JP2003295378A - Heat-developable photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-developable photosensitive material excellent in film strength, rapid processability and inhibition of fogging and having good image preservability. <P>SOLUTION: The heat-developable image recording material comprises on one face of a support at least one photosensitive silver halide, non-photosensitive organic silver salts, a reducing agent for a silver ion and a binder, wherein at least one of the non-photosensitive organic silver salts is the silver salt of a polymer containing a repeating unit derived from a monomer having a carboxyl group or a salt thereof and the average polymerization degree of the polymer is ≤30. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to film strength and rapid processing.
New thermal development feeling that has excellent properties and suppresses fogging
It relates to optical materials. [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.
From the viewpoint of ease of diagnosis
is there. Currently, inkjet printers, electrophotography, etc.
Various hard copy systems using pigments and dyes are common
Although distributed as an image forming system,
There is no satisfactory output system. On the other hand, a thermal image using a reducible silver salt
For example, U.S. Pat. No. 3,152,904
Nos. 3457075 and D.C. Crostabor
(Klosterboer) "The silver system processed by heat
(Thermally Processed SilverSystems) "(Imagen
Processing and Materials (ImagingPr
ocesses and Materials) Neblette 8th edition, J. Sturge
(Sturge), V. Walworth, A. Shepp (S
hepp) Edit, Chapter 9, 279, 1989)
Has been. In particular, a photothermographic material generally has a catalytic activity.
Amount of photocatalyst (eg, silver halide), reducing agent, reduction
Possible silver salt (eg reducible silver salt), silver if necessary
A binder matrix that controls the color tone of the binder
It has a photosensitive layer dispersed therein. Photothermographic material
Is heated to a high temperature (for example, 80 ° C. or higher) after image exposure,
A reducible silver salt (which functions as an oxidizing agent) and a reducing agent
A black silver image is formed by the redox reaction. acid
The reduction reaction is the contact of the latent image of silver halide generated by exposure.
It is promoted by the medium action. Therefore, the black silver image
It is formed in the exposure area. U.S. Patent No. 2910377, JP-B 43-
It is disclosed in many documents including 4924. Reducible for use in these photothermographic materials.
As a silver salt, it is relatively stable to light, but exposure
Photocatalyst (eg latent image of photosensitive silver halide) and return
When heated to 80 ° C or higher in the presence of the base agent
Silver salts that form silver images are conventionally used. This
Such non-photosensitive reducible silver salts are disclosed in JP-A-06-1
30543, 08-314078, 09-127643, 10-62899
Nos. 0048 to 0049, JP-A-10-94074,
No. 10-94075, 18th page of European Patent Publication No. 0803684A1
Pages 24-19, page 37, European Patent Publication No.
0962812A1, 100004930A2, JP 11-349591,
JP 2000-7683, 2000-72711, 2000-112057,
It is described in 2000-155383. Silver salt of organic acid,
Especially long-chain aliphatic (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms)
A silver salt of carboxylic acid is used, for example behenic acid
Silver, silver arachidate, silver stearate, silver oleate,
Silver laurate, silver caproate, silver myristate, palmi
Examples thereof include silver titanate and a mixture thereof.
U.S. Pat. No. 4,504,575 discloses sulfonic acid silver.
Japanese Patent Laid-Open No. 52-137321 discloses a salt.
Conductor silver complexes are disclosed in JP-A-53-116144 and JP-A-5-116144.
58-118638 includes a silver complex of a triazole derivative
Is disclosed. JP 2000-292881 A
For example, methacrylic acid / styrene copolymer polymer
By using silver salt in an environment where silver potential is limited,
A technique for improving the storage stability is disclosed. The photothermographic material is a photosensitive material as described above.
Contains all the chemicals necessary for development.
Just by applying heat without using processing solution.
It has the characteristic that can be formed. That
Therefore, unexposed depending on storage condition and wet heat history before exposure
It is said that image generation at the screen, so-called fogging, is likely to occur.
Has a problem. On the other hand, silver is supplied to AgX with a latent image.
The reducible silver salt is a bulky organic compound.
In general. Therefore, the film thickness of the photosensitive material is
It is about 10 times thicker than conventional silver halide photographic materials.
In the manufacturing process and film strength, there was a problem. Also enthusiastic
Because of image processing, further thinning is desired in terms of rapid processing.
It was rare. In addition, because no processing solution is used,
Photosensitive silver halide and reducible silver salt during storage
It will remain, and image storability with light and heat will be a problem
It was. [0007] SUMMARY OF THE INVENTION The object of the present invention is to
Providing a photothermographic material that solves these problems
It has excellent film strength, rapid processability, and suppression of fogging.
To provide a photothermographic material having excellent image storage stability
is there. [0008] The above object of the present invention is as follows.
This was achieved by the photothermographic material having the structure described above. 1. At least one photosensitivity on one side of the support
Reduction for silver halide, non-photosensitive organic silver, silver ions
A heat-developable image recording material containing an agent and a binder.
And at least one of the non-photosensitive organic silver is carboxyl
Repeats derived from monomers having groups or salts thereof
A silver salt of a polymer containing
-The average degree of polymerization is 30 or less.
Image image recording material. 2. At least one of the non-photosensitive organic silver has the following general formula
The silver salt of the polymer represented by (1), whose average weight
As described in the above item 1, wherein the degree of integration is 2 to 30
A heat-developable image recording material. General formula (1) [0009] [Chemical 1] In the above general formula (1): A is carboxyl
Repeats derived from monomers having groups or salts thereof
Unit (hereinafter also referred to as “repeating unit A”). B
Is derived from an ethylenically unsaturated monomer other than A
Table of repeat units (hereinafter also referred to as “repeat unit B”)
The X is a monovalent group having at least one carbon atom
Represents. Z represents a monovalent group. a and b are copolymerization ratios
It is a mass percentage to represent, a is 5-100 mass%, b is 0.
Represents a range of ~ 95% by mass, a + b = 100% by mass
The 3. In the polymer represented by the general formula (1), a is 5
The above 2 characterized by being in the range of 0 to 100% by mass.
The heat-developable image recording material described in 1. 4). The average degree of polymerization of the polymer represented by the general formula (1) is 2
The above-mentioned 2 or 3, wherein
Photothermographic material. 5). X in the general formula (1) is a monovalent organic group having 4 or more carbon atoms.
Any one of the above 2 to 4, characterized in that
Photothermographic material. 6). X in the general formula (1) is an alkylthio group
The photothermographic material according to any one of 2 to 5 above,
Fee. 7). Z in the general formula (1) is a hydrogen atom,
5. The photothermographic material according to any one of 2 to 4 above. 8). The total film thickness on the image forming layer side of the photothermographic material is 3 μm
1 to 7 above, which is 22 μm or less
The photothermographic material according to any one of the above. 9. The heat development time of the photothermographic material is 3 seconds or more and 24 seconds or less.
9. Any one of 1 to 8 above, wherein
Photothermographic material. 10. That the binder is a polymer latex.
The heat-developable image recording according to any one of 1 to 9 above
Recording material. 11. The glass transition temperature of the binder is −20 ° C. to 80
Any one of 1 to 10 above, wherein
A heat-developable image recording material. [0011] DETAILED DESCRIPTION OF THE INVENTION The present invention is described in further detail below.
To do. The photothermographic material of the present invention is provided on one side of a support.
And at least one photosensitive silver halide, non-photosensitive
Has reducing agent and binder for organic silver, silver ion
A photothermographic material having a small amount of the non-photosensitive organic silver.
At least one of them has a carboxyl group or a salt thereof
Of polymers containing repeating units derived from
It is a silver salt, and the average degree of polymerization of the polymer is 30 or less
It is characterized by that. Non-photosensitive organic that can be used in the present invention
Any polymer that provides silver should meet the above requirements.
There are no particular restrictions. Preferred polymers have the general formula
(1) having an average polymerization degree of 30 or more
Below is the polymer. General formula (1) [0013] [Chemical 2] In the general formula (1): A is a carboxyl group
Or a repeating unit derived from a monomer having a salt thereof.
Position (hereinafter also referred to as “repeat unit A”). B is
Recursions derived from ethylenically unsaturated monomers other than A
A return unit (hereinafter also referred to as “repeat unit B”) is represented.
X represents a monovalent group having at least one carbon atom.
The Z represents a monovalent group. a and b represent copolymerization ratios
It is a mass percentage, a is 5-100 mass%, b is 0-9.
The range is 5% by mass, and a + b = 100% by mass. The repeating unit A of the above general formula (1) is given.
Monomer (hereinafter also referred to as “monomer A”)
A polymerizable monomer containing a xyl group or a salt thereof.
If there is no particular limitation. Generally, the following general formula (2)
Is preferably used. General formula (2) [0016] [Chemical Formula 3]In the above general formula (2), R¹, R², R
^ThreeEach independently represents a hydrogen atom, an alkyl group, a halogen
Or a group represented by -L-COOM. L is
Any group selected from the following linking group group, or those
A divalent linking group formed by combining two or more
The (Linking group group) Single bond, -O-, -CO-, -NR^Four−,
-S-, -SO₂-, -P (= O) (OR^Five)-, Archi
Rene group, arylene group (R^FourIs a hydrogen atom, an alkyl group,
Represents an aryl group or an aralkyl group. R^FiveIs Archi
Represents an alkyl group, an aryl group, or an aralkyl group. ) M represents a hydrogen atom or a cation. More specifically, in the formula, R¹, R²
And R^ThreeEach independently represents a hydrogen atom, an alkyl
Group, halogen atom (for example, fluorine atom, chlorine atom, odor
Elementary atoms, iodine atoms, etc.), or -L-COO described later
A group represented by M, preferably a hydrogen atom, carbon number 1
-6 alkyl group, chlorine atom, represented by -L-COOM
More preferably a hydrogen atom, having 1 to 4 carbon atoms.
An alkyl group, particularly preferably a hydrogen atom and one carbon atom.
It is an alkyl group of ~ 2. Specific examples of the alkyl group
Are methyl, ethyl, n-propyl, n-butyl
Group, sec-butyl group and the like. The alkyl group
May have an appropriate substituent. As the substituent
Is a halogen atom, aryl group, heterocyclic group, alkoxy
Sil group, aryloxy group, alkylthio group, aryl
Thio group, acyl group, hydroxyl group, acyloxy group,
An amino group, an alkoxycarbonyl group, an acylamino group,
Oxycarbonyl group, carbamoyl group, sulfonyl group,
Sulfamoyl group, sulfonamido group, sulfolyl group,
A carboxyl group etc. are mentioned. In addition, the alkyl group
The carbon number does not include the carbon atom of the substituent. Other groups
The same applies to the number of carbon atoms. L is a single bond, -O-, -CO-, -NR
^Four-, -S-, -SO₂-, -PO (OR^Five)-, Archi
Formed by a combination of a rene group, an arylene group or the like
Represents a divalent linking group. Where R^FourIs a hydrogen atom,
Represents an alkyl group, an aryl group, or an aralkyl group; R
^FiveRepresents an alkyl group, an aryl group, or an aralkyl group.
The L is a single bond, -O-, -CO-, -NR^Four
-, -S-, -SO₂-, Alkylene group, arylene group
It is preferable that -CO-, -O-, -NR
^Four-, An alkylene group or an arylene group
Are particularly preferred. When L contains an alkylene group,
The carbon number of the ruxylene group is preferably 1 to 10, more preferably
1 to 8, particularly preferably 1 to 6. Especially preferred
Specific examples of new alkylene groups include methylene and ethylene.
, Trimethylene, tetrabutylene, hexamethylene groups
Etc. When L contains an arylene group,
The carbon number of the -len group is preferably 6 to 24, more preferably
Or 6 to 18, particularly preferably 6 to 12. Especially good
Specific examples of preferred arylene groups include phenylene and naphth
And a thalene group. L is an alkylene group and aryl
A divalent linking group obtained by combining ren groups (ie
(Alkylene group), the carbon number of the aralkylene group is
Preferably 7-34, more preferably 7-26, particularly preferred
It is preferably 7-16. Particularly preferred aralkylene groups
Specific examples of phenylenemethylene group and phenylene ether
Examples include a tylene group and a methylenephenylene group. L and
The groups listed above may have an appropriate substituent.
Yes. As such a substituent, R¹~ R^ThreePlace in
The same substituents as the substituents mentioned can be mentioned.
Yes. The specific structure of L is illustrated below, but the present invention is
It is not limited to these specific examples. [0020] [Formula 4][0021] [Chemical formula 5] The following are preferred examples of the monomer A specific compound.
Although preferred structures are illustrated, the present invention is limited to these specific examples.
It is not specified. [0023] [Chemical 6]Monomer A may be used alone.
However, it is also possible to use any two or more types in combination
It is. M represents a hydrogen atom or a cation. The click
Examples of ON include lithium ion and sodium ion.
On, potassium ion, ammonium ion, etc.
Preferably hydrogen atom, sodium ion
And ammonium ions, particularly preferably hydrogen
Atomic and sodium ions. B in the general formula (1) is at least one kind.
Ethylenically unsaturated monomers (hereinafter referred to as “Monomer B”)
Repeat unit derived from the above
Or the monomer group exemplified below.
