JP2003295396A - Heat-developable photosensitive material and method for developing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-developable photosensitive material which has a small coating weight of silver, can rapidly be processed and has high sensitivity and low fog. <P>SOLUTION: In the heat-developable photosensitive material comprising on one face of a support a photosensitive silver halide, a reducing agent for a silver ion, a binder and non-photosensitive organic silver salt grains and having 0.5-1.9 g/m<SP>2</SP>coating weight of silver, the erucic acid content of the non- photosensitive organic silver salt grains is 0.00001-50 mol% of the total number of moles of behenic acid and silver behenate. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a photosensitive thermal development feeling.
For optical materials, more details
A certain photothermographic material or a small amount of coated silver
Photothermographic materials or photothermographic materials that can be processed quickly
The present invention relates to a material and a developing method thereof. [0002] 2. Description of the Related Art In recent years, the field of medical diagnostic films and photo production
Is it from the viewpoint of environmental conservation and space saving in the plate film field?
Therefore, it is strongly desired to reduce the amount of processing waste liquid. So, laser
-For imagesetters or laser imagers
More efficient exposure, high resolution and sharpness
Physician capable of forming sharp black image with sharpness
Thermal therapy film and photoengraving film
There is a need for techniques relating to image-sensitive materials. These heat
According to development photosensitive materials, solution-type processing chemicals are required.
Thermal development processing system that is simpler and does not damage the environment
Can be supplied to customers. Similar demands in the field of general image forming materials
However, medical diagnostic images are particularly required to be finely depicted.
Therefore, high image quality with excellent sharpness and graininess is required.
In particular, cold black images are preferred from the viewpoint of ease of diagnosis.
There are signs. Currently, inkjet printers, electrophotography
Various hard copy systems using pigments and dyes
Although distributed as a general image forming system, medical images
There is no satisfactory image output 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.
Nos. 7075 and D.C. Cross Tabor (Klos
by terboer) "Thermal processed silver system (Therm
ally Processed Silver Systems) (Imaging
Processes and Materials (Imaging Proc
esses and Materials) Neblette 8th edition, J.E. Star
Sturge, V.M. Walworth, A.C.
Edited by Shepp, Chapter 9, page 279, 198
9 years). In particular, photothermographic materials are
In general, a catalytically active amount of a photocatalyst (eg, silver halide),
Reducing agent, reducible silver salt (eg organic silver salt), as required
Tone that controls the silver tone more
And a photosensitive layer dispersed in the package. Photothermographic exposure
The material is heated to a high temperature (eg, 80 ° C or higher) after image exposure.
Reducible silver salt (functioning as an oxidizing agent) and reducing agent
A black silver image is formed by the redox reaction between
The The oxidation-reduction reaction is the latent of silver halide generated by exposure.
Promoted by image catalysis. Therefore, black silver painting
An image is formed in the exposed area. About photothermographic materials
U.S. Pat. No. 2,910,377 and Japanese Patent Publication No. 43-4924.
And many other documents. [0005] SUMMARY OF THE INVENTION
Oxidation-reduction reaction between reducible silver salt and reducing agent
Proceed with realistic reaction temperature and reaction time,
It is preferable to have a high degree of sensitivity, but high sensitivity and development activity
Photothermographic material with high photoreaction, rapid reaction and low fog
At present, further development of materials is desired. More
Heat-developable photosensitive material that enables a small amount of coated silver or
Photothermographic material capable of rapid processing and development method thereof
The issue is to provide. [0006] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to solve the problem, the following means were achieved.
I found out. (1) On one side of the support, photosensitive silver halide,
Reducing agent, binder and non-photosensitive organic for silver ion
Contains silver salt particles, and the coated silver amount is 1m²0.5g or more per
Heat development feeling of 1.9 g or less (preferably 1.8 g or less)
In an optical material, the non-photosensitive organic silver salt particles contain erucic acid.
The percentage is 0 with respect to the sum of the number of moles of behenic acid and silver behenate.
00001 mol% or more and 50 mol% or less
Photothermographic material. (2) The erucic acid content of the non-photosensitive organic silver salt particles is
0.001 mole per mole of behenic acid and silver behenate
% To 40 mol% (preferably 32 mol% or less)
2. The photothermographic material according to claim 1, wherein the photothermographic material is a photothermographic material. (3) Organic solution of coating solution remaining in photothermographic material
1m of agent²5mg to 1000mg per (preferred
10 mg to 500 mg, more preferably 20 mg
mg to 400 mg)
Item 3. The photothermographic material according to item 1 or 2. (4) The photothermographic material according to claim 1, 2, or 3.
Development temperature of 100 to 140 ° C. and heat development time of 12 seconds or less (preferably
Thermal development characterized by processing in 1 second or more)
Development method of photosensitive material. (5) On one side of the support, photosensitive silver halide,
Reducing agent, binder and non-photosensitive organic for silver ion
Erucic acid containing silver salt particles and the non-photosensitive organic silver salt particles
The content is based on the sum of moles of behenic acid and silver behenate.
Presents photothermographic materials of 0.00001 mol% to 50 mol%
Thermal development time of 12 seconds or less at an image temperature of 100 to 140 ° C. (preferred
Or 1 second or longer)
Development method of optical material. The heat development time is preferably 5 seconds or more 1
1 second or less. (6) The erucic acid content of the non-photosensitive organic silver salt particles is
0.001 mole per mole of behenic acid and silver behenate
% To 40 mol% (preferably 32 mol% or less)
The photothermographic material according to claim 5, wherein
Development method. (7) Organic solution of coating solution remaining in photothermographic material
1m of agent²5mg to 1000mg per (preferred
10 mg to 500 mg, more preferably 20 mg
mg to 400 mg)
Item 7. A method for developing a photothermographic material according to Item 5 or 6. [0007] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method and an implementation of the present invention.
The aspect will be described in detail. (Description of organic silver salt) Organic silver that can be used in the present invention
Salt is relatively stable to light, but exposed to light
In the presence of water-soluble silver halide and a reducing agent
Functions as a silver ion supplier when heated above,
A silver salt that forms a silver image. Organic silver salt as a reducing agent
Any organic substance that can supply more ionizable silver ions
It may be. About such non-photosensitive organic silver salt
Are paragraph numbers 0048 to 0049 of JP-A-10-62899,
European Patent Publication No. 0808374A1, page 18, line 24
Page 19, line 37, European Patent Publication No. 0962812A1,
JP 11-349591, JP 2000-7683, 2000-72711
Etc. are described. Silver salts of organic acids, especially (with 10 carbon atoms
Long chain aliphatic carboxylic acid silver (~ 30, preferably 15-28)
Salts are preferred. Preferred examples of fatty acid silver salts include rigs
Noceric acid, silver behenate, silver arachidate, stearin
Silver oxide, silver oleate, silver laurate, silver caproate,
Silver ristinate, silver palmitate, erucic acid and these
Including a mixture of In the present invention, these fatty acids
Among silver, it contains at least silver behenate.
The silver behenate content is preferably 50 mol% or more
It is preferred to use fatty acid silver. Organic silver salt particles that can be used in the present invention
The erucic acid content is the sum of the moles of behenic acid and silver behenate.
0.00001 mol% or more and 50 mol% or less with respect to
It is a feature that it is 0.001 mol% or more and 40 mol% or less.
Particularly preferred. 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
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 be. 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, percentage of the value divided by the volume weighted average diameter (coefficient of variation)
Is preferably 100% or less, more preferably 80% or less,
Preferably it is 50% or less. As a measuring method, for example, liquid
Scattering of organic silver salt dispersed in laser light
Finding autocorrelation function for light fluctuation over time
Obtained from the particle size (volume weighted average diameter)
You can 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. Incidentally, 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, when mixing two or more organic silver salt water dispersion and 2
Mixing more than one type of photosensitive silver salt aqueous dispersion
This is a method preferably used for sex control. 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 ~ 1.9g / m²It is. In particular, improved image storage
In order to achieve this, the total amount of silver applied is 1.9 g / m²Must be
Is preferred. If the preferred reducing agent of the present invention is used, this
A sufficient image density can be obtained even with a low silver content such as
Is possible. In the present invention, erucic acid and behenic acid
Quantification of organic acid is treated with diazomethane at 40 ° C for 30 minutes.
