphenol compound, bisphenol compound and
Change to a hydrogen-bonding compound capable of hydrogen bonding and adjust the dispersion.
Arranged. The results are shown in Table 5. Example of solid dispersion evaluation
1 was performed. [0203] [Table 5] As shown in Table 5, the organic compounds of the present invention
The method for producing a solid dispersion can remove bubbles efficiently.
Short pre-dispersion process time and repeatability of dispersion process
It can be seen that the production stability is excellent. Also, above
In a method for producing a solid dispersion of a horizontal sand mill (UVM
-2: Agitator Mill L instead of Imex Co., Ltd.
A similar dispersion can be obtained using MK (Ajisawa).
It was. Example 5 <Stability and filterability of solid dispersion over time> Prepared in Example 1
Comparison of organic polyhalogen compound dispersion PH-6 of the present invention
Stability of organic polyhalogen compound dispersion PH-1 with time
And filterability were evaluated. In addition, the present invention prepared in Example 2
Bright phenolic compound dispersion PR-6, comparative pheno
Dispersion PR-1 of the polyol compound, the present invention prepared in Example 3
Dispersion of compounds capable of hydrogen bonding with other phenolic compounds
PD-6, capable of hydrogen bonding with phenolic compounds of comparative examples
The stability over time and filterability of the dispersion PD-1 were evaluated. << Evaluation of stability over time >>
The qualitative property is that 100 ml of the solid dispersion of each compound obtained is
Visually check the condition before and after aging at 40 ° C for 1 week.
Measure and measure the HPLC concentration at the top and bottom of the container.
However, an acceptable range was 2 or more. The results are shown in Table 6.
The [State standard] 3. No change in the dispersion state before and after aging. 2: Slight wrinkles in the dispersed liquid. 1 ... The dispersion and creamy foam separated before and after aging. [HPLC concentration standard] 3 ... Concentration difference between the top and bottom of the container before and after aging is within 1% 2… Concentration difference between upper and lower containers before and after aging is 1-2% 1… Concentration difference between the top and bottom of the container before and after aging is 2% or more <Evaluation method of filterability> Solid dispersion of each of the above compounds
Each 1Kg was put in a plastic bottle and after one week at 40 ℃, Fuji
Photo filter made of polypropylene with a pore size of 3μm
-Filter with FC-3, evaluate according to the following criteria, accept ○
The range. Table 6 shows the results. [Standard] ○: The total amount of 1kg dispersion can be filtered, and there is no problem. ×: Filtration clogged and cannot be used. [0207] [Table 6]As shown in Table 6, prepared by the manufacturing method of the present invention.
The solid dispersion has excellent stability over time and filterability.
I understand that Example 6 Preparation of photosensitive material (Preparation of PET support) Terephthalic acid and ethylene glycol
Inherent viscosity IV = 0.66 (phenol / t
PET measured at 25 ° C in trachlorethane = 6/4 (mass ratio)
Got. After pelletizing this, it was dried at 130 ° C for 4 hours,
After melting at 300 ° C, extruded from a T-die and quenched, after heat setting
Make an unstretched film with a thickness of 175μm.
Made. [0209] This is 3.3 times using a roll with different peripheral speeds.
And then stretched 4.5 times with a tenter.
It was. The temperatures at this time were 110 ° C. and 130 ° C., respectively.
After this, heat set at 240 ° C for 20 seconds and then at the same temperature sideways
Eased 4%. After this, slip the tenter chuck.
And then knurled at both ends and wound up at 4kg / cm2.
As a result, a roll having a thickness of 175 μm was obtained. (Surface corona treatment) Solids manufactured by Pillar
Tate corona treatment machine 6KVA model, using both sides of the support
Treated at room temperature at 20 m / min. Current and voltage at this time
From the reading of 0.375kV ・ A ・ min / m for the support²Where
It turns out that the reason is being done. Processing frequency at this time
Is 9.6kHz, gap clearance between electrode and dielectric roll
Was 1.6 mm. [0211] (Create an undercoat support) (1) Preparation of undercoat layer coating solution Formula (1) (for photosensitive layer side undercoat layer)   65 g of pesresin A-520 (30% by mass solution) manufactured by Takamatsu Yushi Co., Ltd.   Polyethylene glycol monononyl phenyl ether     (Average number of ethylene oxide = 8.5) 10% by mass dissolved 5.0 g   MP-1000 (polymer fine particle, average particle size 0.4μm) 1.1g made by Soken Chemical Co., Ltd.   935ml distilled water [0212] Formula (2) (for back layer 1st layer)   160g of styrene-butadiene copolymer latex   (Solid content 40% by mass, styrene / butadiene mass ratio = 68/32)   2,4-dichloro-6-hydroxy-S-     Triazine sodium salt 8% by weight aqueous solution 20g   10% 1% by weight aqueous solution of sodium laurylbenzenesulfonate   Distilled water 855ml [0213] Formula (3) (for back side second layer)   SnO₂/ SbO (9/1 mass ratio, average particle size 0.038μm, 17 mass% dispersion) 80g   Gelatin (10% by weight aqueous solution) 89.g   Metrows TC-5 (2% by weight aqueous solution) manufactured by Shin-Etsu Chemical Co., Ltd.8.6g   MP-1000 0.01g manufactured by Soken Chemical Co., Ltd.   10% 1% by weight aqueous solution of sodium dodecylbenzenesulfonate   NaOH (1% by mass) 6ml   Proxel (made by ICI) 1ml   805ml of distilled water [0214] Biaxially stretched polyethylene having a thickness of 175 µm.
On both sides of the terephthalate support.
After the discharge treatment, the above undercoat is applied to one side (photosensitive layer side)
The coating amount of the coating solution (1) is 6.
6ml / m²Apply at 180 ° C to apply (per side) 5
Dry for a minute and then apply the undercoat on the back (back)
The coating amount of the coating solution (2) with a wire bar is 5.
7ml / m²And apply at 180 ° C for 5 minutes.
On the back side (back side), apply the above undercoat coating liquid formulation (3).