Selected as independent and free combination copolymers
It is possible. There are no restrictions on the monomers that can be used
Without any normal radical polymerization reaction,
It can be used suitably. Monomer group (1) Alkenes Ethylene, propylene, 1-butene, isobutene, 1-
Hexene, 1-dodecene, 1-octadecene, 1-ray
Kosene, hexafluoropropene, vinylidene fluoride,
Chlorotrifluoroethylene, 3,3,3-trifluoro
Propylene, tetrafluoroethylene, vinyl chloride,
Vinylidene chloride, etc. (2) Dienes 1,3-butadiene, isoprene, 1,3-pentadie
2-ethyl-1,3-butadiene, 2-n-propylene
1,3-butadiene, 2,3-dimethyl-1,3-
Butadiene, 2-methyl-1,3-pentadiene, 1-
Phenyl-1,3-butadiene, 1-α-naphthyl-
1,3-butadiene, 1-β-naphthyl-1,3-buta
Diene, 2-chloro-1,3-butadiene, 1-bromo
-1,3-butadiene, 1-chlorobutadiene, 2-fluoro
Luo-1,3-butadiene, 2,3-dichloro-1,
3-butadiene, 1,1,2-trichloro-1,3-butyl
Tadiene and 2-cyano-1,3-butadiene, 1,4
-Divinylcyclohexane, etc. (3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates Methyl acrylate, ethyl acrylate, n-propi
Acrylate, isopropyl acrylate, n-butyl
Acrylate, isobutyl acrylate, sec-butyl
Til acrylate, tert-butyl acrylate,
Mil acrylate, n-hexyl acrylate, cyclo
Hexyl acrylate, 2-ethylhexyl acrylate
, N-octyl acrylate, tert-octyla
Chryrate, dodecyl acrylate, phenyl acrylate
, Benzyl acrylate, 2-chloroethyl acrylate
Rate, 2-bromoethyl acrylate, 4-chlorobut
Tyl acrylate, 2-cyanoethyl acrylate, 2
-Acetoxyethyl acrylate, dimethylaminoethyl
Acrylate, methoxybenzyl acrylate, 2-
Chlorocyclohexyl acrylate, furfuryl acrylic
Rate, tetrahydrofurfuryl acrylate, 5-H
Droxypentyl acrylate, 2,2-dimethyl-3
-Hydroxypropyl acrylate, 2-methoxyethyl
Acrylate, ω-methoxypolyethylene glycol
Acrylate (number of added moles of polyoxyethylene: n =
2 to 100), 3-methoxybutyl acrylate
, 2-ethoxyethyl acrylate, 2-butoxy
Ethyl acrylate, 2- (2-butoxyethoxy) ester
Tyl acrylate, 1-bromo-2-methoxyethyla
Chlorate, 1,1-dichloro-2-ethoxyethyla
Acrylate, glycidyl acrylate, etc.) (3b) Alkyl methacrylates Methyl methacrylate, ethyl methacrylate, n-propyl
Propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate
, Sec-butyl methacrylate, tert-butyl
Methacrylate, amyl methacrylate, n-hexyl
Methacrylate, cyclohexyl methacrylate, 2-
Ethylhexyl methacrylate, n-octyl methacrylate
Rate, stearyl methacrylate, benzyl methacrylate
Rate, phenyl methacrylate, allyl methacrylate
, Furfuryl methacrylate, tetrahydrofurfururi
Methacrylate, cresyl methacrylate, naphthyl
Methacrylate, 2-hydroxyethyl methacrylate
4-hydroxybutyl methacrylate, triethyl
Glycol monomethacrylate, dipropyleneglycol
Monomethacrylate, 2-methoxyethyl methacrylate
Rate, 3-methoxybutyl methacrylate, ω-meth
Xylethylene glycol methacrylate (Polyoxy
Number of moles of ethylene added: n = 2 to 100
Polyethylene glycol monomethacrylate (Poly)
Number of moles of reoxyethylene added: n = 2 to 100
), Polypropylene glycol monomethacrylate
(Addition mole number of polyoxypropylene: n = 2 to 1
00), 2-acetoxyethyl methacrylate,
2-ethoxyethyl methacrylate, 2-butoxyethyl
Methacrylate, 2- (2-butoxyethoxy) ethyl
Methacrylate, glycerol monomethacrylate, group
Lysidyl methacrylate 3-N, N-dimethylaminop
Lopyl methacrylate, chloro-3-N, N, N-tri
Methyl ammoniopropyl methacrylate, 2-carbo
Xylethyl methacrylate, 3-sulfopropyl methacrylate
Relate, 4-oxysulfobutyl methacrylate, 3
-Trimethoxysilylpropyl methacrylate, allyl
Methacrylate, 2-isocyanatoethyl methacrylate
Etc. (3c) Diester of unsaturated polyvalent carboxylic acid
Kind Dimethyl maleate, dibutyl maleate, itaconic acid
Dimethyl, dibutyl taconate, dibutyl crotonate,
Dihexyl rotonic acid, diethyl fumarate, dimethyl fumarate
Chill etc. (3d) Polyfunctional alcohol esters Ethylene glycol diacrylate, ethylene glycol
Rudimethacrylate, diethylene glycol diacryle
, Diethylene glycol dimethacrylate, trie
Tylene glycol diacrylate, triethyleneglycol
Dimethacrylate, 1,4-cyclohexanediak
Relate, pentaerythritol tetramethacrylate
, Pentaerythritol triacrylate, trimethy
Roll propane triacrylate, trimethylol eta
Triacrylate, dipentaerythritol pentame
Tacrylate, pentaerythritol hexaacryl
1,2,4-cyclohexanetriol trismeta
Chlorate, polypropylene glycol dimethacrylate
(Mole number of polyoxypropylene added: n = 2 to
100 things) (3e) Amides of α, β-unsaturated carboxylic acids
Kind Acrylamide, methacrylamide, N-methyl acrylate
Luamide, N-ethylmethacrylamide, N, N-dimethyl
Tylacrylamide, N-hydroxyethyl methacryl
Amide, N-tertbutylacrylamide, N-te
rt octyl methacrylamide, N-cyclohexyla
Kurylamide, N-hydroxymethylacrylamide,
N-phenylacrylamide, N- (2-acetoacetate
Xylethyl) acrylamide, N-benzylacrylic
Mido, N-acryloylmorpholine, diacetone
Rilamide, itaconic acid diamide, N-methylmaleimi
2-acrylamido-methylpropane sulfonic acid,
Methylenebisacrylamide, dimethacryloyl pipera
Gin etc. (4) Unsaturated nitriles Acrylonitrile, methacrylonitrile, etc. (5) Styrene and its derivatives Styrene, vinyl toluene, ethyl styrene, p-te
rt butyl styrene, methyl p-vinylbenzoate, α-
Methylstyrene, p-chloromethylstyrene, vinyl na
Phthalene, p-methoxystyrene, p-hydroxymethyl
Styrene, p-acetoxystyrene, p-styrenes
Sulfonic acid, p-styrenesulfonic acid sodium salt, p-
Styrene sulfinic acid potassium salt, p-aminomethyls
Tylene, p-divinylbenzene, 4-vinylbenzoic acid
2-acryloyl ethyl ester, etc. (6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, isobutyrate
Vinyl acetate, vinyl benzoate, vinyl salicylate, chloro
Vinyl acetate, vinyl methoxyacetate, vinyl vinyl acetate
Such (7) Vinyl ethers Methyl vinyl ether, ethyl vinyl ether, n-propyl
Propyl vinyl ether, isopropyl vinyl ether,
n-butyl vinyl ether, isobutyl vinyl ether
, Tert-butyl vinyl ether, n-pentylbi
Nyl ether, n-hexyl vinyl ether, n-oct
Til vinyl ether, n-dodecyl vinyl ether, n
-Eicosyl vinyl ether, 2-ethylhexyl vinyl
Ether, cyclohexyl vinyl ether, 2-hydride
Roxyethyl vinyl ether, 3-hydroxypropyl
Vinyl ether, 2-hydroxypropyl vinyl ether
4-hydroxybutyl vinyl ether, 3-hydro
Xylbutyl vinyl ether, 5-hydroxypentylbi
Nyl ether, 6-hydroxyhexyl vinyl ether
, (Fluorobutyl) vinyl ether, (fluorobutyl
Toxiethyl) vinyl ether, etc. (8) Other polymerizable monomers N-vinylimidazole, 4-vinylpyridine, N-bi
Nylpyrrolidone, divinyl sulfone, methyl vinyl keto
, Phenyl vinyl ketone, methoxyethyl vinyl keto
, 2-vinyloxazoline, 2-isopropenyloxy
Sazoline etc. The monomer B is used alone.
Can also be used in combination of two or more
You can also. X in the general formula (1) represents one of the polymer molecules.
Having 1 or more carbon atoms, preferably 4 or more carbon atoms bonded to the end of
It represents the above monovalent group and is special if it satisfies this condition.
There is no limit. As a typical structure, the following general formula (3)
It can also be expressed. [0036] [Chemical 7] Where R⁶Represents an alkyl group or an aryl group
These may have a substituent. Y is a bivalent ream
Represents a bond. More specifically, R⁶Has 1 carbon
Thirty to thirty alkyl groups (eg methyl, ethyl
Group, n-propyl group, n-butyl group, isobutyl group, t
ert-butyl group, n-hexyl group, cyclohexyl
Group, n-octyl group, 2-ethylhexyl group, tert
-Octyl group, isononyl group, n-decyl group, n-dode
Sil group, tetradecyl group, hexadecyl group, octadecyl group
Group, behenyl group, tridecanyl group, etc.)
20 aryl groups (eg phenyl group, 1-naphth
Til group, 2-naphthyl group, 1-anthranyl group, etc.),
These may have a substituent. With substituents
In addition to the alkyl group and aryl group shown above,
Alkoxyl group, acyl group, cyano group, acylamino
General substitution of groups, halogen atoms, acyloxy groups, etc.
The group can be mentioned. R⁶Has 2 to 20 carbon atoms
Substituted or unsubstituted alkyl group (ethyl group, n-butyl)
Group, n-hexyl group, n-dodecyl group, 2-phenyl ether
Til, 2- (2-methoxycarbonyl) butyl, etc.
A substituted or unsubstituted aryl having 6 to 18 carbon atoms
Group (phenyl group, 4-methylphenyl group, 4-ter
t-octylphenyl group, 4-n-nonylphenyl group, etc.
And particularly preferably 4 to 16 carbon atoms.
A substituted or unsubstituted alkyl group having 6 to 15 carbon atoms
A substituted or unsubstituted aryl group. Y is not particularly limited as long as it is a divalent linking group.
Yes. Same as the structure indicated by L in the description of the general formula (1)
It is possible to select freely from the category. Considering the manufacturing method
In this case, it is preferable that the Y structure contains a sulfur atom, and Y is
A sulfur atom is particularly preferred. Therefore, X is a
Preferably an alkyl group, preferably a carbon of the alkyl group.
The numbers are as described above. If Z in the general formula (1) is a monovalent group,
There is no particular limitation. Preferably, a hydrogen atom or the X
In the case of a hydrogen atom, particularly preferred is a group represented by
It is. A and b are mass percentages representing the copolymerization ratio;
Is 5 to 100% by mass, b is in the range of 0 to 95% by mass
A + b = 100% by mass. Preferably a is 25
-100 mass%, b is 0-75 mass%, more preferably
a is 50 to 100% by mass, b is 0 to 50% by mass, particularly preferred
Preferably, a is 70 to 100% by mass and b is 0 to 30% by mass.
This is the case. The average degree of polymerization of the polymer of the present invention is 30 or more.
Below and can take any value between 2 and 30. Like
Or 2 to 25, particularly preferably 4 to 20
Is the value of The polymer of the present invention is a general polymer compound.
One of the features is that this degree of polymerization is small,
In the present specification, these are generally distinguished from general polymer compounds.
For the purpose of distinction, the term “oligomer” or “telomer”
It may be noted. The polymer represented by the general formula (1) of the present invention
The polymerization method is not particularly limited.
For example, cationic polymerization and radical polymerization using vinyl groups,
Alternatively, a polymerization method such as anionic polymerization can be adopted.
Of these, radical polymerization is particularly preferred. As a polymerization initiator for radical polymerization,
Known thermal thermopolymerization initiators and radical photopolymerization initiators
Compounds can be used, especially radical thermogravimetry
It is preferred to use a co-initiator. Where radical
The thermal polymerization initiator is heated above the decomposition temperature,
It is a compound that generates radicals. Such a radio deer
Examples of the thermal polymerization initiator include diacyl peroxide.
Id (acetyl peroxide, benzoyl peroxide)
Id), ketone peroxide (methyl ethyl ketone)
Peroxide, cyclohexanone peroxide
Etc.), hydroperoxide (hydrogen peroxide, tert
-Butyl hydride peroxide, cumene hydropero
Oxides), dialkyl peroxides (di-ter
t-butyl peroxide, dicumyl peroxide,
Dilauroyl peroxide), peroxyester
(Tert-butyl peroxyacetate, tert
-Butyl peroxypivalate, etc.), azo compounds (a
Zobisisobutyronitrile, azobisisovaleronitrile
), Persulfates (ammonium persulfate, sodium persulfate)
Thorium, potassium persulfate, etc.). like this
One radical thermal polymerization initiator should be used alone
Can be used, or a combination of two or more
You can also. The radical polymerization method is particularly limited.
Not emulsion polymerization, suspension polymerization, bulk polymerization, solution weight
It is possible to take legality. Typical radical polymerization
The solution polymerization which is a method will be described more specifically.
The outline of other polymerization methods is the same, and the details are
For example, “Polymer Science Experimental Method” edited by the Society of Polymer Science (Tokyo Kagaku)
Human, 1981). Perform solution polymerization
For this, an organic solvent is used. These organic solvents are
Selectable as long as the purpose and effect of the light are not impaired.
The These organic solvents usually have a boiling point of 50 at atmospheric pressure.
An organic compound having a value in the range of ~ 200 ° C, each
Organic compounds that uniformly dissolve the constituent components are preferred. Good
Examples of preferred organic solvents are isopropanol, butane
Alcohol such as diol, dibutyl ether, ethylene
Glycol dimethyl ether, tetrahydrofuran, di
Ethers such as oxane, acetone, methyl ethyl keto
, Methyl isobutyl ketone, cyclohexanone, etc.
Tons, ethyl acetate, butyl acetate, amyl acetate, γ-butyl
Esters such as tyrolactone, benzene, toluene,
Aromatic hydrocarbons such as silene are listed. In addition, this
These organic solvents are used alone or in combination of two or more.
Can be used. In addition, monomers and produce
Combined use of water in the above organic solvent from the viewpoint of solubility of polymers
A water-mixed organic solvent is also preferably used. Also, solution polymerization conditions are particularly limited
However, for example, within a temperature range of 50 to 200 ° C,
It is preferable to heat for 10 minutes to 30 hours. Furthermore, departure
In order to prevent the generated radicals from being deactivated,
Of course, even before starting the solution polymerization, purge the inert gas.
Preferably it is done. Inert gas is usually nitrogen gas
Are preferably used. The polymer of the present invention has a preferred average degree of polymerization.
In order to obtain this, it is extremely effective to control the conditions during the polymerization
Dilute the polymerization concentration, use a large amount of polymerization initiator, polymerization temperature
The desired average degree of polymerization 30
The following polymers can be obtained: In addition, the po
For the synthesis of limer, radical polymerization using chain transfer agent
Is particularly effective, and using a chain transfer agent is desirable
The functional group can be introduced at the end of the polymer.
Is also highly preferred. The polymer of the present invention is monovalent at the polymer end.
Accurately introduce functional groups and obtain in more preferred molecular weight range
In order to achieve this, a radical polymerization method using a chain transfer agent is particularly used.
It is valid. As a chain transfer agent that can be used,
Mercaptans (eg octyl mercaptan, deci
Rumercaptan, dodecyl mercaptan, tert-dodecy
Lumercaptan, octadecyl mercaptan, thiofe
Norl, p-nonylthiophenol, etc.), polyhalogen
Alkyl halides (eg, carbon tetrachloride, chloroform, 1,
1,1-trichloroethane, 1,1,1-tribromoo
Kutan), low-activity monomers (α-methylstyrene)
Or α-methylstyrene dimer)
Preferably, it has 4 to 16 carbon atoms
Captans. The amount of these chain transfer agents used is
Chain transfer agent activity, monomer combinations, polymerization conditions, etc.
It is significantly affected by and requires precise control.
Is from 0.01 mol% to the total number of moles of monomers used
About 50 mol%, preferably 0.05 mol% to 30 mol
Mol%, particularly preferably 0.08 mol% to 25 mol%
The These chain transfer agents increase the degree of polymerization during the polymerization process.
Be present in the system at the same time as the monomer to be controlled
The addition method is not particularly limited. Monomer
It may be added after dissolving in water, or added separately from the monomer
It is also possible to do. The following can be preferably used in the present invention.
Specific examples of the polymer represented by the general formula (1)
The present invention is not limited to these specific examples. This
Here, the numerical value of a / b is a mass of 100 indicating the composition ratio of each monomer.
The fraction, m represents the degree of polymerization. [0051] [Chemical 8][0052] [Chemical 9]Is the polymer silver salt used in the present invention known?
May be produced by the synthesis method
Experimental Chemistry Course 4th edition, volume 22, p.43-43, 193-22
Please refer to page 7 and the literature described in them.
For example, those skilled in the art can prepare the product. The following is a specific method for synthesizing the polymer of the present invention.
Will be described using Compound P-1 as an example.
The description is not limited to the described method. [Synthesis Example] Synthesis of Compound P-1 5 equipped with stirrer, thermometer, cooling pipe, nitrogen gas introduction pipe
In a 00 ml flask, N, N-dimethylacetamide
120 ml, acrylic acid 72 g (1.0 mol), n-do
Add 121 g (0.6 mol) of decyl mercaptan
Heat the flask temperature to 80 ° C with stirring under an elementary air flow
did. Next, 20 g of N, N-dimethylacetamide was added.
Dissolves 1.2 g of 2,2'-azobisisobutyronitrile
The solution was added and stirred for 12 hours.
To obtain an acrylic acid oligomer solution. Obtained
Add the solution into 10 liters of acetonitrile and let stand overnight
did. Decant the supernatant and re-acetonitrile
10 liters was added and the sediment was washed.
Obtained by drying under reduced pressure at about 1000 Pa for 8 hours.
102.2 g of compound P-1 is obtained in the form of a thick solid
It was. The obtained polymer was gel permeated with DMF as a solvent.
By chromatography chromatography (GPC)
Weight average molecular weight in terms of rioethylene oxide (Mw)
And the molecular weight (Mi) of each monomer used for polymerization and
From the sum of the products of mass percentage (xi),
The average degree of polymerization was calculated. Average degree of polymerization (m) = Mw / Σ (Mi * xi / 100) The silver salt of the polymer used in the present invention (hereinafter referred to as “silver salt”)
Polymer silver salt) and its dispersion method are known in the art.
Methods etc. can be applied. For example, the above-mentioned JP-A-10
-62899, European Patent Publication No. 080363A1, European Patent Publication No. 0
962812A1, JP 11-349591, JP 2000-7683,
2000-72711, Japanese Patent Application No.11-348228-30, 11-203413
No., Japanese Patent Application No. 2000-90093, No. 2000-195621, No. 2000-1912
26, 2000-213813, 2000-214155, 2000-191
You can refer to 226 etc. Incidentally, when the polymer silver salt is dispersed, photosensitive silver is used.
Coexistence with salt increases fog and significantly reduces sensitivity.
Therefore, at the time of dispersion, the photosensitive silver salt should not be substantially contained.
Are more preferable. The present invention relates to an aqueous dispersion to be dispersed.