After conversion, GC-FID measurement was performed. GC-FID conditions are
As a column, DB-1 (30m × 0.25mmφ, df = 0.25μm)
It carried out using. If the concentration is low, use IPA.
Recrystallize the mechanical acid, concentrate the erucic acid remaining in the supernatant,
Measurements were performed. The organic silver salt that can be used in the present invention is:
Particles formed with water solvent, then dried, organic silver salt grains
Obtained as a child. Drying is a flash type jet
Oxygen partial pressure of 15 vol% or less at the pliers 0.01v
It is preferable to carry out at ol% or more, and further 10vol% or less
More preferably, it is carried out at 0.01 vol% or lower. Photosensitivity
When producing the material, the organic silver salt particles are dissolved in a solution such as MEK.
Prepare and use by dispersing in a medium. The photothermographic material of the present invention is a photosensitive halogen.
Contains silver fossil. Formation of photosensitive silver halide for use in the present invention
Methods are well known in the art, eg research
Disclosure No. 17029 of June 1978, and the United States
Using the method described in Japanese Patent No. 3,700,458
Can be. Specific examples that can be used in the present invention
As a method, halogen preparation is included in the prepared organic silver salt.
Part of the organic silver salt silver is made photosensitive by adding the compound
How to convert to silver halide, gelatin or other
Silver supply compound and halogen supply compound in limer solution
To prepare photosensitive silver halide grains by adding
A method of mixing with an organic silver salt can be used. The present invention
Preferably, the latter method can be used. The photosensitive silver halide grain size is determined by the image
Small is preferable for the purpose of keeping the cloudiness after formation low.
More specifically, 0.01μm or more and 0.15μm or less is more preferable.
Or 0.02 μm to 0.10 μm. Silver halide grains
If the child size is too small, the sensitivity will be insufficient.
There may be a problem that the haze of the development photosensitive material is increased.
The grain size here means that the silver halide grains are cubic.
Or in the case of octahedral so-called normal crystals,
This is the length of the ridge of silver halide grains. In addition, silver halide grains
Is the same area as the projected area of the main surface
This is the diameter when converted into a circular image. Other normal crystals
For example, in the case of spherical particles, rod-shaped particles, etc.
The diameter when considering a sphere equivalent to the volume of silver halide grains
Say. The shape of the silver halide grains is a cube,
Octahedron, tabular grain, spherical grain, rod-like grain, potato
In the present invention.
In particular, cubic grains and tabular grains are preferred. Flat-shaped halogen
The average aspect ratio when using silver halide grains is preferred
Is 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further
Also preferred are grains with rounded corners of silver halide grains.
Can be used. Outside photosensitive silver halide grains
There is no particular restriction on the surface index (Miller index) of the surface
However, the spectral sensitization efficiency is high when the spectral sensitizing dye is adsorbed.
It is preferable that the proportion of [100] plane is high. Proportion
Is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. Ratio of Miller index [100] surface increased
Adsorption dependence of [111] and [100] surfaces in dye-sensitive adsorption
T.Tani; J. Imaging Sci., 29, 165 (1985)
It can be determined by the method described. As the halogen composition of the photosensitive silver halide
There is no particular limitation, silver chloride, silver chlorobromide, silver bromide, iodine odor
Silver iodide, silver iodochlorobromide, or silver iodide may be used.
However, in the present invention, silver bromide or silver iodobromide is preferred.
It can be used well. Particularly preferably silver iodobromide
The silver iodide content is 0.1 mol% or more and 40 mol% or less.
Preferably, 0.1 mol% or more and 20 mol% or less is more preferable.
The distribution of halogen composition within the grain may be uniform.
Even if the halogen composition changes stepwise
Or may change continuously, but is preferable
As an example, silver iodobromide grains with high silver iodide content inside the grains
Child can be used. Also preferably core /
Silver halide grains having a shell structure can be used.
The The structure is preferably 2-5 layers, more preferred
Alternatively, it is possible to use core / shell particles with 2-4 layers.
Yes. Photosensitive silver halide grains used in the present invention
Rhodium, rhenium, ruthenium, osnium,
Of a metal selected from lithium, cobalt, mercury or iron
It is preferable to contain at least one complex. these
One kind of metal complex may be used, and the same metal or different metal may be used.
Two or more complexes may be used in combination. Preferred content is 1 silver
From 1 nanomole (nmol) to 10 mmol (mmol) per mole
Preferably in the range of 10 nanomoles (nmol) to 100 microphones
The range of romole (μmol) is more preferred. Concrete metal
The structure of the complex is described in JP-A-7-225449.
Metal complexes having different structures can be used. Cobalt, iron
For these compounds, hexacyano metal complexes are preferably used.
be able to. Specific examples include iron ferricyanate
, Ferrocyanate ion, hexacyanocobaltate ion
On, etc. are mentioned, but it is not limited to these
Absent. Even if the containing phase of the metal complex in the silver halide is uniform,
It may be contained in the core part at a high concentration, or the shell part
There is no particular limitation as long as it may be contained in a high concentration. The photosensitive silver halide grains are obtained by the noodle method,
Water that is known in the industry, such as the accumulation method
Although it can be desalted by washing, it is desalted in the present invention.
You don't have to. The photosensitive silver halide grains in the present invention are
It is preferably chemically sensitized. Preferred chemical sensitization
As the method is well known in the industry, sulfur sensitization
Method, selenium sensitization and tellurium sensitization can be used.
The Gold compounds, platinum, palladium, iridium compounds
Noble metal sensitization method and reduction sensitization method can be used
The Preferred for sulfur sensitization, selenium sensitization and tellurium sensitization
Use known compounds as commonly used compounds
However, the compounds described in JP-A-7-128768 etc.
Can be used. Use of photosensitive silver halide in the present invention
The amount is photosensitive silver halide per mole of organic silver salt.
0.01 mol or more and 0.5 mol or less are preferable, 0.02 mol or more and 0.3 mol or less.
Mol or less is more preferable, 0.03 mol to 0.25 mol or less
Particularly preferred. Separately prepared with photosensitive silver halide
Regarding the mixing method and mixing conditions of machine silver salt,
Use the high-speed stirrer
Ball mill, sand mill, colloid mill, vibration mill, ho
A method of mixing with a modernizer or the like, or organic silver salt
Photosensitive photosensitive drums that have been prepared at any time during preparation
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. As a method for preparing the silver halide used in the present invention,
In some cases, some silver in organic silver salts may be converted to organic or inorganic halogens.
The so-called halide method in which halogenation is performed with fluoride is also preferred.
It is used well. As the organic halide used here
Compounds that react with organic silver salts to form silver halide
N-halogenoimide (N
-Bromosuccinimide), halogenated quaternary nitrogen compounds
Products (such as tetrabutylammonium bromide), halogenated 4
Aggregates of quaternary nitrogen salts and halogen molecules (pyridinium perbromide)
Etc. Organic silver as an inorganic halogen compound
What if it is a compound that reacts with salt to produce silver halide?
May be used, but may be alkali metal halides or alloys.
Ammonium (sodium chloride, lithium bromide, potassium iodide)
Lithium, ammonium bromide, etc.), alkali halides
Earth metals (calcium bromide, magnesium chloride, etc.),
Transition metal transition metal (such as ferric chloride, cupric bromide), halo
Metal complexes with gen ligands (Natribromide iridate)
, Ammonium chloride rhodate), halogen content
There are children (bromine, chlorine, iodine). Also, the desired organic
An inorganic halide may be used in combination. Haridation
The amount of halide added is 1 mol of organic silver salt.
1 to 500 millimoles per halogen atom
Preferably, 10 mmol to 250 mmol is more preferable.
Yes. The photothermographic material of the present invention contains a halogenated material.
A sensitizing dye can also be contained together with the silver particles. Book
Sensitizing dyes applicable to the invention include silver halide grains.