Wet application amount with ear bar is 7.7ml / m²Painted to be
Fabric and dry at 180 ° C for 6 minutes to produce an undercoat support.
It was. (Preparation of back surface coating solution) (Preparation of solid fine particle dispersion (a) of base precursor) Salt
1.5 kg of the group precursor compound-1 and the surface activity
Sex agent (trade name: Demol N, manufactured by Kao Corporation) 225g
937.5 g of phenylsulfone, parahydroxybenzoate
To 15 g of chill ester (trade name: Plating, made by Ueno Pharmaceutical)
Add distilled water and mix to a total volume of 5.0 kg.
Horizontal sand mill (UVM-2: made by Imex Co., Ltd.)
Was used to disperse the beads. Dispersion method averages the mixture
Diaphragm is added to UVM-2 filled with 0.5 mm diameter zirconia beads.
In a state where the internal pressure is 50 hPa or higher,
Dispersion until desired average particle size was obtained. Dispersion
450 nm in spectral absorption of the dispersion was measured by optical absorption measurement
Ratio of absorbance at 650nm to absorbance at 650nm (D450 / D65
0) was dispersed up to 2.2 or more. Obtained
The dispersion is 20% by mass at the concentration of the base precursor.
Dilute with distilled water and filter to remove dust (average fine
(Pore size: 3 μm polypropylene filter)
Used for practical use. (Preparation of dye solid fine particle dispersion) Cyanine
6.0 kg of dye compound-1 and p-dodecylbenzenesulfur
Sodium fonate 3.0kg, Kao Corp. surfactant
Mole SNB 0.6kg and antifoaming agent (trade name: Surfy
Nord 104E, manufactured by Nissin Chemical Co., Ltd.) 0.15kg distilled water
To make the total liquid volume 60 kg. Mix the mixed solution horizontally
Und mill (UVM-2: made by Imex Co., Ltd.)
Dispersed with 0.5 mm zirconia beads. The dispersion is
Spectral absorption measurements were taken to determine the dispersion's spectral absorption at 650n.
Ratio of absorbance at m to absorbance at 750nm (D650 / D75
0) was dispersed up to 5.0 or more. Obtained
The dispersion should be 6% by weight in terms of cyanine dye concentration.
Dilute with distilled water and filter to remove dust (flat
(Equal pore diameter: 1 μm) for practical use. (Preparation of antihalation layer coating solution) Zera
30 g of tin, 24.5 g of polyacrylamide, 1 mol / l of caustic
2.2 g of monodisperse polymethyl methacrylate fine particles (flat
Average particle size 8μm, particle size standard deviation 0.4) 2.4g, benzo
Isothiazolinone 0.08g, the above dye solid fine particle dispersion 35.
9 g of the above-mentioned base precursor solid fine particle dispersion (a) 74.
2g, Sodium polyethylene sulfonate 0.6g, Blue dye
0.21 g of compound-1, 0.15 g of yellow dye compound-1
Crylic acid / ethyl acrylate copolymer latex
(Total ratio 5/95) 8.3 g was mixed and the whole was 8183 with water.
An antihalation layer coating solution was prepared. (Preparation of back surface protective layer coating solution)
Incubate at 40 ° C and flow gelatin 40g, liquid paraffin emulsion.
1.5g as moving paraffin, 35m benzoisothiazolinone
g, 1 mol / l caustic 6.8 g, t-octylphenoxy
Sodium ethoxyethanesulfonate 0.5g, polystyrene
Sodium sulfonate sulfonate 0.27g, fluorosurfactant
(F-1: N-perfluorooctylsulfonyl-N-propyl
Lopyranalanine potassium salt) 37mg, fluorinated surfactant
(F-2: Polyethylene glycol mono (N-perfluo
Looctylsulfonyl-N-propyl-2-aminoethyl)
Ether [ethylene oxide average polymerization degree 15]) 150mg,
Nitrogen-based surfactant (F-3) 64 mg, fluorinated surfactant
(F-4) 32 mg, acrylic acid / ethyl acrylate copolymer
Copolymer (copolymerization mass ratio 5/95) 6.0g, N, N-ethylenebis
(Vinylsulfone acetamide) 2.0g is mixed, and 1 with water
The back surface protective layer coating solution was made 0 liters. (Preparation of silver halide emulsion) <Preparation of silver halide emulsion 1> 1% by mass in 1421 ml of distilled water
Add 3.1 ml of potassium bromide solution and add 0.5 mol / L
Add a solution containing 3.5 ml of sulfuric acid and 31.7 g of phthalated gelatin.
Maintain the liquid temperature at 30 ° C while stirring in a Tenres reaction vessel.
That is, a solution diluted to 95.4ml by adding distilled water to 22.22g of silver nitrate
A, 15.3 g of potassium bromide and 0.8 g of potassium iodide are distilled water.
Solution B diluted to 97.4 ml with a constant flow rate for 45 seconds
The whole amount was added. Then, 3.5 mass% hydrogen peroxide water
Add 10 ml of the solution, and then add 10 mass of benzimidazole
10.8 ml of% aqueous solution was added. Furthermore, steam to 51.86 g of silver nitrate.
Solution C diluted to 317.5 ml with the addition of distilled water and potassium bromide 4
Dilute 4.2g and potassium iodide 2.2g with distilled water to 400ml capacity
Solution D is the total amount of solution C over 20 minutes at a constant flow rate.
Added, solution D controlled while maintaining pAg at 8.1
It added by the dodder jet method. 1 x 10 per mole of silver^-Four
So that potassium hexachloroiridate (III)
10 minutes after starting to add Solution C and Solution D
Added. In addition, 6 cyan after 5 seconds from the end of addition of solution C
An aqueous solution of potassium iron (II) iodide at 3 x 10 per mole of silver^-FourAll moles
An amount was added. Adjust the pH to 3.8 using 0.5 mol / L sulfuric acid.
And the stirring was stopped, and the sedimentation / desalting / water washing step was performed.