The amount of photosensitive silver salt in the solution is 1 mol of polymer silver salt in the solution.
0.1 mol% or less, and positive addition of photosensitive silver salt
It is not to be done. In the present invention, polymer silver salt aqueous dispersion and feeling
It is possible to produce a photosensitive material by mixing a light silver salt aqueous dispersion.
Yes, the mixing ratio of polymer silver salt and photosensitive silver salt (model
Can be selected according to the purpose, but for polymer silver salt
The ratio of the photosensitive silver salt is preferably in the range of 1 to 30 mol%.
The range of 3 to 20 mol%, particularly 5 to 15 mol% is preferred. mixture
2 or more types of polymer silver salt water dispersion and 2 or more types
Mixing the light silver salt water dispersion can be used to adjust the photographic properties.
Therefore, this method is preferably used. The silver salt of the polymer of the present invention is used in the desired amount
Yes, but the silver content is 0.1-5g / m²Is more preferable
Preferably 1-3g / m²It is. Furthermore, the silver salt of the polymer of the present invention is obtained from the present invention.
Used in combination with Mingai's reducible non-photosensitive organic silver salt
The known organic silver salts described below are
Often used preferably for adjustment of photographic performance. (Description of non-photosensitive organic silver salt) General formula (1)
Insensitivity that can be used in combination with the silver salt of the polymer represented by
Light organic silver salt is relatively stable to light, but exposure
Photocatalyst (photosensitive silver halide latent image, etc.) and reduction
When heated to 80 ° C or higher in the presence of an agent
A silver salt that forms a silver image. Non-photosensitive organic silver salt is silver
Can be any organic substance that contains a source that can reduce ions
Yes. Such a non-photosensitive organic silver salt is disclosed in
Paragraph Nos. 0048 to 004 of JP-A-10-62899
9, No. 18 of European Patent Publication No. 0803764A1
Pages 24th to 19th page 37th line, European patent publication
No. 0968212A1, JP-A-11-349591
No., JP-A 2000-7683, 2000-7271
It is described in each publication of No. 1. Silver salt of organic acid, especially
Long chain (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms)
Silver salts of aliphatic carboxylic acids are preferred. Non-photosensitive organic silver salt
Preferred examples of silver behenate, silver arachidate,
Silver stearate, silver oleate, silver laurate, capro
Silver salts of silver, silver myristate and silver palmitate,
And mixtures thereof. In the present invention
Contains silver behenate, among these non-photosensitive organic silver salts
It is preferable to use an organic silver salt having a rate of 75 mol% or more. Non-photosensitive organic that can be used in the present invention
The shape of the silver salt is not particularly limited, and is needle-like, rod-like, flat-plate-like, glue
It may be a flake. In the present invention, flake-shaped non-photosensitive
Organic silver salts are preferred. In this specification, flake shaped
The non-photosensitive organic silver salt is defined as follows. Insensitive
Non-photosensitive organic silver salt observed with an electron microscope
Approximate the shape of the particle with a rectangular parallelepiped and make the side of this rectangular parallelepiped the shortest
It was set as a, b, c from the side of the way (even if c is the same as b
Good. ) When x is calculated from the shorter numerical value a, b by the following formula:
Is calculated. x = b / a Thus, about 200 pieces
X was determined for the particles, and the average value was defined as x (average).
When the relationship of x (average) ≧ 1.5
The shape. Preferably 30 ≧ x (average) ≧ 1.5, and more
Preferably, 20 ≧ x (average) ≧ 2.0. By the way
The shape is 1.5> x (average) ≧ 1. In flake shaped particles, a is a side of b and c
The thickness of the tabular grains whose main plane is
it can. The average of a is preferably 0.01 μm or more and 0.23 μm.
More preferably, it is 0.1μm or more and 0.20μm or less.
Yes. The average of c / b is preferably 1 or more and 6 or less, more preferably
Or 1.05 or more and 4 or less, more preferably 1.1 or less.
Upper 3 or less, particularly preferably 1.1 or more and 2 or less. The particle size distribution of the non-photosensitive organic silver salt is
It is preferable that Monodisperse means short axis and long axis
The standard deviation of the length is divided by the short axis and long axis respectively.
The percentage is preferably 100% or less, more preferably 80%.
% Or less, more preferably 50% or less. Organic silver salt
Non-photosensitive organic silver salt transmission electron
It can be obtained from a microscopic image. Measure monodispersity
Alternatively, the volume-weighted average diameter of the non-photosensitive organic silver salt
There is a method to calculate the standard deviation of
The percentage (variation coefficient) of the measured value is preferably 100% or less
Lower, more preferably 80% or less, still more preferably 50%
It is as follows. As a measuring method, for example, non-dispersed in a liquid
The photosensitive organic silver salt is irradiated with laser light, and the scattered light
By finding the autocorrelation function for the time variation of fluctuations
Obtained from the obtained particle size (volume weighted average diameter)
be able to. Production of non-photosensitive organic silver salt used in the present invention
As for the manufacturing method and its dispersion method, known methods can be applied.
Yes. For example, the above-mentioned JP-A-10-62899, Europe
Patent Publication No. 0803763A1, European Patent Publication No. 096
2812A1, JP-A-11-349591, JP-A-2
000-7683, 2000-72711, Japanese Patent Application
Hei 11-348228-30, 11-203413
No., Japanese Patent Application No. 2000-90093, No. 2000-195
No.621, 2000-191226, 2000-
No. 213813, No. 2000-214155, No. 20
You can refer to each gazette of 00-191226 etc.
Yes. It should be noted that when the non-photosensitive organic silver salt is dispersed,
Coexisting with silver salt increases fog and remarkably increases sensitivity
Therefore, the photosensitive silver salt is not substantially contained at the time of dispersion.
More preferably. Moisture dispersed in the present invention
The amount of light-sensitive silver salt in the dispersion is relative to the organic acid silver salt in the solution.
0.1 mol% or less, and positive addition of photosensitive silver salt
Is not to be done. In the present invention, non-photosensitive organic silver salt water dispersion
The photothermographic material is prepared by mixing the solution and the photosensitive silver salt aqueous dispersion.
It is possible to build. Non-photosensitive organic silver salt and photosensitive silver
The mixing ratio of salt can be selected according to the purpose, but non-photosensitive organic silver
The ratio of the photosensitive silver salt to the salt is in the range of 1 to 30 mol%.
Preferably, the range of 3 to 20 mol% is more preferable,
A range of 15 mol% is particularly preferred. 2 or more types when mixing
Non-photosensitive organic silver salt aqueous dispersion and two or more photosensitive silver salts
Mixing aqueous dispersions is preferred for adjusting photographic properties.
It is a method that is often used. The non-photosensitive organic silver salt of the present invention is used in a desired amount.
Can be used, but the silver amount is 0.1-5g / m²Is preferred
1-3g / m²Is more preferable. In the following description, “reducible silver salt” means book
The polymer silver salt of the invention and the non-photosensitive organic silver salt outside the invention are combined.
Use as a name. (Description of Reducing Agent) Photothermographic material of the present invention
Preferably contains a reducing agent for reducible silver salts
Yes. Reducing agent for reducible silver salt metal silver ion
Any substance (preferably an organic substance) that reduces to silver
Good. Such a reducing agent is disclosed in paragraph No. 11-65021.
Nos. 0043 to 0045 and European Patent Publication No. 0803684A1
Page 7 line 34 to page 18 line 12
It is. In the present invention, the reducing agent is a hindered
Phenol reducing agents and bisphenol reducing agents are preferred
And compounds represented by the following general formula (R) are more preferred:
Yes. [0070] Embedded image (In the general formula (R), R¹¹and
R¹¹Each independently represents an alkyl group having 1 to 20 carbon atoms.
Represent. R¹²And R¹²Each independently represents a hydrogen atom or
Represents a substituent substitutable on the benzene ring. L is -S-
Group or -CHR¹³-Represents a group. R ¹³Is a hydrogen atom or
Represents an alkyl group having 1 to 20 carbon atoms. X¹And X¹’
Each independently can be substituted with a hydrogen atom or a benzene ring
Represents a radical. ) The general formula (R) will be described in detail. R
¹¹And R¹¹Each independently represents a substituted or unsubstituted carbon.
A prime number alkyl group having 1 to 20 alkyl group substituents
Is not particularly limited, but preferably aryl
Group, hydroxy group, alkoxy group, aryloxy group,
Alkylthio group, arylthio group, acylamino group,
Luphonamide group, sulfonyl group, phosphoryl group, acyl
Groups, carbamoyl groups, ester groups, halogen atoms, etc.
I can get lost. R¹²And R¹²Each independently represents a hydrogen atom
Is a substituent which can be substituted on a benzene ring or a benzene ring, and X¹Oh
And X¹′ Are also independently a hydrogen atom or a benzene ring.
Represents a substitutable group. Each can be replaced with a benzene ring
Such groups are preferably alkyl groups, aryl groups,
Examples include a rogen atom, an alkoxy group, and an acylamino group.
The L is a -S- group or -CHR.¹³-Group
The R¹³Is a hydrogen atom or alkyl having 1 to 20 carbon atoms
Represents an alkyl group, and the alkyl group may have a substituent. R
¹³Specific examples of the unsubstituted alkyl group are methyl group, ethyl
Group, propyl group, butyl group, heptyl group, undecyl
Group, isopropyl group, 1-ethylpentyl group, 2,4,
4-trimethylpentyl group etc. are mentioned. Alkyl
Examples of group substituents are R¹¹As the substituents of
Child, alkoxy group, alkylthio group, aryloxy
Group, arylthio group, acylamino group, sulfonamide
Group, sulfonyl group, phosphoryl group, oxycarbonyl
Group, carbamoyl group, sulfamoyl group, etc.
The R¹¹And R¹¹'Is preferably charcoal
A secondary or tertiary alkyl group having a prime number of 3 to 15,
Physically, isopropyl group, isobutyl group, t-butyl
Group, t-amyl group, t-octyl group, cyclohexyl
Group, cyclopentyl group, 1-methylcyclohexyl group,
Examples include 1-methylcyclopropyl group. in
Is more preferably a tertiary alkyl having 4 to 12 carbon atoms.
Among them, t-butyl group, t-amyl group, 1-methylsilane
A cyclohexyl group is more preferred, and a t-butyl group is most preferred.
Good. R¹²And R¹²′ Has 1 to 20 carbon atoms
The alkyl group is preferably exemplified. Specifically, Mechi
Group, ethyl group, propyl group, butyl group, isopropyl
Group, t-butyl group, t-amyl group, cyclohexyl group,
1-methylcyclohexyl group, benzyl group, methoxy group
A til group, a methoxyethyl group, etc. are mentioned. in
Also methyl, ethyl, propyl, isopropyl
Group, t-butyl group is more preferable. X¹And X¹'age
Are preferably a hydrogen atom, a halogen atom, or an alkyl group.
And more preferably a hydrogen atom. L is preferably -CHR.¹³-Group. R
¹³As a hydrogen atom or alkyl having 1 to 15 carbon atoms
Groups are preferred. Examples of the alkyl group include a methyl group and an ether group.
Til, propyl, isopropyl, 2,4,4-to
A limethylpentyl group is preferred. R¹³Especially as preferred
Or hydrogen, methyl, propyl or isopropyl
It is a pill group. R¹³R is a hydrogen atom, R¹²And R
¹²′ Is preferably an alkyl group having 2 to 5 carbon atoms,
The alkyl group is more preferably an ethyl group or a propyl group.
The ethyl group is most preferable. R¹³Is 1 having 1 to 8 carbon atoms
In the case of a secondary or secondary alkyl group, R¹²And R¹²’
Is preferably a methyl group. R¹³1 to 8 carbon primary or
Secondary alkyl groups include methyl, ethyl, and pro
A pill group and an isopropyl group are more preferable.
A til group and a propyl group are more preferable. R¹¹, R¹¹', R
¹²And R¹²When both of 'are methyl groups,
R¹³Is preferably a secondary alkyl group. This place
R¹³Examples of the secondary alkyl group include isopropyl group and a
A sobutyl group and a 1-ethylpentyl group are preferable.
A propyl group is more preferred. The following are represented by the general formula (R) of the present invention.
Although the specific example of the reducing agent of this invention including a compound is shown,
The present invention is not limited to these. [0080] Embedded image[0081] Embedded image[0082] Embedded image In the present invention, the reducing agent is added in an amount of 0.0.
1 to 5.0 g / m²Is preferably 0.1 to
3.0g / m²More preferably, the image forming layer
5 to 50% mol is included with respect to 1 mol of silver on the surface having
Preferably 10 to 40 mol%.
Further preferred. The reducing agent may be included in the image forming layer.
preferable. The reducing agent is in the form of a solution, emulsified dispersion, solid.
Included in the coating solution by any method such as fine particle dispersion form
And may be contained in the light-sensitive material. well known
Emulsion dispersion methods include dibutyl phthalate, tricresi
Ruphosphate, glyceryl triacetate or
Oils such as diethyl phthalate, ethyl acetate and cyclo
Dissolve using an auxiliary solvent such as hexanone and mechanically milk
The method of making a dispersion is mentioned and can be adopted.
Yes. 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 water
The dispersion contains a preservative (eg, benzoisothiazolinone sodium
A lithium salt). (Description of Development Accelerator) Photothermographic photosensitive material of the present invention
In terms of materials, it is disclosed in Japanese Patent Application No. 11-73951 as a development accelerator.
Phenol derivatives represented by the formula (A) described are preferred
Used. (Description 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 is not included,> 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). [0088] Embedded image In the general formula (D), R^{twenty one}~ R^{twenty three}Each
Independently, an alkyl group, an aryl group, an alkoxy group, an
Represents a reeloxy group, an amino group or a heterocyclic group.
These groups may be unsubstituted or have a substituent.
Yes. R^{twenty one}~ R^{twenty three}As 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.
Among them, an alkyl group and an aryl group are preferable,
For example, methyl group, ethyl group, isopropyl group, t-butyl
Group, t-octyl group, phenyl group, 4-alkoxy group
Specific examples include an phenyl group and a 4-acyloxyphenyl group.
Can be mentioned. R^{twenty one}~ R^{twenty three}Specific examples of the alkyl group of
Methyl, ethyl, butyl, octyl, dodecyl
Group, isopropyl group, t-butyl group, t-amyl group,
t-octyl group, cyclohexyl group, 1-methylcyclo
Hexyl, benzyl, phenethyl, 2-phenoxy
Examples include a cypropyl group. As an aryl group,
Specifically, phenyl group, cresyl group, xylyl group, naphthy
Group, 4-t-butylphenyl group, 4-t-octylph
Enyl group, 4-anisidyl group, 3,5-dichloropheny
And the like. Specific examples of alkoxy groups
Methoxy, ethoxy, butoxy, octyloxy
Si group, 2-ethylhexyloxy group, 3,5,5-tri
Methylhexyloxy, dodecyloxy, cyclohexyl
Xyloxy group, 4-methylcyclohexyloxy group,
A benzyloxy group etc. are mentioned. With aryloxy group
Specifically, phenoxy group, cresyloxy group,
Sopropylphenoxy group, 4-t-butylphenoxy
Group, naphthoxy group, biphenyloxy group, etc.
The Specific examples of the amino group include a dimethylamino group and di
Ethylamino group, dibutylamino group, dioctylamino
Group, N-methyl-N-hexylamino group, dicyclohexyl
Silamino group, diphenylamino group, N-methyl-N-
A phenylamino group etc. are mentioned. R^{twenty one}~ R^{twenty three}As an alkyl group, aryl
A ruthenium group, an alkoxy group, and an aryloxy group are preferable. Book
In terms of the effect of the invention, R^{twenty one}Or R^{twenty three}At least
It is preferred that one is an alkyl group or an aryl group
2 or more are alkyl groups or aryl groups
Is more preferable. Also, if you can get it cheaply
In that sense, R^{twenty one}Or R^{twenty three}Are 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
The present invention is not limited to these. [0092] Embedded image [0093] Embedded imageSpecific examples of the hydrogen bonding compound are other than the above.
Listed in Application Nos. 2000-192191 and 2000-194811
It is done. The compound of the general formula (D) is a solution similar to the reducing agent.
Apply in form, emulsified dispersion form, solid dispersion fine particle dispersion form
It can be contained in a solution and used in a photosensitive material.
The compound of the general formula (D) is a phenolic hydroxide in the solution state.
A hydrogen-bonding complex with a group or amino group-containing compound
A combination of a reducing agent and a compound of general formula (D)
Can be isolated in crystalline form as a complex.