When adsorbed, spectroscopic analysis of silver halide grains in the desired wavelength region
Spectral sensation suitable for the spectral characteristics of the exposure light source
A sensitizing dye having a degree can be advantageously selected. Increase
Regarding the dye and the addition method, paragraphs of JP-A-11-65021
Nos. 0103 to 0109, represented by general formula (II) of JP-A-10-186572
A compound represented by the general formula (I) of JP-A-11-119374
Dye and paragraph number 0106, U.S. Pat.No. 5,510,236, ibid.
No. 5,541,054, No. 3,871,887 Color described in Example 5
Disclosed in JP-A-2-96131 and JP-A-59-48753
Dye, European Patent Publication No. 073684A1, page 19, page 3
Line 8-Page 20, line 35, Japanese Patent Application No. 2000-86865, Japanese Patent Application 2000-
No. 102560 etc. These sensitizing dyes alone
Or may be used in combination of two or more. Main departure
The amount of sensitizing dye added in the light depends on the sensitivity and fogging performance.
It can be adjusted to the desired amount.
10 per mole of silver halide^-6~ 1 mole is preferred, and
Preferably 10^-Four~Ten^-1Is a mole. Combination of sensitizing dyes
Is often used for the purpose of supersensitization. Intensifying color
A dye that has no spectral sensitization effect by itself
Or a substance that does not substantially absorb visible light
A substance exhibiting a feeling may be contained in the emulsion. Useful sensitizing colors
Element, combination of pigments exhibiting supersensitization, and supersensitization
Quality: Research Disclosure 176, 17643 (December 1978)
Page 23, Section J, or JP-B-49-25500, 43-
No. 4933, JP-A 59-19032, 59-192242
It is described in the news. The photothermographic material of the present invention has the following general formula:
The compound represented by (I) is used as a reducing agent for silver ions.
Contained. [0030] [Chemical 1] The general formula (I) will be described in detail below.
The In general formula (I), R¹¹And R¹¹’Is German
It is an alkyl group having 1 to 20 carbon atoms. These groups
May further have a substituent, and as a substituent,
Although not particularly limited, an aryl group, hydroxy
Group, alkoxy group, aryloxy group, alkylthio
Group, arylthio group, acylamino group, sulfonamide
Group, sulfonyl group, phosphoryl group, acyl group, carbamo
Yl group, sulfamoyl group, ester group, halogen atom
Etc. are preferable. R¹²And R¹²Each is independently a hydrogen atom,
Or a substituent that can be substituted on the benzene ring, and X¹as well as
X¹′ Is also independently substituted with a hydrogen atom or a benzene ring.
Represents a possible group. Groups that can be substituted on the benzene ring,
An alkyl group, aryl group, halogen atom,
Preferred examples include a alkoxy group and an acylamino group. L is a -S- group or CHR.¹³-Represents a group.
R¹³Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
Specific examples include methyl group, ethyl group, propyl
Group, butyl group, heptyl group, undecyl group, isopropyl group
Group, 1-ethylpentyl group, 2,4,4-trimethyl
A pentyl group and the like are preferable. The alkyl group
It may have a substituent, and examples of the substituent include R¹¹
As the substituents of
Xyl, alkoxy, alkylthio, aryloxy
Si group, arylthio group, acylamino group, sulfonamido
Group, sulfonyl group, phosphoryl group, acyl group, oxy
Carbonyl group, carbamoyl group, sulfamoyl group,
A stealth group etc. are mentioned suitably. R¹¹And R¹¹′ Includes 3 to 3 carbon atoms.
15 secondary or tertiary alkyl groups are preferred, specifically
Are isopropyl, isobutyl, t-butyl, t
-Amyl group, t-octyl group, cyclohexyl group, cycl
Lopentyl group, 1-methylcyclohexyl group, 1-methyl
Preferred examples include a lucyclopropyl group. More preferred
Or a secondary or tertiary alkyl group having 3 to 8 carbon atoms,
Among them, t-butyl group, t-amyl group, 1-methyl
A cyclohexyl group is more preferred, and a t-butyl group is most preferred.
Is also preferable. R¹²And R¹²'Represents an alkyl group
Is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable.
Specifically, methyl group, ethyl group, propyl group, buty
Group, isopropyl group, t-butyl group, t-amyl group,
Cyclohexyl group, 1-methylcyclohexyl group, ben
Zyl group, methoxymethyl group, methoxyethyl group, etc. are preferred
More preferably, methyl group, ethyl group,
Propyl group, isopropyl group, t-butyl group
Yes. X¹And X¹'Represents a hydrogen atom or halogen.
Atoms and alkyl groups are preferred, hydrogen atoms are more preferred
Yes. The L is -CHR.¹³-Group is preferred
Yes. R¹³As a hydrogen atom or carbon number 1-15
An alkyl group is preferable, and a hydrogen atom or carbon number 1 to 12
A primary or secondary alkyl group is more preferred. The alkyl
Groups include methyl, ethyl, propyl, and isop
Lopyl group and 2,4,4-trimethylpentyl group are preferred
Can be mentioned. R¹³Particularly preferred as a hydrogen atom,
A til group, a propyl group or an isopropyl group. R¹³R is a hydrogen atom, R¹²
And R¹²'Is preferably an alkyl group having 2 to 5 carbon atoms.
More preferably an ethyl group or a propyl group.
Is most preferred. R¹³Is a primary having 1 to 12 carbon atoms or
In the case of a secondary alkyl group, the R¹²And R¹²'age
In particular, a methyl group is preferable. R¹³First grade of carbon number 1-12
Or as a secondary alkyl group, a methyl group, an ethyl group,
A propyl group and an isopropyl group are more preferable, and methyl
A group, an ethyl group, and a propyl group are more preferable. Above
R¹¹, R¹¹', R¹²And R¹²'Is a methyl group
R¹³As secondary alkyl groups are preferred
In addition, a secondary alkyl group having 3 to 12 carbon atoms is more preferable.
In this case R¹³As the secondary alkyl group, isopropyl
Group, isobutyl group and 1-ethylpentyl group are preferred,
An isopropyl group is particularly preferred. As the compound represented by the general formula (I)
Is R¹¹And R¹¹'Is independently a secondary class having 3 to 8 carbon atoms.
Or a tertiary alkyl group, R¹²And R¹²'Is German
An alkyl group and L is —CHR¹³The group R
¹³Is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
X¹And X¹′ Is a hydrogen atom, and R¹¹,
R¹¹', R¹²And R¹²′ Is a methyl group, and L is —CH.
R¹³The group R¹³Is a secondary alkyl having 3 to 12 carbon atoms
X and X¹And X¹′ Is a hydrogen atom.
Is preferred. Hereinafter, the compounds represented by the general formula (I)
Examples are shown (Exemplified Compounds I-1 to 22).
It is not limited to these at all. [0040] [Chemical 2][0041] [Chemical 3][0042] [Formula 4] In the present invention, as a reducing agent for organic silver salts
Together with the compound represented by the general formula (I)
A reducing agent may be used in combination. For organic silver salt that can be used together
As a reducing agent, silver ions can be reduced to metallic silver.
It can be any substance (preferably an organic substance).
Such a reducing agent is disclosed in JP-A-11-65021.
Nos. 0043-0045 and European Patent Publication No. 08037
64A1 page 7 line 34 to page 18 page 12
Listed in the line. Among them, hindered feno
Preferred are reducing agents for bisphenols and reducing agents for bisphenols. In the present invention, it is represented by the general formula (I).
The amount of the reducing agent added is 0.01 to 5.0 g / m.²
Is preferably 0.1 to 3.0 g / m.²Is
More preferably, 1 mol of silver on the surface having the image forming layer
Is preferably contained in an amount of 5 to 50 mol%.
More preferably, it is contained in an amount of 0 to 40 mol%. Return
The base agent is preferably contained in the image forming layer. Binder in the photothermographic material of the present invention
-Natural or synthetic resins such as gelatin, polyvinyl chloride
Nilbutyral, polyvinyl acetal, polyvinyl chloride
Loride, polyvinyl acetate, cellulose acetate
Polyolefin, polyester, polystyrene, polyester
Liacrylonitrile, polycarbonate, polyvinyl chloride
Tyral, butyl ethyl cellulose, methacrylate
Polymer, maleic anhydride ester copolymer, police
From ethylene and butadiene-styrene copolymers
Any thing can be used. Of course, Kopoli
Also included are mers and terpolymers. Preferably polybi
Nitrobutyral is 100% by weight or less and 50% by weight or more
Using a binder having a composition as follows. In the present invention
The total amount of binder is sufficient to keep the ingredients in it.