Adjusted to pH 5.9 with 1 mol / L sodium hydroxide
Then, a silver halide dispersion having a pAg of 8.0 was prepared. While stirring the above silver halide dispersion, 38
0.34% by weight of 1,2-benzisothiazoline maintained at ℃
Add 5 ml of -3-one methanol solution, and after 40 minutes spectral sensitization
A 1: 1 methanol solution with a molar ratio of dye A and sensitizing dye B
1.2 × 10 as the sum of sensitizing dyes A and B per mole of silver^-3
Mole was added and the temperature was raised to 47 ° C. after 1 minute. 20 minutes after the temperature rise
Sodium nzenthiosulfonate in methanol solution with silver
7.6 x 10 per mole^-FiveAdd 5 moles and add 5 minutes later
Sensitizer B in methanol solution with 2.9 x 10 per mole of silver^-Four
Mole was added and aged for 91 minutes. N, N’-Dihydroxy-N ”-
Add 1.3 ml of 0.8% by weight methanol solution of diethylmelamine
After another 4 minutes, 5-methyl-2-mercaptobenzoimi
Dazole in methanol solution 4.8 x 10 per mole of silver^-3
Mole and 1-phenyl-2-heptyl-5-mercapto-1,3,4-
Triazole is 5.4 in 1 mol of silver with methanol solution.
× 10^-3A silver halide emulsion 1 was prepared by adding a molar amount. The grains in the prepared silver halide emulsion are:
Average sphere equivalent diameter 0.042μm, sphere equivalent diameter variation coefficient 20%
Silver iodobromide grains uniformly containing 3.5 mol% of copper. grain
The child size is the average of 1000 particles using an electron microscope.
Asked. The [100] face ratio of this particle is
80% using the method. << Preparation of silver halide emulsion 2 >> Halogenation
In the preparation of silver emulsion 1, the liquid temperature at the time of grain formation was 30 ° C to 47 ° C
In Solution B, 15.9 g of potassium bromide is stored in distilled water.
Changed to dilute to 97.4 ml and solution D was potassium bromide
Changed to dilute 45.8g of water to 400ml with distilled water
Then, the addition time of solution C was 30 minutes, and hexacyanoferrate (II) potassium was added.
Silver halide emulsion in the same manner except that the palladium was removed
2 was prepared. Same as silver halide emulsion 1
Desalting / washing / dispersion was performed. Furthermore, spectral sensitizing dye A and spectral
Amount of 1: 1 methanol solution added in the molar ratio of sensitizing dye B
As the sum of sensitizing dye A and sensitizing dye B per mole of silver
7.5 × 10^-FourMole, tellurium sensitizer B was added in 1 mole of silver
1.1 × 10^-FourMole, 1-phenyl-2-heptyl-5-mercap
Of 1,3,4-triazole 3.3 × 10 per mole of silver^-3Mo
Spectral sensitization and chemical sensitization in the same way as Emulsion 1 except that
Sensation and 5-methyl-2-mercaptobenzimidazole, 1-
Phenyl-2-heptyl-5-mercapto-1,3,4-triazol
The silver halide emulsion 2 was obtained. halogen
The emulsion grains of silver halide emulsion 2 have an average equivalent sphere diameter of 0.080 μm and a spherical phase.
It was pure silver bromide cubic grains with a coefficient of variation of 20%. << Preparation of silver halide emulsion 3 >> Halogenation
In the preparation of silver emulsion 1, the liquid temperature at the time of grain formation is 30 ° C.
The silver halide emulsion 3 was prepared in the same manner except that
Made. In addition, as with the silver halide emulsion 1, precipitation /
Desalting / washing / dispersion was performed. Spectral sensitizing dye A and spectral sensitization
Solid dispersion (gelatin aqueous solution) with a molar ratio of dye B of 1: 1
Sensitizing dye A and sensitizing dye B per mole of silver
6 × 10 as the sum of^-3Mol, tellurium sensitizer C addition amount
5.2 x 10 per mole of silver^-FourChange to mole and add tellurium sensitizer
After 3 minutes of addition, 5 x 10 bromoauric acid per mole of silver^-FourMol and Chi
2x10 potassium ocyanate per mole of silver ^-3Mole
The silver halide was the same as Emulsion 1 except that it was added.
Emulsion 3 was obtained. The emulsion grains of silver halide emulsion 3 are average
Iodine with a sphere equivalent diameter of 0.034 μm and a sphere equivalent diameter variation coefficient of 20%
The silver iodobromide grains uniformly contained 3.5 mol%. << Preparation of Mixed Emulsion A for Coating Solution >> Halogenation
70% by weight of silver emulsion 1, 15% by weight of silver halide emulsion 2,
Dissolve 15% by mass of silver halide emulsion 3 and add benzothiazolyl
7x per mole of silver in 1% by weight aqueous solution
Ten^-3Mole was added. Further, 1 kg of mixed emulsion for coating solution
The silver halide content is 38.2g as silver.
Watered. [Preparation of fatty acid silver dispersion A] Henkel
Behenic acid (product name Edenor C22-85R) 87.6Kg, distilled water 423
L, 49.2L of 5mol / L NaOH aqueous solution, t-butyl alcohol
120 L was mixed and stirred at 75 ° C for 1 hour to react.
Sodium acid solution A was obtained. Separately, 40.4 kg of silver nitrate water
206.2 L (pH 4.0) of a solution was prepared and kept warm at 10 ° C. 635
Reaction volume containing L distilled water and 30 L t-butyl alcohol
Keep the vessel at 30 ° C and stir well with the previous sodium behenate.
Constant flow rate of all thorium solution A and silver nitrate aqueous solution
At 93 minutes 15 seconds and 90 minutes respectively. At this time,
Only the aqueous silver nitrate solution is added for 11 minutes after the addition of the aqueous silver nitrate solution is started.
And then sodium behenate solution A
14 minutes and 15 seconds after the addition of the aqueous silver nitrate solution
Ensure that only sodium behenate solution A is added.
It was. At this time, the temperature in the reaction vessel is 30 ° C., and the liquid temperature is
The outside temperature was controlled to be constant. Also behen
Pipe for sodium acid solution A addition system outside the double pipe
Warm water is circulated to keep the addition nozzle tip out.