The The crystal powder isolated in this way is converted into solid dispersed fine particles.
The use as a dispersion is special for obtaining stable performance.
Is preferred. In addition, the reducing agent and the compound of the general formula (D)
Mix with the body and use a suitable dispersant, sand grinder
A method of complexing at the time of dispersion with a mill or the like is also preferably used.
be able to. The compound of general formula (D) 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 used in the range of 30 to 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 can be used. Among them, silver bromide and
Silver iodobromide is preferred. Halogen composition in grains
The distribution of the halogen composition may be uniform
It may have changed in shape or continuously changed
It's okay. Halogen with core / shell structure
Silver halide grains can be preferably used. Good structure
The preferred one has a 2-5 layer structure, more preferably 2-2.
Quadruple core / shell particles can be used. Ma
Of silver bromide on the surface of silver chloride or silver chlorobromide grains
The technique can also be preferably used. 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 a light-sensitive silver halide and then reducible silver salt
A method of mixing is used. Japanese Laid-Open Patent Publication No. 11-119374
The method described in paragraph numbers 0217 to 0224 of Japanese Patent Application No. 11
-98708 and Japanese Patent Application No. 2000-42336 are also preferred. 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.
Specifically, specifically 0.20 μm or less, more preferably
0.01 μm or more and 0.15 μm or less, more preferably
It is preferably 0.02 μm or more and 0.12 μm or less. Here
The grain size is the projected area of silver halide grains (tabular grains
In the case of a child, it is converted into a circular image with the same area as the projected area of the main plane)
The diameter when 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 over 50%
65% or more is more preferable, 80% or more is more preferable
That's right. The ratio of the Miller index [100] surface is important for sensitizing dye adsorption.
T. Tan using the adsorption dependence of [111] and [100] surfaces
i; according to the method described in J. Imaging Sci., 29, 165 (1985)
Can be requested. In the present invention, a hexacyano metal complex is granulated.
Silver halide grains present on the outermost surface of the child are preferred. Six
Examples of cyano metal complexes include [Fe (CN)₆]^Four-, [F
e (CN)₆]^3-, [Ru (CN)₆]^Four-, [Os (C
N)₆]^Four-, [Co (CN)₆] ^3-, [Rh (CN)₆]
^3-, [Ir (CN)₆]^3-, [Cr (CN)₆]^3-, [R
e (CN)₆]^3-Etc. In the present invention
A hexacyano Fe complex is preferred. The hexacyano metal complex is an ionic compound in aqueous solution.
The counter cation is not important because it is
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 mole of silver.
Per 1 × 10^-Five1 x 10 moles or more^-2Less than moles are preferred
More preferably 1 × 10^-Four1 x 10 moles or more^-3Mole
It is as follows. 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. It should be noted that the addition of the hexacyano metal complex is in the form of particles.
Add 96% of the total amount of silver nitrate to be added
May be started from the beginning or after 98% is added
It is more preferable to add 99%.
Yes. 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 form a sparingly soluble salt with silver ions on the surface of the particles. This
The silver salt of hexacyanoiron (II) is less soluble than AgI
Therefore, re-dissolution by fine particles can be prevented and
It is possible to produce silver halide fine grains with small child size
Is possible. The photosensitive silver halide grain of the present invention has a periodicity.
Of the 8th to 10th groups of the chart (showing the 1st to 18th groups)
It can contain metals or metal complexes. Periodic table
A metal of group 8 to group 10 or a central metal of a metal complex
And preferably rhodium, ruthenium or iridium.
is there. These metal complexes may be of one type,
Two or more different metal complexes may be used in combination. preferable
The content is 1 x 10 per mole of silver^-9From mole to 1 × 10^-3
A molar range is preferred. These heavy metals and metal complexes and
Regarding their addition method, JP-A-7-225449, JP-A-11
No. -65021, paragraph numbers 0018 to 0024, paragraph No. 11-119374
Nos. 0227 to 0240. Further, silver halide grains used in the present invention
Metal atoms that can be contained in the child (for example, [Fe (C
N)₆]^Four-), Desalting and chemical sensitization of silver halide emulsions
JP, 11-84574, A paragraph number 0046-0050, JP, 11-84574, A
No. 11-65021, paragraphs 0025-0031, JP-A-11-119374
Paragraph Nos. 0242 to 0250. In the photosensitive silver halide emulsion used in the present invention,
Various gelatins are used as the contained gelatin.
Can. Reduction of photosensitive silver halide emulsions
To maintain a good dispersion state in the silver salt-containing coating solution
In addition, low molecular weight gelatin with a molecular weight of 500-60,000
It is preferable to use These low molecular weight gelatins
Is used during particle formation or dispersion after desalting.
However, it is preferable to use it during dispersion after desalting.
Yes. Examples of sensitizing dyes that can be used in the present invention include
When adsorbed on silver halide grains, halogen in the desired wavelength region
That can spectrally sensitize silver halide grains.
The sensitizing dye having the spectral sensitivity suitable for the property
be able to. Regarding the sensitizing dye and the addition method,
Paragraph Nos. 0103 to 0109 of No. 11-65021, JP-A-10-186572
A compound represented by the general formula (II), one of JP-A-11-119374
Dye represented by general formula (I) and paragraph number 0106, U.S. Pat.
No. 5,510,236, No. 3,871,887 Example 5 dye,
It is disclosed in JP-A-2-96131 and JP-A-59-48753
Dye, European Patent Publication No. 080364A1, page 19, line 38
-Page 20, line 35, Japanese Patent Application No. 2000-86865, Japanese Patent Application 2000-102
No. 560 and Japanese Patent Application No. 2000-205399. these
Sensitizing dyes may be used alone or in combination of two or more
May be. In the present invention, the sensitizing dye is silver halide milk.
The time to add to the agent is after the desalting process until the application.
Preferably, more preferably after desalting and before the start of chemical ripening
It is time until. Addition amount of sensitizing dye in the present invention
Make the desired amount according to the sensitivity and fog performance
10 per mole of silver halide in the photosensitive layer.
^-6~ 1 mol is preferred, more preferably 10^-Four-10
^-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, in 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 the literature described in No. 0030, JP-A-5-31
Compounds represented by general formulas (II), (III) and (IV) in 3284
More preferred. 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
There may be (4) immediately before application. Especially after spectral sensitization
It is preferable that Sulfur and selenium used in the present invention
The amount of tellurium sensitizer used depends on the silver halide used.
Depending on grain, chemical ripening conditions, etc., silver halide
10 per mole^-8-10^-2Moles, preferably 10^-7~
10^-3Use about moles. The condition of chemical sensitization in the present invention
There are no particular restrictions on the conditions, but the pH is 5 to 8, p.
Ag is 6 to 11, and temperature is about 40 to 95 ° C.
It is. The silver halide emulsion used in the present invention contains a European special
According to the method disclosed in allowed publication No. 293,917,
A sulfonic acid compound may be added. 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 0.2 log E or more for each emulsion.
It is preferable to have it. The amount of photosensitive silver halide added was 1 m of photosensitive material.
²Indicated by the amount of applied silver per unit, 0.03 to 0.6 g / m²
Preferably, 0.07 to 0.4 g / m²In
More preferably, 0.05 to 0.3 g / m²so
Most preferably, for every mole of reducible silver salt
The photosensitive silver halide is 0.01 mol or more and 0.5 mol.
Is preferably 0.02 mol or more and 0.3 mol or less.
More preferred. Separately prepared photosensitive silver halide and reduction
For possible silver salt mixing methods and conditions, see
Highly prepared silver halide grains and reducible silver salts
Fast stirrer, ball mill, sand mill, colloid mill, vibration
Mixing with a dynamic mill, homogenizer, etc., or
Prepared at any time during preparation of reducible silver salt
Silver salt that can be reduced by mixing the finished photosensitive silver halide
However, the effects of the present invention are fully manifested.
There are no particular restrictions as far as possible. Also when mixing
Two or more reducible silver salt water dispersions and two or more photosensitivities
Mixing silver salt water dispersion is for adjusting photographic characteristics
This is a preferable method. 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 60 minutes before to 10 seconds ago, how to mix
For the method and mixing conditions, the effect of the present invention is sufficiently exhibited.
As long as there is no limit. As a specific mixing method
The average stagnation calculated from the addition flow rate and the amount of liquid delivered to the coater
Mix in a tank with a desired residence time
By N.Harnby, M.F.Edwards, A.W.Nienow, Takahashi
Translated by Koji “Liquid mixing technology” (Nikkan Kogyo Shimbun, 1989)
Use the static mixer etc. described in Chapter 8 etc.
There is a way to use. (Explanation of Binder) The reducible of the present invention
The binder of the silver salt-containing layer can be any type including latex.
Polymers may be used and suitable binders are transparent or
Translucent, generally colorless, natural resin, synthetic resin, simple
Homopolymers, copolymers, other media forming films,
For example, gelatins, rubbers, poly (vinyl alcohol)
), Hydroxyethylcelluloses, cellulose
Cetates, cellulose acetate butyrate, poly
(Vinyl pyrrolidone), casein, starch, poly
(Acrylic acid), poly (methyl methacrylic acid), poly
Ri (vinyl chloride), poly (methacrylic acid), styrene
-Maleic anhydride copolymers, styrene-acrylonitrile
Tolyl copolymers, styrene-butadiene copolymers,
Poly (vinyl acetal) s (eg, poly (vinyl acetal)
Lumar) and poly (vinyl butyral)), poly (d
Stealth), poly (urethane) s, phenoxy resin, polyethylene
Li (vinylidene chloride), poly (epoxide), poly
(Carbonates), poly (vinyl acetate) s, poly (o
Olefins), cellulose esters, poly (amides)
There is kind. The binder can be water or organic solvent or emulsion.
A coating may be formed from the surface. In the present invention, a layer containing a reducible silver salt
The glass transition temperature of the binder that can be used in combination is -20 ° C.
80 ° C. or higher is preferable (hereinafter referred to as a high Tg binder)
It may be 0 ° C or more and 80 ° C or less.
Preferably, it is 10 ° C or higher and 70 ° C or lower.
More preferably, it is 15 ° C or higher and 60 ° C or lower.
That's right. In this specification, Tg is the following formula:
Is calculated. 1 / Tg = Σ (Xi / Tgi) Where 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 i-th monomer
It is a glass transition temperature (absolute temperature) of the homopolymer. The
However, Σ takes the sum from i = 1 to n. Each monomer
The homopolymer glass transition temperature value (Tgi) of Polyme
r Handbook (3rd Edition) (J.Brandrup, E.H.Immergut
(Wiley-Interscience, 1989)) was adopted. If necessary, two or more binders can be used together.
May be used. Also, glass transition temperature of 10 ° C or higher
In combination with a glass transition temperature of less than 10 ° C
It may be used. 2 or more types of polymers with different Tg
When used in the same manner, its mass average Tg is within the above range.
It is preferable to enclose. In the present invention, the reducible silver salt-containing layer
Is applied using a coating solution in which 30% or more of the solvent is water,
Contains silver salt that can be further reduced when formed by drying
Layer binder is soluble or dispersible in aqueous solvent (aqueous solvent)
Water content, especially at 25 ° C and 60% RH
Performance when the polymer is made of latex of 2% or less
Will improve. The most preferred form has an ionic conductivity of 2.
It was prepared to be 5 mS / cm or less,
As such a preparation method, a separation functional membrane is used after polymer synthesis.
And a purification method. The polymer mentioned here is soluble or dispersed.
Possible aqueous solvents are water or 70% water or less in water.
It is a mixture of miscible organic solvents. Water miscibility
Examples of the organic solvent include methyl alcohol and ethyl alcohol.
Alcohols such as lecol and propyl alcohol, meth
Lucerosolve, ethylcellosolve, butylcellosolve, etc.
Cellosolve, ethyl acetate, dimethylformamide, etc.
Can be mentioned. 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. In addition, “equilibrium water content at 25 ° C. and 60% RH”
"Rate" refers to humidity conditioning equilibrium in an atmosphere of 25 ° C and 60% RH.
Polymer in dry state at a mass W1 of polymer and 25 ° C.
It can be expressed as follows using the mass W0. Equilibrium water content at 25 ° C. and 60% RH = [(W1-W0) /
W0] × 100 (%) 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 has a temperature of 25 ° C. and 60 ° C.
The equilibrium water content at% RH is preferably 2% or less.
However, more preferably 0.01% or more and 1.5% or less,
More preferably, it is 0.02% or more and 1% or less. 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
Some of them are preferred. Dispersed particles
Has an average particle diameter of 1 to 50000 nm, more preferably 5 to 5 nm.
A range of about 1000 nm is preferable. Size of dispersed particles
There is no particular restriction on the cloth, and it has a wide particle size distribution
However, it may have a monodispersed particle size distribution. In the present invention, a polymer dispersible in an aqueous solvent.
As a preferred embodiment of the limer, an acrylic polymer,
Poly (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 polymerized
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 1,000,000 in number average molecular weight, preferably
It is preferably 10,000 to 200,000. Low molecular weight
If it is too high, the mechanical strength of the emulsion layer is insufficient and it is too large.
Those which are not preferred are not preferable because of poor film formability. (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.
The numerical value is% and the molecular weight is the number average molecular weight. Multifunctional monomer
When using-, the concept of molecular weight
Since it is not applicable, it is described as crosslinkable and the molecular weight is omitted.
did. Tg represents the glass transition temperature. Q-1; Latec of -MMA (70) -EA (27) -MAA (3)-
(Molecular weight 37000, Tg61 ℃) Q-2; -MMA (70) -2EHA (20) -St (5) -AA (5)-latex (min
(Child weight 40000, Tg 59 ℃) Q-3; -St (50) -Bu (47) -MAA (3)-latex (crosslinkability, Tg
-17 ℃) Q-4; Latex of -St (68) -Bu (29) -AA (3)-(crosslinkability, Tg1
(7 ℃) Q-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg24
℃) Q-6; -St (70) -Bu (27) -IA (3)-latex (crosslinkable) Q-7; Latex of -St (75) -Bu (24) -AA (1)-(crosslinkability, Tg2
(9 ℃) Q-8; Latex of -St (60) -Bu (35) -DVB (3) -MAA (2)-
sex) Q-9; -St (70) -Bu (25) -DVB (2) -AA (3)-latex
sex) Q-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-
(Molecular weight 80000) Q-11; -VDC (85) -MMA (5) -EA (5) -MAA (5)-latex (min
(Quantity 67000) Q-12; -Et (90) -MAA (10)-latex (molecular weight 12000) Q-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130
000, Tg43 ℃) Q-14; -MMA (63) -EA (35)-AA (2) latex (molecular weight 330
00, Tg47 ℃) Q-15; -St (70.5) -Bu (26.5) -AA (3)-latex (crosslinkable,
(Tg23 ℃) Q-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. Immediately
As an example of an acrylic polymer, Sebian A-463
5,4718, 4601 (above Daicel Chemical Industries), Nipol Lx
811, 814, 821, 820, 857 (made by Nippon Zeon Co., Ltd.), etc.
Examples of poly (esters) include FINETEX ES650, 61
1,675,850 (above Dainippon Ink & Chemicals), WD-size,
Poly (Ureta) such as WMS (Eastman Chemical)
For example, HYDRAN AP10, 20, 30, 40 (greater than
Examples of rubbers such as Nippon Ink Chemical Co., Ltd.
STAR 7310K, 3307B, 4700H, 7132C (End
Chemical Co., Ltd.), Nipol Lx416, 410, 438C, 2507
As an example of poly (vinyl chloride) such as ON
Is a poly (salt) such as G351, G576 (manufactured by Nippon Zeon Co., Ltd.)
Examples of vinylidene compounds include L502 and L513 (above Asahi Kasei)
As an example of poly (olefins) such as Kogyo Co., Ltd.
Is Chemipearl S120, SA100 (Mitsui Chemicals Co., Ltd.)
Can be mentioned. 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 is preferable. In addition, styrene monomer unit
The total amount of copolymer of butadiene monomer units
The occupying ratio is preferably 60 to 99% by mass.
The preferred molecular weight range is the same as described above. Styrene preferably used in the present invention
Examples of the butadiene copolymer latex include the aforementioned Q-3.