Used in minute quantities. That is, it functions as a binder
It is used within the effective range to do. The effective range is
A person skilled in the art can determine appropriately. At least organic
As a guide when retaining silver salt, binder versus organic silver
The proportion of salt is 15: 1 to 1: 3, especially 8: 1 to 1: 2 by weight.
An enclosure is preferred. The photothermographic material of the present invention contains a development accelerator.
As described in JP 2000-267222 A
Phenol derivatives represented by (A) are preferably used
The In the photothermographic material of the present invention, the addition of a color toning agent
JP-A-10-62899
No. 0054-0055, the second of European Patent Publication No. 0803684A1
1 page, lines 23-48, described in Japanese Patent Application No. 10-213487
In particular, phthalazinones (phthalazinone, phthalazine
Non-derivatives or metal salts; eg 4- (1-naphthyl) lid
Radinone, 6-chlorophthalazinone, 5,7-dimethoxyphthal
Radinone and 2,3-dihydro-1,4-phthalazinedio
Phthalazinones and phthalic acids (eg phthalates)
Acids, 4-methylphthalic acid, 4-nitrophthalic acid and tetra
Chlorophthalic anhydride); phthalazines (lids)
Razine, phthalazine derivatives or metal salts; for example 4- (1
-Naphthyl) phthalazine, 6-isopropylphthalazine, 6-
t-Butylphthalazine, 6-chlorophthalazine, 5,7-dimeth
Xylphthalazine and 2,3-dihydrophthalazine); lid
A combination of azines and phthalates is preferred, especially phthalates
A combination of azines and phthalates is preferred. Color preparation
0.1-50% mole per mole of silver on the surface having the imaging layer
Preferably contained in an amount of 0.5 to 20% mol
Is more preferable. The silver halide emulsion used in the present invention or /
And organic silver salts are antifoggants, stabilizers and stabilizers
The precursor further protects against the production of additional fog.
Protected and stabilized against loss of sensitivity during inventory storage
can do. May be used alone or in combination
Suitable antifoggants, stabilizers and stabilizer precursors that can
U.S. Pat.Nos. 2,131,038 and 2,694,716.
Thiazonium salts described in US Pat. No. 2,886,43
Azai described in No. 7 and No. 2,444,605
Nden, JP-A-9-329865 and U.S. Pat.No. 6,083,681
Compounds described in US Pat. No. 2,728,663
Mercury salts described in U.S. Patent 3,287,135
Described in U.S. Pat.No. 3,235,652
Of sulfocatechol, described in British Patent No. 623,448
Oxime, nitrone, nitroindazole, US
Polyvalent metal salts as described in U.S. Pat. No. 2,839,405, US patent
No. 3,220,839, a thyronium salt described in US Pat.
To permit 2,566,263 and 2,597,915
Described palladium, platinum and gold salts, U.S. Pat.No. 4,108,
Halo as described in 665 and 4,442,202
Gen-substituted organic compounds, U.S. Pat.No. 4,128,557,
No. 4,137,079, No. 4,138,365 and the same
Triazines described in US Pat. No. 4,459,350 and the United States
There are phosphorus compounds described in Japanese Patent No. 4,411,985.
The Antifoggant preferably used in the present invention
Is an organic halide, especially polyhalomethyl compounds
Products, particularly triaromethylsulfone compounds are preferred. Yes
Examples of the organic halide are disclosed in JP-A-50-119624, 5
No. 0-120328, No. 51-121332, No. 54-58022
No. 56-70543, No. 56-99335, No. 59-90842
JP, 61-129642, 62-129845, JP
Hei6-208191 gazette, 7-5621 gazette, 7-2781 gazette,
No.8-15809, No.9-160167, No.9-244177
No. 9-244178, No. 9-258367, No. 9-265150
Gazette, 9-319022 gazette, 10-171063 gazette, 11-
212211, 11-231460, 11-242304
US Patent Nos. 5340712 and 5369000
Compound as disclosed in US Pat. No. 5,464,737.
In particular, 2- (tribromomethyls
Luhon) quinoline, 2- (tribromomethylsulfone)
Pyridine, tribromomethylphenylsulfone, tribu
Lomomethylnaphthyl sulfone and the like can be mentioned. Although not necessary to practice the present invention,
Adding mercury (II) salt as antifoggant to the photosensitive layer
May be advantageous. Mercury (II) salt preferred for this purpose
Are mercury acetate and mercury bromide. Used in the present invention
Mercury is preferably added per mole of silver applied.
Or 1 nanomolar (nmol) to 1 millimolar (mmol),
Preferably 10 nanomolar (nmol) to 100 micromolar (μm)
ol). The photothermographic material of the present invention has high sensitivity and fog.
Benzoic acids may be contained for the purpose of preventing the occurrence of odor. Main departure
The benzoic acid used in the light can be any benzoic acid derivative.
However, examples of preferred structures include U.S. Pat. No. 4,784,93.
No. 9, No. 4,152,160, JP-A-9-281637
Gazettes, 9-329864, 9-329865, etc.
The compound of this is mentioned. The benzoic acids used in the present invention are sensitive.
It can be added to any part of the optical material.
It is preferable to add it to the surface layer having the photosensitive layer.
More preferably, it is added to the organic silver salt-containing layer.
The timing of benzoic acid addition is any process for preparing the coating solution.
And may be added to the organic silver salt-containing layer.
Any process from the preparation of the machine silver salt to the preparation of the coating solution is acceptable.
However, it is preferable to apply the organic silver salt immediately after preparation. Benzoic acids
How to add powder, solution, fine particle dispersion, etc.
You may do it by the method. In addition, sensitizing dye, reducing agent, color tone
May be added as a solution mixed with other additives such as
Yes. Any amount of benzoic acid may be added.
Is 1 micromole (μmol) to 2 moles (m
ol) or less, preferably 1 mmol (mmol) to 0.5 mol (m
ol) More preferred: 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.
You can. Where a mercapto compound is used in the present invention
Ar-SM, Ar-S-S-A
What is represented by r is preferable. Where M is a hydrogen atom or
Alkali metal atom, Ar is one or more nitrogen, Io
Aluminium, oxygen, selenium or tellurium atoms
An aromatic ring or a condensed aromatic ring. Preferably heteroaromatic ring
Benzimidazole, Naphthimidazole, Benzo
Thiazole, naphthothiazole, benzoxazole,
Naphsoxazole, benzoselenazole, benzoter
Razole, imidazole, oxazole, pyrazole,
Triazole, thiadiazole, tetrazole, tria
Gin, pyrimidine, pyridazine, pyrazine, pyridine,
Purine, quinoline or quinazolinone. This complex
Aromatic rings are, for example, halogen (e.g. Br and Cl), hydrogen
Droxy, amino, carboxy, alkyl (e.g. 1
Having more than carbon atoms, preferably 1 to 4 carbon atoms
And alkoxy (e.g. one or more carbon atoms,
Preferably having 1 to 4 carbon atoms).
You may have what is selected from a substituent group. Mercap
As a substituted heteroaromatic compound, 2-mercaptoben
Diimidazole, 2-mercaptobenzoxazole, 2-
Mercaptobenzothiazole, 2-mercapto-5-methyl
Benzimidazole, 6-Ethoxy-2-mercaptobenzo
Thiazole, 2,2'-dithiobis- (benzothiazole, 3-
Mercapto-1,2,4-triazole, 4,5-diphenyl-2-yl
Midazole thiol, 2-mercaptoimidazole, 1-d
Til-2-mercaptobenzimidazole, 2-mercapto
Quinoline, 8-mercaptopurine, 2-mercapto-4 (3H)-
Quinazolinone, 7-trifluoromethyl-4-quinolinethio
2,3,5,6-tetrachloro-4-pyridinethiol, 4-
Amino-6-hydroxy-2-mercaptopyrimidine monohydride
Rate, 2-amino-5-mercapto-1,3,4-thiadiazo
3-amino-5-mercapto-1,2,4-triazole, 4-H
Dokirch-2-mercaptopyrimidine, 2-mercaptopyrim
Midine, 4,6-diamino-2-mercaptopyrimidine, 2-me
Lucapto-4-methylpyrimidine hydrochloride, 3-mer
Capto-5-phenyl-1,2,4-triazole, 2-mercapto
-4-phenyloxazole and the like, but the present invention
Is not limited to these. Of these mercapto compounds
The amount added is 0.001 to 1.0 per mole of silver in the photosensitive layer.