The liquid temperature in the mouth was adjusted to 75 ° C. Also, silver nitrate water
Pipe for solution addition system circulates cold water outside the double pipe
To keep warm. Addition of sodium behenate solution A
And the addition position of the aqueous silver nitrate solution centered on the stirring axis
Symmetrical arrangement and height not to contact the reaction solution
Prepared. After completion of the addition of sodium behenate solution A,
Stir at the same temperature for 20 minutes, then increase to 35 ° C over 30 minutes
The temperature was raised, and then aging was performed for 210 minutes. Immediately after ripening
Next, the solid content is separated by centrifugal filtration, and the solid content is transferred to the filtered water.
The water was washed until the degree reached 30 μS / cm. Thus fatty acid silver salt
Got. Do not dry the resulting solids.
Stored as a key. The morphology of the obtained silver behenate particles was examined with an electron microscope.
When evaluated by mirror photography, the average value was a = 0.14μm, b =
0.4μm, c = 0.6μm, average aspect ratio 5.2, average spherical phase
A flake-shaped bond with a diameter of 0.52μm and a coefficient of variation of 15% of the equivalent sphere diameter.
It was a crystal. (A, b, and c are the provisions of the text) A wet cake equivalent to a dry solid content of 260 kg
In contrast, polyvinyl alcohol (trade name: PVA-217) 19.3K
Add g and water to bring the total volume to 1000Kg, then diso
Slurry with luber blades and further pipeline mixer
Pre-dispersed by (Mizho Kogyo Co., Ltd .: PM-10 type). Next, the pre-dispersed stock solution is dispersed into a disperser (commercial product).
Name: Microfluidizer M-610, Microfull
Idex International Corporation
Made by Z-type interaction chamber)
60kg / cm²Adjusted to 3 times, processed silver behenate dispersion
Got. Cooling operation interacts with serpentine heat exchanger
Attach before and after the chamber to adjust the temperature of the refrigerant
The dispersion temperature was set to 18 ° C. << Preparation of fatty acid silver dispersion B >> <Preparation of recrystallized behenic acid> Henkel behenic acid (product
Name Edenor C22-85R) 100Kg, 1200Kg isopropyl alcohol
Mix in liqueur, dissolve at 50 ° C, and filter with 10μm
After filtration, the mixture was cooled to 30 ° C. and recrystallized. Reunion
The cooling speed when crystallizing is controlled at 3 ℃ / hour.
I did. The obtained crystals are filtered by centrifugal filtration, and 100 kg of isopru
After washing with pill alcohol and drying
It was. When the obtained crystals were esterified and GC-FID measurement was performed
At the same time, the silver behenate content was 96%.
It contained 2% acid and 2% arachidic acid. <Preparation of fatty acid silver dispersion B> 88 kg of recrystallized behenic acid, distilled
422 L of water, 49.2 L of 5 mol / L NaOH aqueous solution, t-butyl alcohol
Mix 120L of lecol and stir at 75 ° C for 1 hour to react.
To obtain a sodium behenate solution B. Separately, silver nitrate 40.
Prepare 206.2L of 4kg aqueous solution (pH4.0) and keep it warm at 10 ℃
It was. Add 635L distilled water and 30L t-butyl alcohol
Keep the reaction vessel at 30 ° C and stir well while mixing
The total amount of sodium henate solution B and the total amount of silver nitrate aqueous solution
They were added at a constant flow rate over 93 minutes 15 seconds and 90 minutes, respectively. This
11 minutes after the start of silver nitrate aqueous solution addition
Only be added, and then sodium behenate
14 minutes after the addition of the aqueous solution of silver nitrate
Only sodium behenate solution B is added for 5 seconds
I made it. At this time, the temperature in the reaction vessel is 30 ° C., and the liquid temperature
The external temperature was controlled so that the degree was constant. Also,
The pipe for the addition system of sodium henate solution B is outside the double pipe.
Keep warm by circulating hot water to the side, tip of the addition nozzle
The liquid temperature at the outlet was adjusted to 75 ° C. Nitric acid
The piping of the addition system of the silver aqueous solution circulates cold water outside the double pipe
To keep warm. Sodium behenate solution B
The addition position of the silver nitrate solution and the addition position of the silver nitrate aqueous solution are centered on the stirring axis.
So that it is symmetrical and does not come into contact with the reaction solution.
Adjusted to height. After the addition of sodium behenate solution B,
Stir at the same temperature for 20 minutes, then increase to 35 ° C over 30 minutes
The temperature was raised, and then aging was performed for 210 minutes. Immediately after ripening
Next, the solid content is separated by centrifugal filtration, and the solid content is transferred to the filtered water.
The water was washed until the degree reached 30 μS / cm. Thus fatty acid silver salt
Got. Do not dry the resulting solids.
Stored as a key. The morphology of the resulting silver behenate particles was examined by electron microscopy.
When evaluated by mirror photography, the average value was a = 0.21μm, b =
0.4μm, c = 0.4μm, average aspect ratio 2.1, average spherical phase
This is a crystal with a diameter of 0.51μm and a sphere equivalent diameter variation coefficient of 11%.
It was. (A, b, c are the provisions of the text) A wet cake equivalent to a dry solid content of 260 kg
In contrast, polyvinyl alcohol (trade name: PVA-217) 19.3K
Add g and water to bring the total volume to 1000Kg, then diso
Slurry with luber blades and further pipeline mixer
Pre-dispersed by (Mizho Kogyo Co., Ltd .: PM-10 type). Next, the pre-dispersed stock solution is dispersed into a disperser (product).