~ Q-8, Q-15, commercially available LACSTAR-3307B, 7132C, Nip
ol Lx416 and the like. Reducible silver salt-containing layer of the light-sensitive material of the present invention
If necessary, gelatin, polyvinyl alcohol,
Chill cellulose, hydroxypropyl cellulose, cal
Add hydrophilic polymer such as boxymethylcellulose
May be. The amount of these hydrophilic polymers added is reducible
30% or less of the total binder of the silver-salt-containing layer, more preferred
Or 20% or less. The reducible silver salt-containing layer of the present invention (ie
The imaging layer) was formed using a polymer latex
Those are preferred. Reducible silver salt containing layer binder
The amount is 1/1 of the total binder / reducible silver salt mass ratio
The range of 0-10 / 1, or even 1 / 5-4 / 1 is preferred.
Yes. In addition, such a reducible silver salt-containing layer
Usually contains photosensitive silver halide which is photosensitive silver salt
The photosensitive layer (emulsion layer), and in this case all
The mass ratio of binder / silver halide is 400 / 1-5.
/ 1, more preferably in the range of 200/1 to 10/1.
Good. The total binder amount of the image forming layer of the present invention is:
0.2-30 g / m², More preferably 1 to 15 g / m²
Range. When the polymer silver of the present invention is used, heat development feeling
The total film thickness of the optical material on the image forming layer side is 3 μm or more and 22 μm.
The following can be designed, but it must be 3 μm or more and 20 μm or less
Is preferably 3 μm or more and 14 μm or less.
It is particularly preferably 3 μm or more and 10 μm or less.
Good. (Preferable solvent for coating solution) In the present invention,
The solvent of the reducible silver salt-containing layer coating solution of the photosensitive material (here
For simplicity, the solvent and the dispersion medium are collectively referred to as a solvent. )
Is preferably an aqueous solvent containing 30% or more of water. Other than water
Ingredients include methyl alcohol, ethyl alcohol,
Sopropyl alcohol, methyl cellosolve, ethyl cello
Solve, dimethylformamide, ethyl acetate, etc.
Water miscible organic solvents may be used. Water content of solvent of coating solution
The rate is preferably 50% or more, more preferably 70% or more.
Yes. Examples of preferred solvent compositions include water / medium as well as water.
Chill alcohol = 90/10, water / methyl alcohol =
70/30, water / methyl alcohol / dimethylformua
Mid = 80/15/5, water / methyl alcohol / ethyl
Cellosolve = 85/10/5, water / methyl alcohol /
Isopropyl alcohol = 85/10/5
(The numerical value is mass%). (Description of antifogging agent)
Antifoggant, stabilizer and stabilizer precursor
JP-A-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
Things. Further, the cartridge preferably used in the present invention.
Anti-blur agents are organic halides, and about these
Are disclosed in paragraphs 0111 to 0112 of JP-A-11-65021.
The ones disclosed in Huh are listed. Especially Japanese Patent Application 11-8
Organohalogen compounds represented by formula (P) of No. 7297
Organic polyhalogenation represented by general formula (II) of 0-339934
Compound, organic polyhalogenation described in Japanese Patent Application No. 11-205330
Compounds are preferred. (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 the general formula (H), Q is an alkyl group, aryl
A group or a heterocyclic group, Y represents a divalent linking group,
n represents 0 or 1, Z₁And Z₂Is a halogen atom
X represents a hydrogen atom or an electron-withdrawing group. General formula
In (H), Q is preferably Hammett's substituent constant.
Phenyl substituted with an electron-withdrawing group having a positive value for σp
Represents a group. For Hammett's substituent constants, see Journal
of Medicinal Chemistry, 1973, Vol. 16, No. 11, 1207-1216
 Etc. can be referred to. Such an electron withdrawing
Examples of the group include a halogen atom (fluorine atom (σp
Value: 0.06), chlorine atom (σp value: 0.23), bromine
Atoms (σp value: 0.23), iodine atoms (σp value: 0.
18)), trihalomethyl group (tribromomethyl (σp
Value: 0.29), trichloromethyl (σp value: 0.3)
3), trifluoromethyl (σp value: 0.54)),
Ano group (σp value: 0.66), Nitro group (σp value: 0.
78), aliphatic, aryl or heterocyclic sulfonyl groups
(For example, methanesulfonyl (σp value: 0.72)),
Aliphatic, aryl or heterocyclic acyl groups (eg
Cetyl (σp value: 0.50), benzoyl (σp value:
0.43)), an alkynyl group (for example, C≡CH (σp
Value: 0.23)), aliphatic, aryl or heterocyclic o
A xoxycarbonyl group (for example, methoxycarbonyl (σp
Value: 0.45), phenoxycarbonyl (σp value: 0.
44)), carbamoyl group (σp value: 0.36), sulfur
A famoyl group (σp value: 0.57), a sulfoxide group,
A heterocyclic group, a phosphoryl group, etc. are mentioned. σp value
Preferably in the range of 0.2 to 2.0, more preferably
Is in the range of 0.4 to 1.0. As an electron-withdrawing group
Particularly preferred are carbamoyl groups, alkoxycarbo
Nyl group, alkylsulfonyl group, alkylphosphoryl group
Of these, a carbamoyl group is most preferred. X is preferably an electron withdrawing group.
More preferably, a halogen atom, an aliphatic sulfonyl group, an ant
Sulfonyl group, heterocyclic sulfonyl group, aliphatic acyl
Group, arylacyl group, heterocyclic acyl group, aliphatic oxy
Carbonyl group, aryloxycarbonyl group, heterocyclic o
Xoxycarbonyl group, carbamoyl group, sulfamoyl group
And particularly preferably a halogen atom. halogen
Among atoms, preferably chlorine atom, bromine atom, iodine
An atom, more preferably a chlorine atom or a bromine atom.
Particularly preferred is a bromine atom. Y is preferably-
C (= O)-, -SO- or -SO₂-Represents more
Preferably -C (= O)-, -SO₂-Especially good
Preferably -SO₂-. n represents 0 or 1,
Preferably it is 1. Specific examples of the compound of the general formula (H) are shown below.
Show. [0145] Embedded image[0146] Embedded imageCompounds represented by the general formula (H) of the present invention
Is 10 per mole of non-photosensitive silver salt of the image forming layer.^-Four~
It is preferable to use in the range of 1 mol, more preferably
10 ^-3In the range of ~ 0.8 mol, more preferably 5x
10^-3Used in the range of ~ 0.5 mol. In the present invention
As a method of adding an antifoggant to the photosensitive material
Includes the method described in the method for containing a reducing agent, and
Add polyhalogen compounds with solid fine particle dispersion.
It is preferable to add. (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
Triazine compound according to claim 9 of 52624, JP-A-6-11
791 compound represented by general formula (III), 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene and the like. The heat-developable image recording material in the present invention is a turnip.
An azolium salt may be contained for the purpose of prevention of waste. A
As the zolium salt, a general formula described in JP-A-59-193447 is disclosed.
A compound represented by (XI), a compound described in JP-B-55-12581
A compound represented by the general formula (II) described in JP-A-60-153039
Compound may be mentioned. Azolium salts can be used in any photosensitive material.
It may be added to the site, but the additive layer has a photosensitive layer.
It is preferable to add it to the surface layer, and a reducible silver salt
More preferably, it is added to the containing layer. Azolium salt
As for the timing of the addition of any of the steps in the coating solution preparation
It can be reduced when added to a reducible silver salt-containing layer.
Any process from the preparation of a functional silver salt to the preparation of a coating solution
However, it is preferable to prepare a reducible silver salt and immediately before coating. A
Zorium salt can be added by powder, solution, or fine particle dispersion.
Any method may be used. Also sensitizing dye,
Added as a solution mixed with other additives such as base agent and colorant
You may do it. In the present invention, the amount of azolium salt added
Can be any amount, but 1 x 10 per mole of silver^-6
Preferred is 1 mol or more and 2 mol or less.^-3More than mole
0.5 mol or less is more preferable. In the present invention, development is suppressed or promoted.
In order to control the image and improve the spectral sensitization efficiency,
Mercapto to improve preservability before and after images
Contains compounds, disulfide compounds, and thione compounds
Paragraph numbers 0067 to 0069 of JP-A-10-62899,
Compounds represented by general formula (I) of JP-A-10-186572 and
As specific examples, paragraph numbers 0033 to 0052, European Patent Publication No. 08
03764A1 page 20, lines 36-56, Japanese Patent Application No.11-273670
Etc. are described. Among them, mercapto-substituted heteroaromatics
Compounds are preferred. (Description of Toning Agent) Heat-developable image recording of the present invention
In the material, the addition of a color preparation is preferred.
Japanese Patent Laid-Open No. 10-62899, paragraph numbers 0054 to 0055, European patent publication
No. 0808374A1 page 21, lines 23-48, JP 2000-35
It is described in No. 6317 and Japanese Patent Application No. 2000-187298.
Dinones (phthalazinone, phthalazinone derivatives or
Metal salts; for example 4- (1-naphthyl) phthalazinone, 6-chloro
Phthalazinone, 5,7-dimethoxyphthalazinone and 2,3-
Dihydro-1,4-phthalazinedione); with phthalazinones
Phthalic acids (e.g. phthalic acid, 4-methylphthalic acid, 4-
Nitrophthalic acid, diammonium phthalate, sodium phthalate
Thorium, potassium phthalate and tetrachloroanhydrofuran
In combination with phthalic acid; phthalazines (phthalazine, phthalates)
Razine derivatives or metal salts; for example 4- (1-naphthyl)
Talazine, 6-isopropylphthalazine, 6-t-butyl fura
Tagine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine
And 2,3-dihydrophthalazine) are preferred,
The combination of phthalazines and phthalic acids is particularly preferred
Yes. (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 Application No. 11-223898, paragraph numbers 0136 to 0193, Japanese Patent Application No. 11-
No. 87297, compounds of formula (H), formulas (1) to (3), formulas (A) and (B),
Compounds of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652
(Specific compounds: Chemical formula 21 to Chemical formula 24), Contrast enhancer
JP-A-11-65021 paragraph number 0102, JP-A-11-223898
It is described in 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. Superhigh contrast agent in the heat-developable image recording material of the present invention
Is used, the acid formed by hydration of diphosphorus pentoxide or
Is preferably used in combination with a salt thereof. Dipentylpentoxide
As an acid or salt thereof formed by hydration of
Acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), three
Phosphoric acid (salt), tetraphosphoric acid (salt), hexametaphosphoric acid
(Salt) etc. can be mentioned. Especially preferably used
Hydrated diphosphorus pentoxide or its salt
Use orthophosphoric acid (salt), hexametaphosphoric acid (salt)
Can be mentioned. Specific salt is orthophosphoric acid
Sodium, sodium dihydrogen orthophosphate, hexame
Sodium taphosphate, ammonium hexametaphosphate
There is. Acid formed by hydration of diphosphorus pentoxide or its
Amount of salt used (photosensitive material 1m²Per application amount) is the sensitivity and
A desired amount may be set according to the performance such as fog, but 0.1
~ 500mg / m²Is preferred, 0.5-100 mg /
m²Is more preferable. The preparation temperature of the image forming layer coating solution of the present invention is:
30 to 65 ° C. is preferable, more preferable temperature
Is 35 ° C. or more and less than 60 ° C., more preferably 35 ° C. or less.
Above 55 ° C. In addition, polymer latex added directly
The temperature of the subsequent image forming layer coating solution is 30 ° C. or higher and 65 ° C. or lower.
Preferably it is maintained. The image forming layer of the present invention is further layered on the support.
Or more layers. When it is composed of one layer
Reducible silver salts, photosensitive silver halides, reducing agents and
It consists of an inder, and if necessary, a color toning agent, a coating aid and
Includes additional materials as desired, such as other adjuvants. 2 layers or more
When configured above, the first image-forming layer (usually adjacent to the support)
Reducing silver salt and photosensitive halogenation in the contact layer)
Contains silver and some other in the second imaging layer or both layers
Must contain the ingredients. Multicolor photothermographic photo
The composition of the material includes a combination of these two layers for each color.
Also described in US Pat. No. 4,708,928
As shown, all components may be included in a single layer.
In the case of a multi-dye multicolor photothermographic material, each emulsion layer is
Generally, as described in US Pat. No. 4,460,681
And a functional or non-functional barrier between each photosensitive layer
-Use layers to keep them separated from each other
The 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)
Can. For these, WO98 / 36322, JP
It is described in detail in Hei 10-268465, 11-338098, etc.
The (Explanation of layer structure) Photothermographic materials are generally used.
In addition to the photosensitive layer, it has a non-photosensitive layer. Non-photosensitive layer
(1) on the photosensitive layer (farther than the support)
(2) between the plurality of photosensitive layers
And an intermediate layer provided between the photosensitive layer and the protective layer, (3)
An undercoat layer provided between the light-sensitive layer and the support, (4)
It can be classified into a back layer provided on the opposite side of the light layer. F
The filter layer is a photosensitive material as the layer (1) or (2).
Is provided. Antihalation layer is (3) or
The layer (4) is provided on the photosensitive material. The heat-developable image recording material in the present invention is an image.
Providing a surface protective layer for the purpose of preventing adhesion of the formation layer
Can do. The surface protective layer may be a single layer or multiple layers.
May be. Regarding the surface protective layer, JP-A-11-65021
No. 0119-0120, described in Japanese Patent Application No. 2000-171936
The As a binder for the surface protective layer of the present invention, gelatin is used.
Is preferable, but polyvinyl alcohol (PVA) is used.
It is also preferable to use them in combination. As gelatin
Inert gelatin (eg Nitta Gelatin 750), phthalates
Use gelatinized gelatin (eg Nitta Gelatin 801)
You can. PVA is disclosed in JP-A-2000-171936.
No. 0009-0020 are listed, complete saponification
Product PVA-105, partially saponified product PVA-205,
PVA-335, modified polyvinyl alcohol MP-2
03 (above, Kuraray Co., Ltd. trade name) is preferred
Can be mentioned. Polyvinyl alcohol for protective layer (per layer)
Coating amount (support 1m²As per) 0.3 ~
4.0 g / m²Is preferable, 0.3 to 2.0 g / m²Gayo
More preferable. Especially for printing applications where dimensional change is a problem.
When using a bright heat-developable image recording material, a surface protective layer
It is preferable to use polymer latex for the back layer
Yes. For such polymer latex, please refer to “Synthetic Tree”.
Fat emulsion (from Taira Okuda, Hiroshi Inagaki, published by Polymer Publishing Association)
Line (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%) /
Tyl acrylate (50%) / methacrylic acid (16.5%) copolymer
-Latex, methyl methacrylate (47.5%) / pig
Latex of Diene (47.5%) / Itaconic Acid (5%) Copolymer
Of ethyl acrylate / methacrylic acid copolymer
Latex, methyl methacrylate (58.9%) / 2-eth
Ruhexyl acrylate (25.4%) / Styrene (8.6%) / 2
-Hydroxyethyl methacrylate (5.1%) / acrylic acid
(2.0%) Copolymer latex, methyl methacrylate
(64.0%) / Styrene (9.0%) / Butyl acrylate (20.0
%) / 2-hydroxyethyl methacrylate (5.0%) / Ac
Such as latex of lauric acid (2.0%) copolymer.
The Furthermore, as a binder for the surface protective layer,
A combination of polymer latex of 11-6872 specification,
Described in paragraph Nos. 0021 to 0025 of Japanese Patent Application No. 11-143058
Technology, paragraphs 0027 to 0028 of Japanese Patent Application No. 11-6872
The technology described in paragraph No. 002 of Japanese Patent Application No. 10-199626
The techniques described in 3 to 0041 may be applied. Surface protective layer
The ratio of polymer latex is more than 10% of the total binder
90% or less is preferable, and 20% or more and 80% or less is particularly preferable.
Good. All binders (water) in the surface protective layer (per layer)
(Including soluble polymers and latex polymers)
(Support 1m²Per) as 0.3 to 5.0 g /
m²Is preferable, 0.3 to 2.0 g / m²Is more preferred
Yes. In the heat-developable image recording material of the present invention,
The antihalation layer is far from the light source with respect to the photosensitive layer
Can be provided on the side. For anti-halation layer
JP-A-11-65021, paragraph numbers 0123 to 0124, JP-A-11-2
23898, 9-230531, 10-36695, 10-104779
11-231457, 11-352625, 11-352626, etc.
It is described in. The anti-halation layer has an exposure wave
Contains antihalation dyes with long absorption.
If the exposure wavelength is in the infrared region, use an infrared absorbing dye.
In that case, a dye that does not absorb in the visible range
preferable. Hareshi using dyes with absorption in the visible range
When performing image prevention, the color of the dye is actual after image formation.