The molar range is preferred, more preferably 1 mole of silver.
An amount of 0.01 to 0.3 mol per unit. Possible to be used for the photosensitive layer of the present invention.
Regarding the plasticizer and lubricant, paragraph number of JP-A-11-65021
0117, Ultrahigh contrast agent for ultrahigh contrast image formation and its addition
Regarding the method and amount, paragraph number 0118 of the same issue, JP-A-11-22389
No. 8 paragraph numbers 0136 to 0193, Japanese Patent Application No. 11-87297 formula (H), formula
(1)-(3), compounds of formula (A), (B), described in Japanese Patent Application No. 11-91652
Of the general formulas (III) to (V) (specific compounds:
21 to 24), and the high contrast accelerator is disclosed in JP-A-11-65021.
Paragraph No. 0102, Japanese Patent Laid-Open No. 11-223898, Paragraph Nos. 0194 to 019
It is described in 5. In the present invention, the photosensitive silver halide grains are contained.
The layered layer has an absorption (absorbance) at the exposure wavelength of 0.1 to 0.6.
Preferably, it is preferably 0.2 or more and 0.5 or less.
Is preferred. If the absorption is large, Dmin will rise and the image will be recognized.
It becomes difficult, and if the absorption is low, the sharpness is impaired. Main departure
To absorb light-sensitive silver halide layers in light
Although any method may be used, it is preferable to use a dye. Dyeing
As long as the fee meets the above absorption requirements
For example, pyrazoloazole dyes, ant
Laquinone dye, azo dye, azomethine dye, oxono
Dye, carbocyanine dye, styryl dye, trifer
Nylmethane dyes, indoaniline dyes, indopheno
Dyes, squarylium dyes, and the like. The present invention
Preferred dyes for use in an anthraquinone dye
(For example, compounds 1 to 9 described in JP-A-5-341441, JP-A-5-341441
Compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147
Azomethine dyes (described in JP-A-5-341441)
Compounds 17 to 47), indoaniline dyes (e.g.
Nos. 11-19 and JP-A-5-341441 described in JP-A-289227
Compound 47 described in the gazette, compound described in JP-A-5-165147
Azo dyes (described in JP-A-5-341441)
Compounds 10 to 16) and squarylium dyes (Japanese Patent Laid-Open No. Hei 10-
104779 compounds 1-20, US Patent 5,380,635
Compounds 1a to 3d) described in the specification. Of these dyes
Addition methods include solutions, emulsions, solid fine particle dispersions,
Any method such as mordanted with molecular mordant
Yes. The amount of these compounds used depends on the desired absorption.
Generally, it is 1m²1μg or more per 1g range
It is preferable to use in. In the present invention, photosensitive silver halide grains are contained.
Any part other than the layer absorbs at the exposure wavelength 0.1 to 3.0
Preferably, it is 0.3 or more and 2.0 or less
Is more preferable in terms of preventing halation. The dew
Photosensitive halogenation as part having absorption at light wavelength
The layer on the opposite side of the silver particle-containing layer support (back
Layer, back surface undercoat or undercoat layer, back layer protection
Layer) or photosensitive silver halide grain-containing layer and support
A space (undercoat or undercoat layer) is preferred. Photosensitive
When silver halide grains are spectrally sensitized in the infrared region
Absorbs to parts other than the photosensitive silver halide grain-containing layer.
Any method can be used, but absorption in the visible region
The convergence maximum is preferably 0.3 or less. Used for coloring
As a dye, it absorbs the photosensitive silver halide layer
The same dyes that can be used for
The dye used in the silver halide layer may be the same or different
Yes. Photosensitive silver halide grains are dispersed in the visible region.
If sensitized, contains photosensitive silver halide grains
Any method can be used to absorb parts other than the layer.
However, dyes that can be decolored by heat treatment or decoloration by heat treatment
The combination of the compound to be erased and the dye to be erased.
Are preferred. Examples of colored layers to be erased are as follows:
However, the present invention is not limited to this.
Yes. JP-A-52-139136, 53-132334, 56
-501480, 57-16060, 57-68831
No. 57-101835, No. 59-182436, JP-A-7-
No. 36145, No. 7-199409, No. 48-33692
No. 50-16648, JP-B-2-41734, US Special
No. 4,088,497, No. 4,283,487, No.
Nos. 4,548,896 and 5,187,049 are disclosed.
ing. The amount of these compounds used depends on the intended absorption.
Generally, 1m²1μg or more per 1g
It is preferable to use within a range. In the present invention, the photosensitive material is a photosensitive layer (image type).
Provide a surface protective layer for the purpose of preventing adhesion
Can do. Any binder for the surface protective layer
Polymers may be used. As an example of the binder
Polyester, gelatin, polyvinyl alcohol,
There are cellulose derivatives, but cellulose derivatives are preferred.
Good. Examples of the cellulose derivative are listed below.
It is not limited to that. For example, cellulose acetate,
Cellulose acetate butyrate, cellulose propio
Nate, hydroxypropyl cellulose, hydroxypropyl
Propylmethylcellulose, methylcellulose, hydroxy
Siethylcellulose, carboxymethylcellulose, etc.
Or a mixture of these. Of the surface protective layer in the present invention
The thickness is preferably from 0.1 to 10 μm, particularly preferably from 1 to 5 μm.
Good. As the surface protective layer, any adhesion preventing material
Fees may be used. Examples of adhesion prevention materials include
, Liquid paraffin, silica particles, styrene-containing error
Stomer block copolymers (e.g. styrene-butane
Diene-styrene, styrene-isoprene-styrene), vinegar
Cellulose acid, cellulose acetate butyrate, cell
Loin propionate and mixtures thereof. Photosensitive layer or photosensitive layer in the present invention
For the protective layer, U.S. Pat.No. 3,253,921, U.S. Pat.
No. 74,782, No. 2,527,583 and No. 2,9
A light-absorbing substance as described in the specification of US Pat.
And filter dyes can be used. Also, compare
Dyes as described in U.S. Pat.
Can be mordanted. As the amount of filter dye used
Is preferably 0.1 to 3.0 as the absorbance at the exposure wavelength, 0.2
-1.5 is particularly preferred. The photosensitive layer in the present invention
The protective layer of the photosensitive layer contains a matting agent such as starch,
Titanium oxide, zinc oxide, silica, U.S. Pat.No. 2,992,101
Species described in the specification and No. 2,701,245
May contain polymer beads including other types of beads
it can. In addition, the emulsion surface has a small matte degree in the image area.
There is no so-called stardust failure that causes injury and light leakage.
It doesn't matter, but the Beck smoothness is 200 seconds
More preferably, it is preferably not less than 10,000 seconds, especially 300 seconds to 10000 seconds.
Below is preferred. The photosensitive layer in the photothermographic material of the present invention
Consists of one or more layers on a support. one
In the case of layer structure, organic silver salt, silver halide, reducing agent and
Binders, toning agents, coating aids and other additives
Must contain additional materials as desired, such as auxiliaries
Yes. In the case of a two-layer structure, the first photosensitive layer (usually next to the substrate)
In the contact layer) contains organic silver salt and silver halide,
Without some other ingredients in two or both layers
Don't be. Single photosensitive layer and protective layer containing all components
A two-layer construction comprising a top coat is also conceivable. Multicolor
The composition of the photosensitive photothermographic material is the same for each color.
A combination of two layers may also be included, and also U.S. Pat. No. 4,708,92.
All components within a single layer as described in Specification 8.