Name: Microfluidizer M-610, Microfull
Idex International Corporation
Made by Z type interaction chamber)
50kg / cm²Adjusted to 3 times, processed silver behenate dispersion
Got. Cooling operation interacts with serpentine heat exchanger
Attach before and after the chamber to adjust the temperature of the refrigerant
The dispersion temperature was set to 18 ° C. (Preparation of reducing agent dispersion) << Preparation of Reducing Agent Complex-1 Dispersion >> Reducing Agent Complex-1 (6,
6'-di-t-butyl-4,4'-dimethyl-2,2'-butylidene
1: 1 phenol and triphenylphosphine oxide
Complex) 10Kg, triphenylphosphine oxide 0.12Kg
And modified polyvinyl alcohol (Kuraray Co., Ltd., Pova
10 kg of water is added to 16 kg of 10 wt% aqueous solution of
Mix well to obtain a preliminary dispersion. This preliminary dispersion
Zirco with an average diameter of 0.5 mm, delivered by a diaphragm pump
Horizontal sand mill filled with near beads (UVM-2: Aimee
While cooling to 40 ° C or lower during dispersion with
After 4 hours and 30 minutes of dispersion, benzoisothiazolinone sodium
Add 0.2g of lithium salt and water to reduce the concentration of the reducing agent to 22% by mass.
Thus, a reducing agent complex-1 dispersion was obtained. This way
The reducing agent complex particles contained in the reducing agent complex dispersion obtained in
The dianne diameter was 0.45 μm, and the maximum particle diameter was 1.4 μm or less. Gain
The resulting reducing agent complex dispersion is polypropylene with a pore size of 3.0 μm.
Filter with a filter to remove foreign substances such as dust
Stowed. << Preparation of Reducing Agent-2 Dispersion >> Reducing Agent-2
(6,6'-di-t-butyl-4,4'-dimethyl-2,2'-butylide
Diphenol) 10 kg and modified polyvinyl alcohol
16kg 10% aqueous solution of Laval Co., Poval MP203)
Add 10 kg of water and mix well to make a preliminary dispersion.
It was. This pre-dispersion is sent with a diaphragm pump and
Horizontal sand filled with zirconia beads with a uniform diameter of 0.5 mm
3 hours and 30 minutes in the mill (UVM-2: made by Imex Co., Ltd.)
After dispersion, 0.2 g of benzoisothiazolinone sodium salt
And water are added so that the concentration of the reducing agent is 25% by mass.
Thus, a reducing agent-2 dispersion was obtained. Reducing agent dispersion obtained in this way
Reducing agent particles contained in the product have a median diameter of 0.40 μm and the largest particles
The child diameter was 1.5 μm or less. The resulting reducing agent dispersion is porous.
Filtration through a polypropylene filter with a diameter of 3.0 μm
Foreign matter such as dust was removed and stored. << Preparation of Hydrogen Bonding Compound-1 Dispersion >> Water
Elemental binding compound-1 (tri (4-t-butylphenyl)
Phosphine oxide) 10Kg and modified polyvinyl alcohol
10% by weight aqueous solution 16K (Kuraray Co., Ltd., Poval MP203)
Add 10 kg of water to g and mix well to make a preliminary dispersion.
It was. This pre-dispersion is sent with a diaphragm pump and
Horizontal sand filled with zirconia beads with a uniform diameter of 0.5 mm
3 hours 30 minutes at the mill (UVM-2: made by Imex Co., Ltd.)
After dispersion, benzoisothiazolinone sodium salt 0.
Add 2 g and water to adjust the concentration of the reducing agent to 25% by mass.
To obtain a hydrogen bonding compound-1 dispersion. Thus obtained
The reducing agent particles contained in the reducing agent dispersion have a median diameter of 0.35.
The maximum particle size was 1.5 μm or less. Hydrogenation obtained
The compatible compound dispersion is a polypropylene film having a pore size of 3.0 μm.
Filter with a filter to remove foreign substances such as dust and store.
It was. << Development Accelerator-1 Preparation of Dispersion >> Development Acceleration
10 kg of Agent-1 and modified polyvinyl alcohol (Kuraray Co., Ltd.)
Made by Poval MP203), 10kg water
Was added and mixed well to obtain a preliminary dispersion. This spare
Dispersion liquid is sent by diaphragm pump, average diameter 0.5mm
Horizontal sand mill filled with zirconia beads (UVM-
2: Made by IMEX Co., Ltd.)
Benzisothiazo after dispersing for 3 hours 30 minutes
The concentration of reducing agent is 20 with the addition of 0.2 g linone sodium salt and water.
Prepared so as to be a mass%, and obtained a development accelerator-1 dispersion.
It was. The reducing agent particles contained in the reducing agent dispersion thus obtained are
The median diameter was 0.48 μm, and the maximum particle size was 1.4 μm or less.
The resulting reducing agent dispersion is made of polypropylene with a pore size of 3.0 μm.
Filter with a filter to remove foreign substances such as dust.
I paid. Development accelerator-2, development accelerator 3 and color tone
The solid dispersion of modifier-1 is the same as development accelerator-1.
Dispersion was carried out by the same method to obtain a 20 mass% dispersion. (Preparation of dispersion of polyhalogen compound) << Preparation of organic polyhalogen compound-1 dispersion >>
Halogen compound-1 (tribromomethanesulfonylben
Zen) 10kg modified polyvinyl alcohol (Kuraray Co., Ltd.)
10 kg of 20% by weight aqueous solution of Poval MP203) and triisopropyl
20% by mass aqueous solution of sodium lopyrnaphthalenesulfonate
Add 0.4kg of liquid and 14kg of water and mix well.
These were combined into a preliminary dispersion. This preliminary dispersion is used as a diaphragm.
Zirconia beads with an average diameter of 0.5 mm
Type horizontal sand mill (UVM-2: Imex
Benzisothiazoli after 5 hours dispersion
Organic polyhalogenation by adding 0.2 g of non-sodium salt and water
Prepare a compound with a concentration of 26% by mass,
Rogen compound-1 dispersion was obtained. The polyhalo thus obtained
Organic polyhalogen compound grains contained in a gen compound dispersion
The child has a median diameter of 0.41 μm and a maximum particle size of 2.0 μm or less.
It was. The resulting organic polyhalogen compound dispersion has a pore size of 10.0.