It is preferable not to leave qualitatively, and heat of heat development
It is preferable to use a means for decoloring,
Add heat decoloring dye and base precursor to the light-sensitive layer
It is preferable to function as an anti-halation layer.
These techniques are described in JP-A-11-231457.
It is. 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
The concentration is preferably 0.2-2. like this
The amount of dye used to obtain the optical density is generally 0.00
1-1g / 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 recording material. Similarly, two kinds
More than one kind of base precursor may be used in combination. like this
In thermal decolorization using a special decoloring dye and base precursor
Is a base precursor as described in JP-A-11-352626.
Substance that lowers the melting point by 3 ° C (deg) or more when mixed with
(For example, diphenylsulfone, 4-chlorophenyl
(Phenyl) sulfone) combined with heat decolorization
This is preferable. In the present invention, the silver tone and the temporal change of the image.
Has an absorption maximum at 300 to 450 nm for the purpose of improving
Coloring agents can be added. Such colorants
JP-A-62-210458, 63-104046, 63-103235
, 63-208846, 63-306436, 63-314535,
It is described in Japanese Patent Application Laid-Open No. 01-61745, Japanese Patent Application No. 11-276751, etc.
ing. Such colorants are typically 0.1 mg / m²
~ 1g / m²It is added in the range of
A back layer provided on the opposite side of the light layer is preferred. The heat-developable image recording material in the present invention has a support.
At least one layer of silver halide emulsion on one side of the carrier
Having a photosensitive layer containing and having a back layer on the other side
A so-called single-sided photosensitive material is preferred. In the present invention, in order to improve the transportability, a map is used.
It is preferable to add a matting agent.
JP-A-11-65021, paragraph numbers 0126 to 0127
The Matting agent is photosensitive material 1m²Indicated by the amount applied per unit
Case, preferably 1 to 400 mg / m²More preferred
5 to 300 mg / m²It is. Also, emulsion surface mat
It doesn't matter if the stardust failure does not occur.
The smoothness is preferably 30 seconds or more and 2000 seconds or less, particularly
It is preferably 40 seconds or more and 1500 seconds or less. Beck smoothness
Japan Industrial Standards (JIS) P8119 “Paper and paperboard
Test method for smoothness using a tester and TAPPI standard method T
It can be easily obtained from 479. 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 seconds or less and 20 seconds or more are preferable, and more preferable.
Or 500 seconds or less and 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. A back layer applicable to the present invention.
JP-A-11-65021, paragraph numbers 0128 to 0130
It is. The heat-developable image recording material of the present invention has a heat-development treatment.
The pre-treatment membrane surface pH is preferably 7.0 or less.
More preferably, it is 6.6 or less. The lower limit is especially limited.
There is no limit, but it is about 3. The most preferred pH range is 4
It is in the range of ~ 6.2. Adjustment of membrane surface pH is induced by phthalic acid
Organic acids such as the body, non-volatile acids such as sulfuric acid, ammonia
Using a volatile base such as reduces the membrane surface pH
It is preferable from the viewpoint of producing. Especially ammonia volatilizes
It is easy to remove before applying and heat development.
Therefore, it is preferable to achieve a low film surface pH. Also hydroxy
Sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.
It is also preferable to use volatile base and ammonia together
I can. The method for measuring the membrane surface pH is described in Japanese Patent Application No. 11-872.
It is described in paragraph number 0123 of the 97 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 (vinyl sulfone)
Nacetamide), N, N-propylenebis (vinylsulfur)
Polyacetal metals described on page 78 of the same book.
Aeon, U.S. Pat.No. 4,281,060, JP-A-6-208193, etc.
Polyisocyanates such as US Patent 4,791,042
Epoxy compounds, vinyl compounds such as JP-A 62-89048
Phon compounds are preferably used. The hardening agent is added as a 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 concrete 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" (Nikkan Kogyo Shimbun, 1989)
Use the static mixer described in Chapter 8 etc.
There is a way to do it. Regarding surfactants applicable to the present invention,
It is described in JP-A-11-65021, paragraph number 0132,
However, regarding fluorine-based surfactants, Japanese Patent Application Nos. 2001-203462, 2
The compounds described in 001-242357 and 2001-264110 are preferable.
For the solvent, paragraph No. 0133 of JP-A-11-65021, support
JP-A No. 11-65021, paragraph number 0134, antistatic or
For the conductive layer, paragraph No. 0135 of JP-A-11-65021,
Japanese Unexamined Patent Publication No. 11-65021 paragraph No.
No. 0136, and for the slip agent, paragraph number of JP-A-11-84573
Nos. 0061 to 0064 and Japanese Patent Application No. 11-106881 paragraph numbers 0049 to 0062
It is listed. 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. Thermally developed image for medical use
In the case of a recording material, the transparent support is a blue dye (e.g.
Even if it is colored with dye-1) described in Example of Hei 8-240877
It may be good or uncolored. For the support, JP-A-11-84574
No. 10 water soluble polyester, No. 10-186565
Tadiene copolymer, Japanese Patent Application Laid-Open No. 2000-39684 and Japanese Patent Application No. 11-10688
No. 1 paragraph numbers 0063-0080 vinylidene chloride copolymer, etc.
It is preferable to apply an undercoating technique. In addition, antistatic
Stopping layer or undercoating JP-A-56-143430, 56-
143431, 58-62646, 56-120519, JP-A-11-84
573, paragraphs 0040-0051, U.S. Pat.No. 5,575,957,
Techniques described in paragraph numbers 0078 to 0084 of JP-A-11-223898
Can be applied. The heat-developable image recording material is a monosheet type (receiver).
Without using other sheets such as image material,
The type that can form an image on the recording material)
Yes. The heat-developable image recording material further includes an antioxidant.
Stopper, stabilizer, plasticizer, UV absorber or coating aid
An agent may be added. Various additives are used in the photosensitive layer or
Is added to any of the non-photosensitive layers. WO about them
98/36322, EP803764A1, JP-A-10-186567, 10-
Reference can be made to 18568. How is the heat-developable image recording material in the present invention?
It may be applied by the following method. Specifically, Xtre
Version coating, slide coating, carte
Coating, dip coating, knife coating
, Flow coating, or U.S. Pat.
Extrusion coating using a hopper of the type
 Various coating operations are used, including Stephen F.
“LIQUID FILM COATIN” by Kistler and Petert M. Schweizer
G ”(CHAPMAN & HALL, 1997) pp. 399-536
Extrusion coating or slide co
Preferably used, particularly preferably a slide
A coating is used. Used for slide coating
An example of the shape of the slide coater used is Fi.
in gure 11b.1. In addition, if desired, pages 399-5
Page 36, U.S. Pat.No. 2,761,791 and British
2 layers or more by the method described in Perm 837,095
These layers can be coated simultaneously. Coating of reducible silver salt-containing layer in the present invention
The liquid is preferably a so-called thixotropic fluid.
Yes. For this technology, refer to JP-A-11-52509.
be able to. Reducible silver salt-containing layer coating in the present invention
The cloth liquid has a shear rate of 0.1S.^-1Viscosity at 400 mP
a · s to 100,000 mPa · s is preferred
More preferably, 500 mPa · s or more 20,000
0 mPa · s or less. Also, shear rate 1000S
^-11mPa · s to 200mPa · s
Is more preferable, and more preferably 5 mPa · s or more and 80
mPa · s or less. Use in the heat-developable image recording material of the present invention.
As technologies that can be used, EP803764A1, EP883022A1,
WO 98/36322, JP 56-62648, 58-62644, JP
9-43766, 9-281637, 9-297367, 9-304869
No. 9-311405 No. 9-329865 No. 10-10669 No. 10
-62899, 10-69023, 10-186568, 10-90823
, 10-171063, 10-186565, 10-186567,
10-186569-10-186572, 10-197974, 10-
197982, 10-197983, 10-197985 to 10-19798
No. 7, No. 10-207001, No. 10-207004, No. 10-221807,
10-282601, 10-288823, 10-288824, 10-
307365, 10-312038, 10-339934, 11-7100
11-15105, 11-24200, 11-24201, 11
-30832, 11-84574, 11-65021, 11-109547
No. 11-125880 No. 11-129629 No. 11-133536
11-133539, 11-133542, 11-133543, 11-
223898, 11-352627, 11-305377, 11-30537
No. 8, No. 11-305384, No. 11-305380, No. 11-316435,
11-327076, 11-338096, 11-338098, 11-
No. 338099, No. 11-343420, No. 2000-187298, No. 2000
-10229, 2000-47345, 2000-206642, 2000-
98530, 2000-98531, 2000-112059, 2000-1
12060, 2000-112104, 2000-112064, 2000-
There is also 171936. (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. Packaging with low oxygen permeability and / or moisture permeability
Specific examples of the material include, for example, JP-A-8-254793.
issue. Described in JP 2000-206653 A
Packaging material. (Description of thermal development) Thermal development image recording of the present invention
The material can be developed in any way, but is usually imaged.
Develop by developing the temperature of the heat-developable image recording material
Is done. The preferred development temperature is 80 to 250 ° C.
More preferably 100 to 160 ° C.
Especially preferably, it is 110 to 150 ° C. This
The heat development temperature here refers to the image formation of the photothermographic material.
It is defined by the surface temperature on the layer side, and the time to reach the temperature
The maximum temperature that lasted for more than 1 second. The development time is 1 second or more and 60 seconds or less.
The Preferably it is 3 seconds or more and 30 seconds or less, and 3 seconds or more 2
More preferably 4 seconds or less, particularly 3 seconds or more and 15 seconds or less.
preferable. The development time here is 10 from the heat development temperature.
If the photosensitive material is exposed to a temperature higher than the temperature minus
It is the total amount of time. As a thermal development system, a plate heater method is used.
The formula is preferred. Thermal development method by plate heater method
Is preferably a method described in JP-A-11-133572, and a latent image
Heat-developing image recording material formed with a heating means in a heat developing section
This is a thermal development device that obtains a visible image by contacting
The heating means comprises a plate heater, and the
Multiple presser rollers along one surface of the plate heater
Are arranged opposite to each other, and the presser roller and the plate heater
The thermal development image recording material is passed between
It is a heat developing apparatus to be performed. Plate heater divided into 2-6 stages
For the tip, lower the temperature by about 1-10 ° C.
Is preferred. Such a method is also described in JP-A-54-30032.
Moisture contained in heat-developable image recording material
And organic solvents can be excluded from the system.
Heat-development image by heat-development image recording material being heated
It is also possible to suppress changes in the shape of the recording material support. The light-sensitive material of the present invention can be exposed by any method.
However, laser light is preferable as the exposure light source.
As the laser light according to the present invention, a gas laser (Ar
⁺, He-Ne), YAG laser, dye laser, half
A conductor laser or the like is preferable. Also with semiconductor laser
A second harmonic generation element or the like can also be used. Like
Or red to infrared emitting gas or semiconductor laser
The A medical array having an exposure section and a heat development section.
Fuji Medical Dry Laser as the imager
-Imager FM-DP L.
For FM-DPL, Fuji Medical Review No.
8, page 39-55, and those technologies are
As a laser imager for bright heat-developable image recording materials
It goes without saying that it applies. In addition, DICOM standard
Fuji Medical as a network system adapted to
Laser system in the "AD network" proposed by the system
It can also be used as a heat-developable image recording material for majors.
You can. The heat-developable image recording material of the present invention is a silver image.
Heat-developable image recording material for medical diagnosis
, Heat developed image recording material for industrial photography, heat developed image for printing
Used as recording material, heat development image recording material for COM
It is preferable that [0187] EXAMPLES The present invention will be specifically described below with reference to examples.
However, the present invention is not limited to these. Example 1 (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))
Obtained. This was pelletized and then dried at 130 ° C for 4 hours.
After melting at 0 ° C, it is extruded from a T-die and quenched, and after heat setting
Create unstretched film with a thickness of 175μm
Made. 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.
After finishing, knurled both ends, 4kg / cm²Winding with
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. [0191] (Create an undercoat support) (1) Preparation of undercoat layer coating solution Formula (for photosensitive layer side undercoat layer)   59g pesresin A-520 (30% solution) manufactured by Takamatsu Yushi Co., Ltd.   Polyethylene glycol monononyl phenyl ether 5.4g     (Average number of ethylene oxide = 8.5) 10% solution   MP-1000 (polymer fine particle, average particle size 0.4μm) 0.91g by Soken Chemical Co., Ltd.   935ml distilled water [0192] Formula (for back layer 1st layer)   Styrene-butadiene copolymer latex 158g  (Solid content 40%, styrene / butadiene mass ratio = 68/32)   2,4-dichloro-6-hydroxy-S-     Triazine sodium salt 8% aqueous solution 20g   10% 1% aqueous solution of sodium laurylbenzenesulfonate   Distilled water 854ml [0193] Formula (for back layer 2nd layer)   SnO₂/ SbO (9/1 ratio, average particle size 0.038μm, 17% dispersion) 84g   Gelatin (10% aqueous solution) 89.2g   Metroise TC-5 (2% aqueous solution) manufactured by Shin-Etsu Chemical Co., Ltd. 8.6g   MP-1000 0.01g made by Soken Chemical Co., Ltd.   10% 1% aqueous solution of sodium dodecylbenzenesulfonate   NaOH (1%) 6ml   Proxel (made by ICI) 1ml   805ml of distilled water (Preparation of undercoat support) Thickness of 175 μm
Biaxially stretched polyethylene terephthalate support
Each was subjected to the above corona discharge treatment and then one side (photosensitive
Apply the above undercoat coating formulation to the adhesive layer surface with a wire bar.
Et coating amount is 6.6ml / m²Paint to be (per side)
Cloth and dry at 180 ° C for 5 minutes, then back side (back
Surface) with a wire bar
G coating amount is 5.7ml / m²And apply at 180 ° C for 5 minutes.
And then dry the above undercoat coating solution on the back (back surface).
With a wire bar, the wet coating amount is 7.7ml / m²become
And then dry at 180 ° C for 6 minutes.
Created. (Preparation of back surface coating solution) (Preparation of solid fine particle dispersion (a) of base precursor) Salt
64g of precursor precursor compound 11, diphenylsulfone
Steamed 28g and Kao's surfactant Demol N 10g
Mix with 220 ml of distilled water and mix the mixture with a sand mill (1/4 Gallon
Sand grinder mill, made by IMEX Co., Ltd.)
The base precursor with an average particle size of 0.2μm dispersed in beads
A solid fine particle dispersion (a) of a sir compound was obtained. (Preparation of Dye Solid Fine Particle Dispersion) Cyanine
9.6 g of dye compound 13 and p-dodecylbenzenesulfo
Mix 5.8g of sodium nitrate with 305ml of distilled water,
Sand Mill (1/4 Gallon Sand Grinder Mill, Eye
(Mex Co., Ltd.)
A 0.2 μm dye solid fine particle dispersion was obtained. (Preparation of antihalation layer coating solution) Zera
Chin 17g, polyacrylamide 9.6g, the above base precursor
Sir solid fine particle dispersion (a) 70 g, the above dye solid fine particle content
56g of dispersion, monodisperse polymethyl methacrylate fine particles (flat
Average particle size 8, particle size standard deviation 0.4) 1.5 g, benzoiso
Thiazolinone 0.03g, polyethylene sulfonate sodium
2.2g of um, 0.2g of blue dye compound 14, yellow dye compound 15
3.9g, 844ml of water mixed, anti-halation layer coating solution
Was prepared. (Preparation of back surface protective layer coating solution)
Incubate at 40 ° C and flow gelatin 40g, liquid paraffin emulsion.
1.5 g of kinetic paraffin, benzoisothiazolinone 3
5mg, 1mol / L caustic 6.8g, t-octylphenoxy ethoxy
Sodium sietansulfonate 0.5g, polystyrene
Sodium sulfonate 0.27g, fluorosurfactant (F-
1) 37mg, fluorosurfactant (F-2) 0.15g, foot
Basic surfactant (F-3) 64mg, Fluorosurfactant
(F-4) 32 mg, acrylic acid / ethyl acrylate copolymer
6g of copolymer (copolymerization mass ratio 5/95), N, N-ethylenebis (vinyl
(Lusulfonacetamide) 2.0g, mixed with water and 10 liters
A back surface protective layer coating solution was used as a liquid. (Preparation of silver halide emulsion) <Preparation of silver halide emulsion 1> 1% bromide in 1421 ml of distilled water
Add 3.1 ml of potassium solution and add 0.5 mol / L sulfuric acid.