May contain minutes. Multi-dye multi-color photothermographic material
In the case of coating materials, each photosensitive layer is generally described in US Pat. No. 4,460,68.
As described in the specification No. 1, there is a public space between each photosensitive layer.
By using a functional or non-functional barrier layer
Thus, they are distinguished from each other and held. The photothermographic material of the present invention is a supporting material.
Containing at least one silver halide emulsion on one side of the body.
Has a photosensitive layer and a back layer on the other side.
A loose single-sided photosensitive material is preferred. The photothermographic material of the present invention has improved transportability.
Therefore, a matting agent may be added. Matting agent is general
These are fine particles of organic or inorganic compounds that are insoluble in water.
Any matting agent can be used.
No. 1,939,213, 2,701,245, 2,32
No. 2,037, No. 3,262,782, No. 3,539,344
Specified in each specification such as the specification and 3,767,448 specification
Machine matting agent, No. 1,260,772, No. 2,192,241
, No. 3,257,206, No. 3,370,951, No. 3,
In each specification such as 523,022 specification and 3,769,020 specification
Use the well-known inorganic matting agents in the industry.
Can be. For example, specifically as a matting agent
Examples of organic compounds that can be
Examples of nyl polymers include polymethyl acrylate, polymer
Til methacrylate, polyacrylonitrile, acrylo
Nitrile-α-methylstyrene copolymer, polystyrene,
Styrene-divinylbenzene copolymer, polyvinylacetate
Tate, polyethylene carbonate, polytetrafluor
Examples of cellulose derivatives such as ethylene include methyl
Cellulose, cellulose acetate, cellulose acetate
Examples of starch derivatives such as thiopropionate
Xyl starch, carboxynitrophenyl starch, urea-form
Cured with a known curing agent such as mualdehyde-starch reactant
Hardened gelatin and coacervate microcapsules
It is preferable to use hardened gelatin as a hollow particle.
it can. Examples of inorganic compounds include silicon dioxide and titanium dioxide.
Tan, magnesium dioxide, aluminum oxide, sulfate
Lilium, calcium carbonate, chloride desensitized by known methods
Silver, silver bromide, glass, diatomaceous earth, etc. are preferably used
Can. The above matting agents are different as needed
A mixture of types of substances can be used. Matting agent
There is no particular limitation on the size and shape, and those of any particle size are used
Can be. In the practice of the present invention, 0.1 μm to 30
It is preferable to use one having a particle size of μm. Also mat
The particle size distribution of the agent may be narrow or wide. Meanwhile, matting agent
Does this significantly affect the haze and surface gloss of photosensitive materials?
In addition, it can be used during matting preparation or by mixing multiple matting agents.
The particle size, shape and particle size distribution as required.
It is preferable. In the present invention, a layer containing a matting agent
As the outermost layer of the photosensitive layer surface and the back surface (photosensitive
Layer, back layer) or protective layer, undercoat
Such as the outermost surface layer or the outermost surface layer.
Contained in a layer that functions as an outer layer or close to the outer surface.
It is preferable that it is contained in a layer acting as a so-called protective layer.
Preferably. In the present invention, the back surface
The degree of smoothness is preferably 250 seconds or less and 10 seconds or more as the Beck smoothness.
More preferably, it is 180 seconds or less and 50 seconds or more. Binder suitable for the back layer in the present invention
Is transparent or translucent, generally colorless, and is a natural polymer
-Synthetic resins, polymers and copolymers, other films
Forms a medium such as: gelatin, gum arabic, po
Li (vinyl alcohol), hydroxyethyl cellulose,
Cellulose acetate, cellulose acetate butyrate
Poly (vinyl pyrrolidone), casein, starch,
Li (acrylic acid), poly (methyl methacrylic acid), poly (salt
Vinyl chloride), poly (methacrylic acid), copoly (styrene-none
Maleic acid), copoly (styrene-acrylonitrile)
 , Copoly (styrene-butadiene), poly (vinylaceta)
(E.g. poly (vinyl formal) and poly (vinyl
Nylbutyral)), poly (esters), poly (urethane)
Phenoxy resin, poly (vinylidene chloride), poly (ethylene
Poxides), poly (carbonates), poly (vinyl acetate)
Tate), cellulose esters, and poly (amides).
The Is the binder water, organic solvent or emulsion?
Further, a coating may be formed. US Pat. No. 4,460,681 and above
Backside resistive heating layer as shown in US Pat. No. 4,374,921
(Backside resistive heating layer)
You may provide in a photosensitive material. Photosensitive layer, protective layer, back in the present invention
A hardener may be used for each layer such as a layer. Examples of hardeners and
U.S. Pat.No. 4,281,060, JP-A-6-20819
Polyisocyanates described in No. 3 publication, etc.,
U.S. Pat.No. 4,791,042
Poxy compounds, described in JP-A-62-89048, etc.
The vinyl sulfone type compound etc. which are used are used. The purpose of the present invention is to improve coatability and charging.
A surfactant may be used. As an example of surfactant
Is nonionic, anionic, cationic, fluorine
Any one can be used as appropriate. Specifically,
No. 62-170950, U.S. Pat.No. 5,380,644, etc.
Fluoropolymer surfactants described in JP-A-60-244945
Fluorine series as described in Japanese Patent Laid-Open No. 63-188135
Surfactant, as described in U.S. Pat.No. 3,885,965
Polysiloxy acid surfactants, JP-A-6-301140, etc.
Polyalkylene oxide and anionic surface activity
Sex agent etc. are mentioned. Examples of solvents used in the present invention include the new version
Listed in Solvent Pocket Book (Ohm, 1994)
However, the present invention is not limited to this. Ma
In addition, the boiling point of the solvent used in the present invention is 40 ° C or higher and 180 ° C.
The thing below ℃ is preferred. Examples of solvents used in the present invention and
Hexane, cyclohexane, toluene, methanol
, Ethanol, isopropanol, acetone, methyl
Ethyl ketone, ethyl acetate, 1,1,1-trichloroethane,
Tetrahydrofuran, triethylamine, thiophene,
Trifluoroethanol, perfluoropentane, xyl
Len, n-butanol, phenol, methyl isobutyl ketone
T, cyclohexanone, butyl acetate, diethyl carbonate,
Chlorobenzene, dibutyl ether, anisole, ethyl
Lenglycol diethyl ether, N, N-dimethylform
Amides, morpholines, propane sultone, perfluoro
Examples include tributylamine and water. In the present invention, the photosensitive layer may have various supports.
It can be coated on top. Typical supports are poly
Ester film, primer polyester film, poly
(Ethylene terephthalate) film, polyethylene na
Phthalate film, cellulose nitrate film, cellulose
Sester film, poly (vinyl acetal) film
Lum, polycarbonate film and related or
Includes resinous materials, as well as glass, paper, metal, and the like.
Flexible substrates, especially partially acetylated, or
Is a baryta and / or α-olefin polymer,
Polyethylene, polypropylene, ethylene-buteneco
C2-C10 α-olefin polymers such as polymers
A paper support coated with is typically used.
The support may be transparent or opaque,
It is preferable to be clear. The photothermographic material of the present invention is antistatic or antistatic.
Are conductive layers, eg soluble salts (eg chloride, nitrate)
Etc.), vapor deposited metal layer, US Pat. No. 2,861,056
And ionic polymers as described in US Pat. No. 3,206,312.
As described in Limar or U.S. Pat. No. 3,428,451.
It may have a layer containing such an insoluble inorganic salt. A color image is produced using the photothermographic material of the present invention.
An image can also be obtained, as disclosed in JP-A-7-13295.
No.10 page 10 left column line 43 to 11 left column line 40
There is. In addition, as a color dye image stabilizer
No. 1,326,889, U.S. Pat.No. 3,432,300
, No. 3,698,909, No. 3,574,627,
No. 3,573,050, No. 3,764,337 and
Use what is illustrated in the specification of 4,042,394
Yes. The heat-developable photographic emulsion in the present invention has an immersion coating.