Filter with a μm polypropylene filter
Foreign matter such as mist was removed and stored. << Preparation of organic polyhalogen compound-2 dispersion
Product >> Organic polyhalogen compound-2 (N-butyl-3-to
Libromomethanesulfonylbenzoamide) 10kg
1 of Livinyl alcohol (Kuraray Co., Ltd. Poval MP203)
20kg of 0 mass% aqueous solution and triisopropyl naphthalene
Mixed dissolution with 0.4kg of 20% aqueous solution of sodium sulfonate
It was added to the liquid and mixed well to obtain a preliminary dispersion. This schedule
The dispersion liquid is fed with a diaphragm pump, and the average diameter is 0.5 m.
Horizontal sand mill filled with zirconia beads (UVM-
2: Median diameter is 0.35μm by Imex Co., Ltd.
After dispersing until below, heat treatment at 40 ° C for 5 hours
And 0.2 g of benzoisothiazolinone sodium salt and water
In addition, the concentration of the organic polyhalogen compound is 30% by mass.
To prepare an organic polyhalogen compound-2 dispersion.
Obtained. Included in the polyhalogen compound dispersion thus obtained.
The organic polyhalogen compound particles have a median diameter of 0.40 μm,
The maximum particle size was 1.3 μm or less. Obtained organic polyhalo
Gen compound dispersion is a polypropylene film with a pore size of 3.0μm.
Filter with a filter to remove foreign substances such as dust and store.
It was. << Preparation of Phthalazine Compound-1 Solution >> 8 kg
1 made of modified polyvinyl alcohol MP203 made by Kuraray Co., Ltd.
Dissolved in 74.57Kg, then triisopropylnaphthalene
3.15 kg of 20% by weight aqueous solution of sodium sulfonate and phthala
70 masses of gin compound-1 (6-isopropylphthalazine)
14% 28% aqueous solution was added to the phthalazine compound-1
A volume% solution was prepared. (Preparation of mercapto compound) << Preparation of Mercapto Compound-1 Aqueous Solution >> Mercapto Compound
-1 (1- (3-sulfophenyl) -5-mercapto
7 g of tetrazole sodium salt) is dissolved in 993 g of water and 0.
A 7% by mass aqueous solution was obtained. << Preparation of Mercapto Compound-2 Aqueous Solution >>
Lucapto compound-2 (1- (3-methylureido) -5
-Mercaptotetrazole sodium salt) 20g in water 980
Dissolved in g to give a 2.0 mass% aqueous solution. << Preparation of Pigment-1 Dispersion >> C.I. Pigment Bl
64 g of ue 60, 6.4 g of Kao's Demol N, and 250 g of water
And mixed well to obtain a preliminary dispersion. Average diameter 0.5mm
Prepare 800g of zirconia beads together with the preliminary dispersion
Place in a vessel and disperser (1 / 4G sand grinder
(L: Imex Co., Ltd.) and dispersed for 25 hours.
1 dispersion was obtained. Faces contained in the pigment dispersion thus obtained
The material particles had an average particle size of 0.21 μm. << Preparation of SBR Latex Liquid >> Tg = 22 ° C.
The SBR latex was prepared as follows. Polymerization initiator
As ammonium persulfate, anionic interface as emulsifier
Using activator, styrene 70.0 mass, butadiene 2
7.0 mass and 3.0 mass of acrylic acid are emulsion polymerized
Then, aging was performed at 80 ° C. for 8 hours. Then 40
Cool to 0 ° C, adjust to pH 7.0 with aqueous ammonia,
Sanyo Chemical Co., Ltd. sandet BL to 0.22%
Added to. Next, add 5% aqueous sodium hydroxide solution.
pH 8.3 and pH 8.4 with aqueous ammonia
Adjusted as follows. Na used at this time⁺Ion and NH_Four ⁺B
The molar ratio of on was 1: 2.3. Furthermore, this liquid 1
7% benzoisothiazolinone sodium salt against Kg
An SBR latex solution was prepared by adding 0.15 ml of an aqueous solution. (SBR Latex: -St (70.0) -Bu (27.0) -AA
(3.0) -latex) Tg22 ℃, average particle size 0.1μm, concentration 4
3% by mass, equilibrium water content at 25 ° C and 60% RH, 0.6% by mass,
Conductivity 4.2mS / cm (Ion conductivity is measured by TOA
Using a conductivity meter CM-30S manufactured by Co., Ltd., latex stock solution (43 mass
%) At 25 ° C.), pH 8.4. SBR latex with different Tg
Cox changed the ratio of styrene and butadiene as appropriate.
It can be adjusted by the method. << Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1 >>
To 1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, Pigment-1
33.2 g of dispersion, 21 g of organic polyhalogen compound-1 dispersion,
Organic polyhalogen compound-2 dispersion 58g, phthalazine compound
-1 solution 173g, SBR latex (Tg: 22 ° C) solution 1082g, return
299 g of base agent complex-1 dispersion, 6 g of development accelerator-1 dispersion,
9 ml of rucapto compound-1 aqueous solution, mercapto compound-2
27ml of aqueous solution is added in order and mixed with silver halide just before coating
Add Emulsion A117g and mix well.
The solution was fed to the coating die as it was and applied. Where
Polyhalogen compound-1 dispersion and -2 dispersion, reducing agent
Complex-1 dispersion and development accelerator-1 dispersion
The thing within 3 days was used. The viscosity of the emulsion layer coating solution is B type from Tokyo Keiki.
Measured with a viscometer, 2 at 40 ° C (No. 1 rotor, 60 rpm)
5 [mPa · s]. Rheometrics Far East
Using an RFS fluid spectrometer manufactured by Co., Ltd.
The viscosity of the coating solution at 25 ° C is a shear rate of 0.1, 1, 10, 10
230, 60, 46, 24, 18 at 0 and 1000 [1 / second] respectively
[mPa · s]. The amount of zirconium in the coating solution is about 1 g of silver.