A solution containing 3.5 ml of phthalated gelatin and 31.7 g of phthalated gelatin
While stirring in a reaction vessel made of less, keep the liquid temperature at 30 ℃,
Solution A diluted with distilled water to 95.4 ml with 22.22 g of acid silver and odor
Potassium iodide 15.3g and potassium iodide 0.8g in distilled water
Solution B diluted to a volume of 97.4ml was added at a constant flow rate over 45 seconds.
An amount was added. Then 10ml of 3.5% hydrogen peroxide solution
Add 10.8% 10% aqueous solution of benzimidazole.
ml was added. Furthermore, add distilled water to 51.86 g of silver nitrate and add 31
Solution C diluted to 7.5ml, potassium bromide 44.2g and potassium iodide
Solution D obtained by diluting 2.2g of Lithium with distilled water to a volume of 400ml
Add the entire amount of solution C over 20 minutes at a constant flow rate,
D is a controlled double jet while maintaining pAg at 8.1.
The addition was carried out by the batch method. 1 x 10 per mole of silver^-FourIt ’ll be a mole
Uranium hexachloride iridium (III) potassium salt was added to solution C and
The total amount was added 10 minutes after the start of the addition of Solution D. Ma
In addition, iron (II) hexacyanide potash 5 seconds after completion of the addition of solution C
3 × 10 per 1 mol of silver^-FourThe whole molar amount was added.
Adjust the pH to 3.8 with 0.5 mol / L sulfuric acid and stir.
Stopped and settled / desalted / washed. 1mol / L concentration
Adjust the pH to 5.9 with sodium hydroxide and adjust the pH
A silver halide dispersion was prepared. While stirring the above silver halide dispersion, 38
Maintained at ℃, 0.34% 1,2-benzisothiazoline-3-
Add 5 ml of ON methanol solution, spectral sensitizing color after 40 minutes
A 1: 1 methanol solution with a molar ratio of element A and sensitizing dye B
1.2 x 10 as the sum of sensitizing dyes A and B per mole of silver^-3Mo
1 minute later, the temperature was raised to 47 ° C. Ben 20 minutes after the temperature rise
Sodium zenthiosulfonate in silver with methanol solution
7.6 x 10 per mole ^-FiveAdd 5 moles and add 5 minutes later
Sensitizer B in methanol solution 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% methanol solution of diethylmelamine,
After another 4 minutes, 5-methyl-2-mercaptoben ヅ imidazo
4.8 x 10 per mole of silver in methanol solution^-3Mole and
1-phenyl-2-heptyl-5-mercapto-1,3,4-tria
5.4x10 sol per mole of silver with methanol solution^-3
Mole and 1- (3-Methylureido) -5-mercaptoteto
8.5 × 1 sol with sodium chloride
0^-3A silver halide emulsion 1 was prepared by adding a molar amount. The grains in the prepared silver halide emulsion were:
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 was added 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
And 1- (3-methylureido) -5-mercaptotetrazo
Sodium salt with an aqueous solution of 4.7 x 10^-3
Spectral sensitization in the same manner as Emulsion 1 except that the molar addition was changed.
Chemical sensitization and 5-methyl-2-mercaptoben ヅ imidazole
1-phenyl-2-heptyl-5-mercapto-1,3,4-tri
An azole was added to obtain a silver halide emulsion 2. C
Emulsion grains of silver halide emulsion 2 have an average sphere equivalent diameter of 0.080μ
m, pure silver bromide cubic grains with a sphere equivalent diameter variation coefficient of 20%
It was. << 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 B addition amount
5.2 x 10 per mole of silver^-FourSame as Emulsion 1 except for changing to mol
Thus, a silver halide emulsion 3 was obtained. Silver halide milk
The emulsion grains of agent 3 have an average sphere equivalent diameter of 0.034 μm and a sphere equivalent diameter.
Iodobromide containing 3.5 mol% of iodine with a coefficient of variation of 20%
It was silver particles. << Preparation of Mixed Emulsion A for Coating Solution >> Halogenation
70% silver emulsion 1, 15% silver halide emulsion 2, halogen
Dissolve 15% of silver halide emulsion 3 and add benzothiazolium iodide
7 x 10 per mole of silver in 1% aqueous solution^-3Add mole
It was. Furthermore, silver halide per kg of mixed emulsion for coating solution
Water so that the content of silver becomes 38.2 g as silver,
1- (3-methyl) to give 0.34g / kg of mixed emulsion
Luureido) -5-mercaptotetrazole sodium salt
Was added. << Preparation of reducible silver salt dispersion >> Preparation of reducible silver salt dispersion A << Preparation of flake fatty acid silver salt >> Henkel behenic acid
(Product name Edenor C22-85R) 87.6g,
423 ml of distilled water, 5 mol / liter-NaOH aqueous solution
Mix 49.2 ml of liquid and 120 ml of tert-butanol.
And stirred for 1 hour at 75 ° C to react with sodium behenate.
A lithium solution was obtained. Separately, an aqueous solution containing the amount of silver nitrate in Table 1
Prepare 206.2 ml of liquid (pH 4.0) at 10 ° C.
Keep warm. 635 ml distilled water and 30 ml tert-
The reaction vessel containing butanol is kept warm at 30 ° C and stirred.
While the total amount of sodium behenate solution and silver nitrate aqueous solution
The total amount of liquid is 62 minutes 10 seconds and 60 minutes at a constant flow rate.
Added. At this time, 7 minutes after the start of silver nitrate aqueous solution addition
Only add the aqueous silver nitrate solution for 20 seconds.
After that, start adding sodium behenate solution and add silver nitrate water.
9 minutes and 30 seconds after the end of the solution addition,
Only the liquid was added. At this time, inside the reaction vessel
The temperature of the tank is 30 ° C, and the external temperature is adjusted so that the liquid temperature is constant.
It was controlled. Addition of sodium behenate solution
The piping of the system is kept warm by steam tracing and added nose
Steam is opened so that the liquid temperature at the outlet of the pipe tip is 75 ° C.
The degree was adjusted. Moreover, the piping of the addition system of the silver nitrate aqueous solution is
It was kept warm by circulating cold water outside the double tube.
Addition position of sodium behenate solution and silver nitrate aqueous solution
Addition position should be symmetrical about the stirring axis.
The height was adjusted so as not to contact the reaction solution. Nato behenate
After the addition of the lithium solution, the mixture is stirred for 20 minutes at the same temperature.
The mixture was left stirring and cooled to 25 ° C. Then solid by suction filtration
And the filtered water has a conductivity of 30 μS / cm or less.
Washed with water until. Thus, fatty acid silver salt A was obtained. Obtained
Silver salt is not completely dried and is taken as a wet cake.
I put it out. The content of non-volatile components in the wet cake is shown in Table 1.
It was written together as a solid content in mass percentage (mass%). The morphology of the resulting fatty acid silver salt particles was examined with an electron microscope.
When evaluated by microscopic photography, the average value was a = 0.14.
μm, b = 0.4 μm, c = 0.6 μm, average aspect
G ratio 5.2, average sphere equivalent diameter 0.52 μm, sphere equivalent diameter change
It was a flake-like crystal with a dynamic coefficient of 15%. (A, b, c
Is the provision of the text) Fatty acid silver salt A corresponding to 100 g of dry solids
Weigh the wet cake and add polyvinyl alcohol (Povar
Le PVA-217, manufactured by Kuraray Co., Ltd., average polymerization degree of about 17
00) 7.4g and water added to make the total amount 385g
Then, it was predispersed with a homomixer. Next pre-dispersed
Dispersing machine (stock name: Microfluidizer M)
-110S-EH, Microfluidics Inter
G10Z Interact, made by National Corporation
The pressure of the pressure chamber is 175.0 MPa.
Save and process three times and have a solids concentration of 26% by weight
A dispersion of fatty acid acid silver A was obtained. Cooling operation is a helical tube heat exchange
Attached to the front and back of the interaction chamber
The temperature of the refrigerant is adjusted to a dispersion temperature of 18 ° C.
Set. Reducible fatty acid silver salt dispersions B to C, present
Inventive polymer silver salt dispersions PB-1 to PB-13,
Preparation of Mingai Polymer Silver Salt Dispersion PBC-1 to PBC-2
In the preparation of the above reducible silver salt dispersion A,
Instead of behenic acid, the carboxylic acid compounds listed in Table 1 were replaced with silver.
The carboxyl group of behenic acid used in the preparation of salt dispersion A and
Weigh the amount to be equimolar, otherwise the method described above
In the same way as above, each carvone with a solid concentration of 26% by mass
An acid silver salt dispersion was obtained. [0208] [Table 1] (Preparation of reducing agent dispersion) << Preparation of Reducing Agent-1 Dispersion >> Reducing agent-1 (1,1-bis (2-
Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethyl
Hexane 10kg and modified polyvinyl alcohol (Kuraray)
10kg of 20% aqueous solution of Poval MP203), 16kg of water
Was added and mixed well to obtain a slurry. This slurry
The liquid is pumped with a diaphragm pump and an average diameter of 0.5 mm
Horizontal sand mill filled with Luconia beads (UVM-2: A
After 3 hours and 30 minutes of dispersion with Imex Co., Ltd.
Nzoisothiazolinone sodium salt 0.2g and water
Prepared so that the concentration of the base agent is 25%, reducing agent-1 dispersion
I got a thing. Reducing agent contained in the reducing agent dispersion thus obtained
Particles have a median diameter of 0.42 μm and a maximum particle diameter of 2.0 μm or less.
there were. The resulting reducing agent dispersion is a polypor with a pore size of 10.0 μm.
Filter with a ropylene filter to remove foreign matter such as dust.
Removed and stored. << Preparation of Reducing Agent-2 Dispersion >> Reducing Agent-2
(2,2'-isobutylidene-bis- (4,6-dimethylphenol
Nord)) 10Kg and modified polyvinyl alcohol (Kuraray)
10kg of 20% aqueous solution of Poval MP203), 16kg of water
Was added and mixed well to obtain a slurry. This slurry
The liquid is pumped with a diaphragm pump and an average diameter of 0.5 mm
Horizontal sand mill filled with Luconia beads (UVM-2: A
After 3 hours and 30 minutes of dispersion with Imex Co., Ltd.
Nzoisothiazolinone sodium salt 0.2g and water
Prepared so that the concentration of the base agent is 25% and dispersed the reducing agent-2
I got a thing. Reducing agent contained in the reducing agent dispersion thus obtained
Particles have a median diameter of 0.38μm and a maximum particle diameter of 2.0μm or less
there were. The resulting reducing agent dispersion is a polypor with a pore size of 10.0 μm.
Filter with a ropylene filter to remove foreign matter such as dust.
Removed and stored. << Preparation of Reducing Agent Complex-3 Dispersion >> Reducing Agent Complex
-3 (2,2'-methylenebis- (4-ethyl-6-tert-butyl
Phenol) and triphenylphosphine oxide 1:
1 complex) 10Kg, triphenylphosphine oxide 0.12Kg
And modified polyvinyl alcohol (Kuraray Co., Ltd.
In addition, 7.2 kg of water is added to 16 kg of 10% aqueous solution of
Mix well to make a slurry. This slurry is
Zirconia beads with an average diameter of 0.5 mm, delivered by a ram pump
Type horizontal sand mill (UVM-2: Imex
After 4 hours and 30 minutes of dispersion (made by Co., Ltd.)
Concentration of reducing agent by adding 0.2 g of azolinone sodium salt and water
To 25% to obtain a reducing agent complex-3 dispersion
It was. The reducing agent complex contained in the reducing agent complex dispersion thus obtained.
Body particles have a median diameter of 0.46 μm and a maximum particle size of 1.6 μm or less
Met. The resulting reducing agent complex dispersion has a pore size of 3.0 μm.
Filter with a polypropylene filter to remove dust, etc.
Foreign matter was removed and stored. (Preparation of polyhalogen compound) << Preparation of organic polyhalogen compound-1 dispersion >>
Halogen compound-1 (2-tribromomethanesulfonyl
Naphthalene) 10Kg and modified polyvinyl alcohol (Kuraray)
10kg of 20% aqueous solution of Poval MP203) and triiso
20% aqueous solution of sodium propylnaphthalenesulfonate
Add 0.4Kg and 16Kg of water, mix well and make slurry
did. This slurry is fed with a diaphragm pump,
Horizontal sand filled with zirconia beads with a uniform diameter of 0.5 mm
Disperse for 5 hours in a mill (UVM-2: manufactured by Imex Co., Ltd.)
After that, 0.2 g of benzoisothiazolinone sodium salt and water
To add organic polyhalogen compound concentration of 23.5%
To obtain an organic polyhalogen compound-1 dispersion
It was. Included in the polyhalogen compound dispersion thus obtained
Organic polyhalogen compound particles have a median diameter of 0.36 μm
The large particle size was 2.0 μm or less. Obtained organic polyhalo
Gen compound dispersion is made of polypropylene film with a pore size of 10.0μm.
Filter with a filter to remove foreign substances such as dust and store
did. << Preparation of organic polyhalogen compound-2 dispersion
Made by organic polyhalogen compound-2 (tribromomethanes
(Lufonylbenzene) 10Kg and modified polyvinyl alcohol
10 kg of a 20% aqueous solution of (Kuraray Co., Ltd. Poval MP203)
20 of sodium triisopropylnaphthalene sulfonate
Add 0.4 kg of aqueous solution and 14 kg of water, mix well, and mix.
It was rally. This slurry is sent with a diaphragm pump.
Horizontally filled with zirconia beads with an average diameter of 0.5 mm
5 hours with a type sand mill (UVM-2: made by Imex Co., Ltd.)
After dispersion, benzoisothiazolinone sodium salt
Add 0.2g and water, the concentration of organic polyhalogen compound is 26%
Prepared to be an organic polyhalogen compound-2 dispersion
I got a thing. The polyhalogen compound dispersion thus obtained contained
Organic polyhalogen compound particles to be rolled have a median diameter of 0.41μ
m, and the maximum particle size was 2.0 μm or less. Obtained organic
The rehalogen compound dispersion is polypropylene with a pore size of 10.0μm.
To remove foreign substances such as dust.
And stored. << Preparation of organic polyhalogen compound-3 dispersion
Product >> Organic polyhalogen compound-3 (N-butyl-3-to
Libromomethanesulfonylbenzamide) 10Kg and denatured poly
1 of Livinyl alcohol (Kuraray Co., Ltd. Poval MP203)
20kg of 0% aqueous solution and triisopropylnaphthalenesulfo
Add 0.4 kg of 20% aqueous solution of sodium phosphate and 8 kg of water.
And mixed well to obtain a slurry. Die this slurry
Zirconia with an average diameter of 0.5 mm, delivered by an Afram pump
Horizontal sand mill filled with beads (UVM-2: IMEC
Benzisothiazo after dispersion for 5 hours
Organic polyhalogen by adding 0.2 g of linone sodium salt and water
The compound concentration was adjusted to 25%. This dispersion
Is heated at 40 ° C. for 5 hours to give an organic polyhalogen compound-3.
A dispersion was obtained. Polyhalogen compound dispersion thus obtained
Organic polyhalogen compound particles contained in the median diameter is 0.
It was 36 μm and the maximum particle size was 1.5 μm or less. Obtained
The polyhalogen compound dispersion is a polypropylene with a pore size of 3.0 μm.
Filter with a pyrene filter to remove foreign substances such as dust.
I stored it away. << 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
3.15kg of 20% aqueous solution of sodium sulfonate and phthalazine
70% aqueous solution of compound-1 (6-isopropylphthalazine)
Add 14.28 kg and prepare a 5% solution of phthalazine compound-1.
Made. << Preparation of Mercapto Compound-1 Aqueous Solution >>
Lucapto Compound-1 (1- (3-sulfophenyl) -5
-7g of mercaptotetrazole sodium salt)
To make a 0.7% 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 slurry. G with an average diameter of 0.5 mm
Prepare 800g of Luconia beads and add them together with the slurry.
Place in cell and disperser (1 / 4G sand grinder mill:
Dispersed for 25 hours with Imex Co., Ltd., pigment-1 minute
I got a splinter. Pigment particles contained in the pigment dispersion thus obtained
The children had an average particle size of 0.21 μm. << Preparation of SBR Latex Liquid >> Tg = 23 ° C.
The SBR latex was prepared as follows. Polymerization initiator
As ammonium persulfate, anionic interface as emulsifier
Using activator, styrene 70.5, butadiene 26.