Coating, air knife coating, flow coating
Or the species described in US Pat. No. 2,681,294
Various coatings, including extrusion coating using a class of hoppers
It can be coated by a coating operation. As desired
U.S. Pat.No. 2,761,791 and British Patent 83
Two or more layers by the method described in the specification of No. 7,095
These layers can be coated simultaneously. Added to the photothermographic material of the present invention.
Layers, eg dye acceptors for receiving moving dye images
Layer, opaque layer when reflective printing is desired, protective top
Primers known in the coating layer and photothermographic techniques
Layers can be included. The photothermographic material of the present invention is
It is preferable that images can be formed with only one photosensitive material.
In addition, the photosensitive layer has a functional layer required for image formation such as an image receiving layer.
It is preferable not to be a fee. The photothermographic material of the present invention can be produced by any method.
May be developed, but usually imagewise exposed to heat
The development photosensitive material is heated and developed. Preferred development temperature
As 80 to 250 ° C., more preferably 100 to 140 ° C.
° C. The development time is preferably 1 to 25 seconds, and 1 to 12
Second is more preferable, and 5 to 11 seconds is more preferable. Development temperature
The degree is 110 to 140 ° C. and the development time is 5 to 11
preferable. For development methods, use a heat drum.
There is no particular restriction such as the method using a panel heater or the method,
It is preferable to perform development using a heat drum. Main departure
The bright photothermographic material may be exposed by any method.
However, laser light is preferred as the exposure light source. According to the present invention
As laser light, gas laser, dye laser,
A semiconductor laser or the like is preferable. Also semiconductor laser
Use YAG laser and second harmonic generation element
You can also. [0075] The invention is illustrated in more detail by the following examples.
As will be apparent, the invention is not limited to these examples.
There is no. Example 1 <Preparation of light-sensitive silver halide emulsion>
Rucarbamoyl gelatin 88.3g, PAO compound (HO (CH2CH2
O) n- (CH (CH3) CH2O) 17- (CH2CH2O) m-H; m + n = 5
~ 7) 10% methanol aqueous solution 10ml, potassium bromide 0.32g
0.67mol / l silver nitrate aqueous solution in the solution dissolved at 45 ℃
659ml liquid and 0.703mol KBr and 0.013mo per liter
l Solution of KI dissolved in JP 58-58288, 58-58289
Using a mixing stirrer shown in No.
Nucleation by adding 4 minutes 45 seconds by simultaneous mixing method
It was. After 1 minute, add 20 ml of 0.63N potassium hydroxide solution.
It was. After 6 minutes, 1 liter of 1976 ml of 0.67 mol / l silver nitrate aqueous solution was added.
0.657 mol KBr, 0.013 mol potassium iodide per t
And 30 μmol of dipotassium hexachloroiridate
While controlling the solution at 45 ° C and pAg8.09
It was added over 14 minutes and 15 seconds by the mixing method. Stir for 5 minutes
Thereafter, the temperature was lowered to 40 ° C. To this, add 18 ml of 56% acetic acid aqueous solution.
To precipitate the silver halide emulsion. Settling part 2
Remove the supernatant liquid and add 10 liters of water.
After stirring, the silver halide emulsion was precipitated again. More
Leave 1.5 liter of sediment and remove the supernatant.
Add 10 liters, and after stirring, silver halide emulsion
Was allowed to settle. Leave the sedimented portion 1.5 liters and supernatant
After removing 1.72 g of anhydrous sodium carbonate in 151 ml of water
The dissolved solution was added, and the temperature was raised to 60 ° C. Stir for another 120 minutes
It was. Finally, adjust the pH to 5.0 and hit 1 mol of silver.
Water was added to 1161 g. This emulsion has an average grain
Child size 0.058μm, particle size variation coefficient 12%, [100] surface
They were monodisperse cubic silver iodobromide grains with a ratio of 92%. << Preparation of powdered organic silver salts A to H >> <Purification of behenic acid and lignoceric acid> Behekel manufactured by Henkel
Acid (product name Edenor C22-85R) 100Kg, 1200Kg iso
Mix in propyl alcohol and dissolve at 50 ° C.
After filtering with a filter, cool to 30 ° C and recrystallize.
It was. The cooling speed during recrystallization is 3 ℃ / hour.
Controlled. Centrifugal filtration of the obtained crystals, 100Kg
After washing with isopropyl alcohol,
The recrystallization was repeated twice and dried.
The obtained crystals were esterified and subjected to GC-FID measurement.
The behenic acid content was 98% and lignoceric acid 2%.
It was. In addition, erucic acid was 0.000001% or less. <Purification of arachidic acid> 100K arachidic acid manufactured by Tokyo Chemical Industry
g in 1200 kg isopropyl alcohol and dissolve at 50 ° C.
And filter with a 10 μm filter and cool to 20 ° C.
Rejected and recrystallized. Cooling speed for recrystallization
The temperature was controlled at 3 ° C./hour. The obtained crystal
Filtration of the heart and washing with 100 kg of isopropyl alcohol
And then recrystallizing twice more
It was. Then, the precipitate at the initial stage of recrystallization is filtered to remove arachidin.
Carboxylic acid having a chain length longer than that of the acid was removed and drying was performed.
The obtained crystals were esterified and subjected to GC-FID measurement.
The silver arachidate content was 100%. In addition, D
Lucaic acid was 0.000001% or less. <Purification of stearic acid> 100K stearic acid made by Tokyo Chemical Industry
g in 1200 kg isopropyl alcohol and dissolve at 50 ° C.
And filter with a 10 μm filter and cool to 20 ° C.
Rejected and recrystallized. Cooling speed for recrystallization
The temperature was controlled at 3 ° C./hour. The obtained crystal
Filtration of the heart and washing with 100 kg of isopropyl alcohol
And then recrystallizing twice more
It was. Thereafter, the precipitate at the initial stage of recrystallization is filtered to obtain stearin.
Carboxylic acid having a chain length longer than that of the acid was removed and drying was performed.
The obtained crystals were esterified and subjected to GC-FID measurement.
The silver stearate content was 100%. In addition, D
Lucaic acid was 0.000001% or less. Erucic acid is Tokyo Kasei
The product was used. In 4720 ml of pure water at the ratio shown in Table 1,
Henic acid, arachidic acid, stearic acid, lignoserine
Add a total of 0.7552 mol of acid and erucic acid and dissolve at 80 ° C.
After dissolving, add 540.2 ml of 1.5N sodium hydroxide aqueous solution.
Add 6.9 ml of concentrated nitric acid, cool to 55 ° C, and add organic acid.
A sodium solution was obtained. Of the above organic acid sodium solution
While maintaining the temperature at 55 ° C, 45.3 g of the above silver halide emulsion
And 450 ml of pure water were added, and IKA JAPAN homogenizer (U
LTRA-TURRAXT-25) 13200 rpm (mechanical vibration frequency)
(21.1 KHz) for 5 minutes. Next, 1 mol / l silver nitrate
Add 702.6 ml of solution over 2 minutes, stir for 10 minutes,
A mechanical silver salt dispersion was obtained. The resulting organic silver salt dispersion
Transfer to a water-washing container, add deionized water, stir, and leave still.
Let the organic silver salt dispersion float and separate,
Was removed. Then, until the drainage conductivity reaches 2 μS / cm.
Repeated water washing with deionized water, draining, and centrifugal dehydration
10% by volume until the weight loss disappears at 40 ℃
Dry with a circulating drier with warm air with an oxygen partial pressure of
Machine silver salts A to H were obtained. Table 2 shows the shapes of organic silver salts A to H.
The state was shown. [0077] [Table 1] [0078] [Table 2]<< Preparation of photosensitive emulsion dispersion >>
Methyl tilal powder (Monsant Butvar B-79) 14.57g in methyl
Dissolve in 1457 g of ethyl ketone (MEK), and use VMA-GETZMANN
Dissolver DISPERMAT CA-40M powder with stirring
Add 500g of organic silver salt gradually and mix well to form a slurry
It was. GM-2 type pressure type made by SMT Co., Ltd.