0.38 mg. << Preparation of emulsion layer (photosensitive layer) coating solution-2 >>
To 1000 g of the fatty acid silver dispersion obtained above, 276 ml of water, Pigment-1
32.8 g of dispersion, 21 g of organic polyhalogen compound-1 dispersion,
Organic polyhalogen compound-2 dispersion 58g, phthalazine
Compound-1 solution 173g, SBR latex (Tg: 20 ° C) solution 1082g,
Reducing agent-2 dispersion 155 g, hydrogen bonding compound-1 dispersion 55
g, Development accelerator-1 dispersion 6 g, Development accelerator-2 dispersion 2
g, Development accelerator-3 dispersion 3g, Color tone modifier-1 dispersion 2
g, Mercapto compound-2 aqueous solution 6ml was added in order and applied.
Immediately before adding silver halide mixed emulsion A117g and mixing well
The prepared emulsion layer coating solution is fed directly to the coating die.
And applied. Where organic polyhalogen compound-1 dispersion
And -2 dispersion, reducing agent -2 dispersion and development accelerator -2
Dispersion, development accelerator-3 Dispersion is within 3 days of refrigeration after production
The thing of was used. The viscosity of the emulsion layer coating solution is
Measured with a B-type viscometer at 40 ° C (No. 1 rotor, 60 rpm)
40 [mPa · s]. Rheometrics Far Ease
Using RFS fluid spectrometer
The viscosity of the coating solution at 25 ° C is a shear rate of 0.1, 1, 10, 10
530, 144, 96, 51, 28 at 0 and 1000 [1 / second], respectively
[mPa · s]. The amount of zirconium in the coating solution is about 1 g of silver.
It was 0.25 mg. << Preparation of Emulsion Surface Intermediate Layer Coating Solution >> Polyvinyl
Alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) 1000 g, 5 mass of pigment
% Dispersion 272g, methyl methacrylate / styrene / butyl
Acrylate / hydroxyethyl methacrylate / acrylic
Luric acid copolymer (copolymerization mass ratio 64/9/20/5/2) Latex 19
Aerosol OT (American Cyana)
27 ml of 5% by weight aqueous solution (made by Mido), diammonium phthalate
135ml of 20% by weight aqueous solution of um salt, total amount 10000g
Add water and adjust with NaOH so that the pH is 7.5.
9.1ml / m as an interlayer coating solution²Coat da to be
The solution was sent to A. The viscosity of the coating solution is 40 ° C (No.
It was 58 [mPa · s] at 60 rpm. << Preparation of coating liquid for emulsion layer protective layer first layer >>
Dissolve 64 g of gelatine in water and add methyl methacrylate
/ Styrene / Butyl acrylate / Hydroxyethyl meta
Chrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20
/ 5/2) 80 g of latex 27.5 mass% solution, 10 mass of phthalic acid
23 ml of methanol solution, 10% by mass of 4-methylphthalic acid
23 ml of aqueous solution, 28 ml of 0.5 mol / L sulfuric acid, aerosol
5m of 5% aqueous solution of OT (American Cyanamid)
l, phenoxyethanol 0.5g, benzoisothiazolino
Add 0.1 g of water sequentially and add water to make a total amount of 750 g.
Immediately before application of 26% 4% chrome alum as a cloth liquid
18.6ml / m mixed with static mixer²Nina
The solution was sent to the coating die. The viscosity of the coating solution is
20 [mPa · s] at 40 ° C (No. 1 rotor, 60rpm)
Met. << Preparation of coating liquid for emulsion layer protective layer second layer >>
Methyl methacrylate is dissolved in water
/ Styrene / Butyl acrylate / Hydroxyethyl meta
Chrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20
/ 5/2) 27.5% latex by weight 102g, fluorinated surface activity
Agent (F-1: N-perfluorooctylsulfonyl-N-
3.2 ml of 5% by mass solution of propylalanine potassium salt)
Fluorosurfactant (F-2: Polyethylene glycol
Mono (N-perfluorooctylsulfonyl-N-propyl-2
-Aminoethyl) ether [average degree of polymerization of ethylene oxide =
15]) 2% by weight aqueous solution, 32 ml of aerosol OT (American
23 ml of 5% by mass solution of Kanthianamide), polymethy
Polymethacrylate fine particles (average particle size 0.7μm) 4g, polymer
Cyl methacrylate fine particles (average particle size 4.5μm) 21g, 4-
1.6 g of methylphthalic acid, 4.8 g of phthalic acid, 0.5 mol / L sulfur
Sequentially add 44 ml of acid and 10 mg of benzoisothiazolinone, total amount
Add water to make 650g and add 4% by mass of chromium
445 ml of an aqueous solution containing a bag and 0.67% by weight phthalic acid
The surface mixed with a static mixer just before coating
8.3ml / m as a protective coating solution²Coat da to be
The solution was sent to A. The viscosity of the coating solution is 40 ° C (No.
19 [mPa · s] at 60 rpm). << Preparation of photothermographic material-A >> The above undercoat
Apply the antihalation layer coating solution to the back side of the support.
The amount of latin applied is 0.04g / m²And back surface protection
The coating amount of gelatin is 1.7g / m²Same as
A multi-layer coating was applied and dried to form a back layer. [0257] From the undercoat surface to the emulsion layer on the surface opposite to the back surface
(Use emulsion layer coating solution-1), intermediate layer, protective layer first layer,
Simultaneously by slide bead coating method in order of protective layer second layer
Multi-layer coating was applied to prepare a photothermographic material sample. This
Emulsion layer and intermediate layer at 31 ° C, protective layer first layer at 36 ° C,
The temperature of the protective layer first layer was adjusted to 37 ° C. Emulsion layer compounds
Coating amount (g / m²) Is as follows. [0258] Silver behenate 8.00 Pigment (C.I.Pigment Blue 60) 0.04 Polyhalogen compound-1 (H-1) 0.06 Polyhalogen compound-2 (H-8) 0.70 Phthalazine Compound-1 0.20 SBR latex 10.05 Reducing agent complex-1 1.41 Development accelerator-1 0.025 Mercapto Compound-1 0.003 Mercapto compound-2 0.015 Silver halide (as Ag) 0.09 The coating and drying conditions are as follows. Coating
Is performed at a speed of 160 m / min, and the tip of the coating die is supported.