5 and acrylic acid 3 after emulsion polymerization,
Time aging was performed. Then cool to 40 ° C and
PH 7.0 with ammonia water, and Sanyo Chemical Co., Ltd.
Made Sandet BL was added to 0.22%. next
Add 5% aqueous sodium hydroxide solution to adjust pH to 8.3.
In addition, adjust the pH to 8.4 with aqueous ammonia.
It was. Na used at this time⁺Ion and NH_Four ⁺Ion molar ratio
Was 1: 2.3. Furthermore, for 1 kg of this liquid,
Nzoisothiazolinone sodium salt 7% aqueous solution 0.15
ml was added to prepare an SBR latex solution. [0219]  (SBR latex: Latex of -St (70.5) -Bu (26.5) -AA (3)-) Tg23 ℃ Including equilibrium at an average particle size of 0.1μm, concentration of 43%, and 25 ° C, 60% RH
Water content 0.6%, ionic conductivity 4.2mS / cm (measurement of ionic conductivity
Uses a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd.
Stock solution (43%) measured at 25 ° C), SB with a pH of 8.4 Tg
R latex is appropriately changed ratio of styrene and butadiene
And it adjusted by the same method. << Preparation of emulsion layer (photosensitive layer) coating solution-1 >>
The reducible silver salt dispersion B or PB-5 obtained above is used.
1000 g, water 125 ml, reducing agent-1 dispersion 113 g, reducing agent-2 minutes
91 g of powder, 27 g of pigment-1 dispersion, organic polyhalogen compound
-1 dispersion 82g, organic polyhalogen compound-2 dispersion 40
g, phthalazine compound-1 solution 173 g, amount of SBR latte in Table 2
(Tg: 20.5 ° C), 9 g of mercapto compound-1 aqueous solution
Add 158g of silver halide mixed emulsion immediately before coating.
The emulsion layer coating solution was obtained by adding and mixing well. Emulsion layer coating
The cloth liquid is fed as it is to the coating die and used for coating.
It was. << Preparation of emulsion layer (photosensitive layer) coating solution-2 >>
Reducible silver salt dispersions A to C, PB-1 to P obtained above
1000g B-13 and PBC-1 to PBC-2, 104m water
l 、 Pigment-1 dispersion 30g 、 Organic polyhalogen compound-2min
21g powder, 69g organic polyhalogen compound-3 dispersion, lid
173 g of Razine Compound-1 solution, SBR latex in the amount shown in Table 2
(Tg: 23 ° C.) liquid, reducing agent complex-3 dispersion 258 g, mercapto
Add 9g of Compound-1 solution sequentially and halogenate just before coating
Emulsion layer coating solution with well-mixed silver mixed emulsion A110g
The solution was fed directly to the coating die and applied. << Preparation of Emulsion Surface Intermediate Layer Coating Solution >> Polyvinyl
10% water of alcohol (Poval PVA-205, manufactured by Kuraray Co., Ltd.)
772 g of solution, 5.3 g of 20% pigment dispersion, methyl methacrylate
/ Styrene / Butyl acrylate / Hydroxyethyl
Tacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/2
0/5/2) 27.5% latex solution 226g with aerosol OT (American
2 ml of 5% aqueous solution of Licancyanamid), phthalic acid
10.5ml of 20% aqueous solution of diammonium salt, total volume 880g
Add water so that the pH is 7.5 and adjust with NaOH.
10ml / m²Cotin to be
Liquid was fed to Gudai. The viscosity of the coating solution was 40 ° C (No.
1 rotor, 60 rpm), and 21 [mPa · s]. << 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) 80g of 27.5% latex, 10% methanoic acid phthalic acid
23 ml of solution, 23 ml of 10% aqueous solution of 4-methylphthalic acid,
28 ml of 0.5 mol / L sulfuric acid, aerosol OT (USA
5 ml of 5% aqueous solution of phenoxye)
Add 0.5 g of tanol and 0.1 g of benzoisothiazolinone
Add water so that the amount reaches 750 g to make the coating solution, and 4% black
Mix 26 ml of alum with a static mixer immediately before application.
18.6ml / m of the combined²Coating die to be
The solution was sent to. The viscosity of the coating solution is B-type viscometer 40 ℃ (No.1 low
17 [mPa · s] at 60 rpm). << Preparation of coating solution 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
3.2 ml of 5% solution of Agent (F-1), fluorinated surfactant
32 ml of 2% by weight aqueous solution of (F-2), aerosol OT (a
23 ml of 5% by weight solution of (Merikan Cyanamide)
4g methyl methacrylate fine particles (average particle size 0.7μm)
Limethyl methacrylate fine particles (average particle size 4.5μm) 21
g, 1.6g of 4-methylphthalic acid, 4.8g of phthalic acid, 0.5mol / L concentration
Degree of sulfuric acid 44ml, benzoisothiazolinone 10mg total amount 650g
Add water to make 4% chrome alum and 0.6%
Immediately before applying 445 ml of an aqueous solution containing 7% phthalic acid
What is mixed with the tic mixer
8.3ml / m²To the coating die so that
It was. The viscosity of the coating solution is B type viscometer 40 ℃ (No.1 rotor, 60rp
m) was 9 [mPa · s]. << Emulsion layer (photosensitive layer) coating solution-1 was used.
Preparation of photothermographic material-1 series >>
The anti-halation layer coating solution is dyed on the surface side
The solid content of the coating material is 0.04 g / m²And back again
Surface protective layer coating solution with a gelatin coating amount of 1.7 g / m²To be
At the same time, a multilayer was applied and dried to form a back layer. [0226] From the undercoat surface to the emulsion layer on the surface opposite to the back surface
(Photosensitive layer) Emulsion layer, intermediate layer, protection using coating solution-1
How to apply slide beads in order of layer 1st layer and protective layer 2nd layer
Samples of photothermographic material 1B ~
1PB-5 was prepared. At this time, with the emulsion layer
Intermediate layer at 31 ° C, protective layer first layer at 36 ° C, protective layer first layer
The temperature was adjusted to 37 ° C. Coating amount of each compound in the emulsion layer (g /
m²) Is as follows. [0227]   Reducible silver salt (as Ag) 1.49   Reducing agent-1 0.67   Reducing agent-2 0.54   Pigment (C.I.Pigment Blue 60) 0.032   Polyhalogen compound-1 0.46   Polyhalogen compound-2 0.25   Phthalazine Compound-1 0.21   SBR latex listed in Table 2   Mercapto Compound-1 0.002   Silver halide (as Ag) 0.145 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 photothermographic material thus prepared has a matte degree of
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. << Emulsion layer (photosensitive layer) Coating solution-2 was used.
Preparation of two photothermographic materials >> For photothermographic material-1
Change the coating solution to emulsion layer (photosensitive layer) coating solution-2
In addition, yellow dye compound 15 from the antihalation layer
Except for the above, heat development was performed in the same manner as the photothermographic material-1 series.
Photosensitive material series 2 (sensitive materials 2A to 2C, 2PB-1 to 2PB
-13, 2PBC-1 to 2PBC-2). [0231] [Table 2] At this time, the coating amount of each compound in the emulsion layer (g /
m²) Is as follows. Reducible silver salt (as Ag) 1.49 Pigment (C.I.Pigment Blue 60) 0.036 Polyhalogen compound-2 0.13 Polyhalogen compound-3 0.41 Phthalazine Compound-1 0.21 SBR latex listed in Table 2 Reducing agent complex-3 1.54 Mercapto Compound-1 0.002 Silver halide (as Ag) 0.10 The compounds used in the examples of the present invention are shown below.
The academic structure is shown. [0234] Embedded image[0235] Embedded image[0236] Embedded image [0237] Embedded image[0238] Embedded image -Evaluation of film quality (evaluation of workability)
The top blade is 1 °, the top blade is 89 °, and the top blade is 89 °.
Use a lower blade with a tip angle of 90 °, fix the lower blade, and cut the upper blade.
The pea was cut at 1 m / sec against the lower blade. Disconnected trial
Observe both cut surfaces of the material with an optical microscope at a magnification of 100 to evaluate the film quality.
Was carried out. Evaluation, A: No film peeling occurs and the cut surface is smooth ○: No film peeling but rough surface Δ: The film is peeled off, but peeled off after rubbing by hand.
There is no problem in practical use. X: The film peels off and is peeled off by hand. Went. The results are shown in Table 3. ・ Evaluation of sensitivity The obtained sample was cut into half-cut sizes and a ring at 25 ° C and 50%
Wrapped in the following packaging materials under the environment, 4 weeks environment at 25 ° C
It was stored underneath, and the sensitivity was evaluated after opening the package. (Packaging material) PET 10μm / PE 12μm / Aluminum foil 9μm / Ny 1
Polyethylene containing 5μm / carbon 3% 50μm Oxygen permeability: 0ml / atm · m²・ 25 ℃ ・ day, moisture permeability: 0g
/ atm ・ m²・ 25 ℃ ・ day ・ Evaluation of fogging The obtained sample was cut into half-cut sizes and a ring at 25 ° C and 65%
Wrapped in the following packaging materials under the environment, and the environment at 35 ° C for 4 weeks
Store underneath, after opening the package, measure the density of the unexposed areas after development.
The fog was evaluated. Notated as Dmin in the table
did. -Evaluation of image storage stability The exposed and developed sample prepared in the above sensitivity evaluation is 60
Store in a dark place at ℃ for 24 hours.
The rise value was measured. In the table, it is expressed as ΔDmin. In addition, the evaluation of sensitivity and the evaluation of fogging
In this case as well, the sample must be
Jar FM-DP L (660nm half of maximum 60mW (IIIB) output)
Image obtained by exposure and thermal development with a conductor laser)
Was evaluated with a densitometer. Sensitivity is photothermographic material
Material 1B treated at 135 ° C for 12 seconds is defined as 100
Relative evaluation. [0242] [Table 3] From the results shown in Table 3, the photothermographic material of the present invention is used.
Shows good processability and excellent film strength.
Karu. Further, the photothermographic material of the present invention has a low temperature (120
℃) for a short time (12 seconds).
It can be seen that the yellowtail density is small and that it is suitable for rapid processing.
In particular, even in the development processing at a relatively high temperature, the heat of the present invention.
Developed photosensitive materials have a low fog density value and are excellent.
Maintained photographic performance. [0244] The photothermographic material of the present invention has a photographic property and a film.
It has excellent quality and suitability for rapid processing.
Excellent as a film for rum and photoengraving.

──────────────────────────────────────────────────── ───
[Procedure Amendment] [Submission Date] October 18, 2002 (2002.10.
18) [Procedure Amendment 1] [Document Name to be Amended] Description [Item Name to be Amended] 0023 [Correction Method] Change [Content of Amendment] [0023] [Procedure Amendment 2] [Name of Document to be Amended] Description [Name of Item to be Amended] 0047 [Correction Method] Change [Content of Amendment] [0047] In order to obtain the polymer of the present invention with a preferable average degree of polymerization, the polymerization reaction is performed. The specific polymerization degree of 30 is desired by a specific method such as diluting the polymerization concentration, using a large amount of polymerization initiator, and increasing the polymerization temperature.
It is possible to obtain the following polymer. [Procedure Amendment 3] [Document Name to be Amended] Description [Item Name to be Amended] 0056 [Correction Method] Change [Details of Amendment] [0056] In addition, if the photosensitive silver salt is allowed to coexist when the polymer silver salt is dispersed, It is more preferable that the photosensitive silver salt is not substantially contained at the time of dispersion because fog increases and sensitivity is remarkably lowered . The amount of the photosensitive silver salt water dispersion to be distributed is, 0.1 mol with respect to the polymer silver 1mol of the liquid in
%, And no positive photosensitive silver salt is added. [Procedure Amendment 4] [Document Name to be Amended] Description [Item Name to be Amended] 0117 [Correction Method] Change [Content of Amendment] (Description of Binder) The binder of the reducible silver salt-containing layer of the present invention is Any polymer may be used, including latex, suitable binders are transparent or translucent and generally colorless, natural resins, synthetic resins, homopolymers, copolymers, other media forming films,
For example, gelatin, rubber, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl Methacrylic acid) s, poly (vinyl chloride) s, poly (methacrylic acid) s, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers,
Poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resins, poly (vinylidene chloride) s, poly (epoxides), Poly (carbonates), poly (vinyl acetate) s, poly (olefins), cellulose esters, poly (amides)
There is kind. The binder may be formed from a solution or emulsion of water or an organic solvent. [Procedure Amendment 5] [Document Name to be Amended] Description [Item Name to be Amended] 0220 [Correction Method] Change [Correction Details] << Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1 >>
The reducible silver salt dispersion B or PB-5 obtained above is used.
1000 g, water 125 ml, a reducing agent-1 dispersion 113 g, the reducing agent-2 dispersion 91g, organic polyhalogen compound-1 dispersion 82 g, the organic polyhalogen compound-2 dispersion 40 g, phthalazine compound-1 solution 173 g, Table 2 amount of SBR latex (Tg: 20.5 ℃),
9 g of an aqueous solution of mercapto compound-1 was sequentially added, and 158 g of silver halide mixed emulsion A was added and mixed well immediately before coating to obtain an emulsion layer coating solution. The emulsion layer coating solution was directly fed to a coating die and used for coating. [Procedure Amendment 6] [Document Name to be Amended] Description [Item Name to be Amended] 0221 [Correction Method] Change [Content of Amendment] << Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-2 >>
Reducible silver salt dispersions A to C, PB-1 to P obtained above
1000g B-13 and PBC-1 to PBC-2, 104m water
l, organic polyhalogen compound-2 dispersion 21g, organic polyhalogen compound -3 dispersion 69 g, phthalazine compound-1 solution 173 g, the amount of Table 2 SBR latex (Tg: 23 ℃) liquid, a reducing agent complexes -3 258 g of the dispersion and 9 g of the mercapto compound-1 solution were sequentially added, and the emulsion layer coating solution in which 110 g of the silver halide mixed emulsion A was added and mixed well immediately before coating was directly fed to the coating die for coating. [Procedure Amendment 7] [Document Name to be Amended] Description [Item Name to be Amended] 0222 [Correction Method] Change [Content of Amendment] << Preparation of Emulsion Surface Intermediate Layer Coating Solution >> Polyvinyl alcohol (Poval PVA-205, 10% of Kuraray Co., Ltd.
772 g of aqueous solution, 5.3 g of pigment- 1 dispersion, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer mass ratio 64/9/2
0/5/2) 27.5% of latex 27.5% solution, 2 ml of 5% aqueous solution of Aerosol OT (American Cyanamid), 10.5 ml of 20% aqueous solution of diammonium phthalate, water to a total volume of 880 g Was adjusted with NaOH to a pH of 7.5 to obtain an intermediate layer coating solution, and the solution was fed to the coating die so as to be 10 ml / m ² . The viscosity of the coating solution was 40 ° C (No.
1 rotor, 60 rpm), and 21 [mPa · s]. [Procedure Amendment 8] [Document Name to be Amended] Description [Item Name to be Amended] 0227 [Correction Method] Change [Content of Amendment] Reducible Silver Salt (As Ag) 1.49 Reducing Agent-1 0. 67 reducing agent-2 0.5 4 Po Riharogen compounds -1 0.46 polyhalogen compound-2 0.25 phthalazine compound-1 0.21 SBR latex table 2, wherein the mercapto compound-1 0.002 silver halide (as Ag ) 0.145 [Procedure Amendment 9] [Document Name to be Amended] Description [Item Name to be Amended] 0232 [Correction Method] Change [Content of Amendment] [0232] At this time, the coating amount of each compound in the emulsion layer (g /
m ² ) is as follows. Reducible silver salt (Ag as) 1.4 9 Po Riharogen compound-2 0.13 Polyhalogen compound -3 0.41 phthalazine compounds -1 0.21 SBR latex Table 2, wherein the reducing agent complexes -3 1.54 mercapto Compound-1 0.002 Silver halide (as Ag) 0.10

Continued front page    (72) Inventor Yoshihisa Tsukada             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. (72) Inventor Shinichi Yamanouchi             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H123 AB00 AB03 AB23 AB28 CB00                       CB03

Claims (1)

What is claimed is: 1. Heat development comprising at least one photosensitive silver halide, non-photosensitive organic silver, a reducing agent for silver ions and a binder on one side of a support. An image recording material, wherein at least one of the non-photosensitive organic silver is a silver salt of a polymer containing a repeating unit derived from a monomer having a carboxyl group or a salt thereof, and the average degree of polymerization of the polymer is 30 A heat-developable image recording material characterized by the following.