Photosensitive milk by dispersing 2 baths with a homogenizer
An agent dispersion was prepared. At this time, the processing pressure for one bus is 280 kg
/cm²The processing pressure for 2 buses is 560kg / cm²It was. << Adjustment of photosensitive layer coating solutions 1 to 13 >>
Type emulsion dispersion (50 g) with 15.1 g of MEK added, dissolver type
Incubate at 1000rpm with a homogenizer and keep at 21 ° C
N, N-dimethylacetamide 2 molecules / odoric acid 1 molecule / bromine 1
Add 390 μl of a 10% methanol solution of molecular aggregates, 1
Stir for hours. Furthermore, 10% by mass of calcium bromide methano
494 μl of the solution was added and stirred for 20 minutes. Followed by 1
5.9% by weight dibenzo-18-crown-6 and 4.9% by weight acetate acetate
Add 167 mg of methanol solution containing lithium for 10 minutes
After stirring, 0.24% by weight of dye A, 18.3% by weight of 2-chloro
Benzoic acid, 34.2% by weight salicylic acid-p-toluenesulfone
And 4.5% by weight of 5-methyl-2-mercaptobenzii
2.6 g of a midazole MEK solution was added and stirred for 1 hour. So
Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. 13
Polyvinyl butyral (Monsant)
Butvar B-79) 13.31 g was added and stirred for 30 minutes, then 9.4
15 minutes after adding 1.08 g of tetrachlorophthalic acid solution of mass%
Stir for a while. 20% by weight of the above reduction while continuing stirring
10.0 g of agent I-2 was added and 1.1% by mass of 4-methylphthal
Add 12.4 g of MEK solution of formic acid and dye 1 and add 10% by weight of De
smodur N3300 (Mobay aliphatic isocyanate) 1.5g
Subsequently, 7.4% by mass of tribromomethyl-2-
MEK of azaphenylsulfone and 7.2% by weight phthalazine
4.27 g of solution was added and organic acid silver AH as shown in Table 3 and
And photosensitive layer coating solution by controlling the amount of silver applied
1-13 were obtained. [0081] [Chemical formula 5] << Preparation of surface protective layer coating solution >>
While stirring, cellulose acetate butyrate (Eastman
 Chemical Co., CAB171-15) 96g, polymethylmethacrylic acid
(Rohm & Haas, Paraloid A-21) 4.5g, 1,3-Di
(Vinylsulfonyl) -2-propanol 1.5 g, benzoto
Riazole 1.0g, fluorinated active agent (Asahi Glass Co., Surflo
After adding 1.0 g of KH40) and dissolving, 13.6% by weight of cellulose
Sacetobutyrate (Eastman Chemical, CAB171-
15) and 9% by weight calcium carbonate (Speciality Minerals
, Super-Pflex200) to MEK as a dissolver type homogenization
Add 30 g of dispersion at 8000 rpm for 30 minutes in the
The surface protective layer coating solution was prepared by stirring. << Production of Support >> Concentration 0.170 (Konica Corporation)
Densitometer PDA-65) colored blue, thickness 175μm
8W / m on both sides of PET film²・ Apply minona corona discharge treatment
did. <Back side application> Do not stir 830 g of MEK.
Cellulose acetate butyrate (Eastman Chemi
cal, CAB381-20) 84.2g and polyester resin (Bostic
VitelPE2200B) (4.5 g) was added and dissolved. This dissolved
0.30 g of dye B was added to the solution, and 43.2 g of methanol was added.
Fluoroactive agent dissolved in (Asahi Glass Co., Surflon KH40)
4.5g and fluorinated activator (Dainippon Ink and Mega-Fag
Add F120K) 2.3g and stir well until dissolved
It was. Finally, the methyl ethyl ketone has a concentration of 1% by weight.
Silica (W.R.G) dispersed with a dissolver type homogenizer
Race, Syloid 64X6000) 75g added, stirred, back
A surface coating solution was prepared. Back surface coating adjusted in this way
Push the cloth liquid onto the support so that the dry film thickness is 3.5 μm.
Coating and drying were performed with a take-out coater. Drying temperature 100 ° C,
It dried for 5 minutes using the drying wind with an outdoor temperature of 10 degreeC. [0085] [Chemical 6] << Preparation of photothermographic material >> Application of photosensitive layer
Liquids 1 to 13 and the surface protective layer coating liquid
By simultaneously applying multiple layers on a support with a coated surface.
Thus, photothermographic materials 1 to 13 were prepared. Apply surface protection
The protective layer was formed to have a dry film thickness of 2.5 μm. That
Then, using drying air with a drying temperature of 75 ° C and a dew point temperature of 10 ° C,
Dried for minutes. The photothermographic material thus obtained was subjected to the following conditions.
The solvent content is the sum of MEK and methanol content
It was. 46.3cm as film area²Cut out 5mm
Finely chopped and stored in a special vial, septum
After sealing with aluminum cap, Hewlett-Packard
Gas chromatograph (GC) 5971 type head
Space sampler set to HP7694 type. GC
The detector is a flame ionization detector (FID) and the column is J & W.
DB-624 made from was used. The main measurement conditions are head space.
The sampler is heated at 120 ° C for 20 minutes.
The temperature was raised from 45 ° C. for 3 minutes to 100 ° C. at 150 ° C. and 8 ° C./min.
The calibration curve is dedicated to a certain amount of butanol dilution of each of the above solvents.
Obtained by measuring in the same manner as above after storing in a vial.
It was prepared using the peak area of the chromatogram. Izu
These photothermographic materials also have a solvent content of 30-50 mg / m.²of
It was in range. Photosensitive material 100cm²Cut out the photosensitive layer
Peeled in K. Micro digest A30 made by Prolab
Sulfuric acid decomposition with type 0 microwave wet cracking equipment
VG Elemental PQ-Ω type ICP-MS (Inductive coupling plasm
The analysis was performed using the calibration curve method with a mass spectrometer.
The Zr content in the light-sensitive material is 10 μg or less per 1 mg of Ag.
It was. (Exposure and development processing) Wavelength by high frequency superposition
800nm ~ 820nm vertical multimode semiconductor laser
We made a prototype of an exposure machine that used as an exposure source and made it as described above.
From the emulsion side of the photosensitive material, laser exposure is performed by this exposure machine.
Exposure by inspection was given. At this time, to the exposed surface of the photosensitive material
Record an image with a scanning laser beam incident angle of 75 degrees
It was. Then using an automatic processor with a heat drum
Ensure that the protective layer of the photothermographic material is in contact with the drum surface
The images obtained by thermal development at 124 ° C for 9 seconds, 11 seconds, and 13 seconds
Was evaluated with a densitometer. At that time, exposed and developed parts
The shop was 23 ° C and 50% RH. Normal scanning laser
Scanning laser light on the exposed surface of photothermographic material using light
Recorded by a normal image recording method with an incident angle of 90 degrees
Compared to the case, the image quality is less deteriorated due to uneven interference in the image.
And unexpectedly good sharpness and contrast
Obtained. <Evaluation of photographic performance>
After performing laser exposure and heat development by the above method,
The relative sensitivity and minimum concentration (Dmin) of each sample were measured.
At that time, the photothermographic material 7 was exposed for 11 seconds in Experiment No. 19.
Required to obtain a minimum density plus a blackening density of 1.0.
The reciprocal of the exposure amount was taken as 100 and expressed as a relative value. The value is large
It shows that sensitivity is so high. The results are shown in Table 3. [0089] [Table 3]As is apparent from the results in Table 3, the present invention
Depending on the embodiment, it is possible to obtain high sensitivity with less fog.
Yes. Especially with small amount of coated silver or short heat development time
Good results with high sensitivity and few blurs
The [0091] According to the present invention, high sensitivity and low fog are obtained.
Thermal development that enables rapid processing with a small amount of coated silver
A photosensitive material can be provided.

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Claims (1)

What is claimed is: 1. A photosensitive silver halide, a reducing agent for silver ions, a binder and non-photosensitive organic silver salt particles are contained on one side of a support, and the amount of coated silver There 1m ² per 0.
In the photothermographic material of 5 g to 1.9 g, the erucic acid content of the non-photosensitive organic silver salt particles is 0.00001 mol% to 50 mol% with respect to the sum of the number of moles of behenic acid and silver behenate. A heat-developable photosensitive material, characterized in that