The gap with the holder is 0.10 to 0.30 mm, and the pressure in the decompression chamber is atmospheric
The pressure was set to 196 to 882 Pa lower than the pressure. Support is before coating
Static electricity was removed with ion wind. In the subsequent chilling zone,
No contact after cooling the coating liquid with air at a dry bulb temperature of 10-20 ° C
The mold is transported, and the dry bulb temperature is changed with a spiral-type non-contact dryer.
The film was dried with a drying air having a temperature of 23 to 45 ° C and a wet bulb temperature of 15 to 21 ° C.
After drying, the humidity is adjusted to 40-60% RH at 25 ° C, and the film surface is 70
Heated to ~ 90 ° C. After heating, film surface up to 25 ° C
Cooled down. The matte degree of the photothermographic material thus prepared is
Smooth surface is 550 seconds on the photosensitive layer side and 130 seconds on the back surface.
there were. Also, when the pH of the film surface on the photosensitive layer side was measured
It was 6.0. << Preparation of Photothermographic Material-B >> Photothermographic Photosensitivity
Emulsion layer coating solution-1 is used as the emulsion layer coating solution for material-1.
Change to 2, and further yellow dye from the antihalation layer
Except for compound 15, the back side protective layer and emulsion side protective layer
The fluorine-based surfactants are F-1, F-2, F-3 and F-.
4 to F-5, F-6, F-7 and F-8 respectively
Except for the change, the photothermographic feel was the same as photothermographic material-1.
Optical material-2 was produced. At this time, for each compound in the emulsion layer
Application amount (g / m²) Is as follows. [0262] Silver behenate 5.00 Pigment (C.I.Pigment Blue 60) 0.03 Polyhalogen compound-1 (H-1) 0.20 Polyhalogen compound-2 (H-8) 0.30 Phthalazine Compound-1 0.20 SBR latex 9.80 Reducing agent-2 (R-4) 0.63 Hydrogen bonding compound-1 (D-7) 0.33 Development accelerator-1 (A-1) 0.03 Development accelerator-2 0.020 Development accelerator-3 0.015 Color tone adjuster-1 0.020 Mercapto compound-2 0.003 Silver halide (as Ag) 0.095 << Preparation of photothermographic material-C-1 to C-2 >>
For developing photosensitive material-A, emulsion layer coating solution-1
Rogen Compound-2 was converted to polyhalo after the aging in Table 5 of Example 5.
Photothermographic material-A, except that it was changed to a gen compound dispersion
Photothermographic materials -C-1 to C-2 were prepared in the same manner as described above.
(Table 7). << Preparation of photothermographic material-D-1 to D-2 >> Photothermographic material
Polyhalogen compound of emulsion layer coating solution-1 for -B
-2 in combination with compounds after aging in Table 5 of Example 5
Except for the changes, the photothermographic feel was the same as for photothermographic material-B
Optical materials -D-1 to D-2 were prepared (Table 7). The compounds used in the examples of the present invention are shown below.
The academic structure is shown. [0265] Embedded image [0266] Embedded image[0267] Embedded image[0268] Embedded image[0269] Embedded image (Evaluation of performance) The obtained sample is half-cut size
And wrapped in the following packaging material in an environment of 25 ° C and 50%
And store it at room temperature for 2 weeks.
It was. (Packaging material) PET 10μm / PE 12μm / Aluminum foil 9μm / Ny 15
Laminate made of 50μ polyethylene containing 3% μm / carbon
The oxygen permeability is substantially 0ml / Pa · m at 25 ° C.²・ S,
Water permeability is substantially 0g / Pa · m at 25 ° C.²・ S (Note: Actual
Qualitative 0 means below the measurement limit). <Evaluation of photographic performance> Fuji Medical Dry
Laser imager FM-DPL (up to 60mW (IIIB)
Exposure and thermal development with a powerful 660nm semiconductor laser (112)
4 panel heat set to ℃ -119 ℃ -121 ℃ -121 ℃
Photothermographic material-A and photothermographic material-C-1 to C-
2 is a total of 24 seconds, photothermographic material-B and photothermographic material
Material-D-1 to D-2 were 14 seconds in total) and the resulting solid development image
Image sensitivity and density were evaluated according to the following criteria. <Sensitivity> Photothermographic material-For C-1 to C-2, heat development
Relative sensitivity is shown with the sensitivity of Photosensitive Material-A being 100, and 98 to 102
The allowable range. For photothermographic materials-D-1 to D-2
Shows the relative sensitivity, assuming that the sensitivity of photothermographic material-B is 100.
And 98-102 was made into the tolerance | permissible_range. <Density> For photothermographic materials -C-1 to C-2, heat development
Relative density is shown with the density of photosensitive material-A being 100, and 98 to 102
The allowable range. For photothermographic materials-D-1 to D-2
Shows the relative density with the density of photothermographic material-B as 100.
And 98-102 was made into the tolerance | permissible_range. The evaluation results are shown in Table 7.
The [0271] [Table 7] As is clear from the results shown in Table 7,
Heat using a solid dispersion prepared by the manufacturing method of the invention
Development photosensitive materials have no problem in terms of photographic performance (density and sensitivity).
It was not. On the other hand, when the preliminary dispersion of the present invention,
When using a solid dispersion that has not been performed, the sensitivity and
Variation in concentration was observed. [0273] The defoaming treatment before dispersion according to the present invention is achieved by the dispersion.
Stable manufacturing by preventing creaming due to liquid air
Manufacture of dispersions that provide processes and reduce manufacturing time
It turns out to provide a method. And in this way
By using the manufactured dispersion, the coated surface is improved.
It has become possible to provide a photothermographic material.

Claims (1)

What is claimed is: 1. A photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent and a binder are contained on at least one surface of a support, and at least one of the constituent layers. A process for producing a photothermographic material comprising a solid dispersion of an organic compound, wherein the solid dispersion is produced through a defoaming step during preliminary dispersion before dispersion.