JP2003295380A - Heat-developable image recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-developable image recording material excellent in film strength and rapid processability 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, a non- photosensitive organic silver salt, a reducing agent for a silver ion and a binder, wherein the silver salt of a polymer having a specified structure having a carboxyl group is used as the non-photosensitive organic silver salt. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention is excellent in film strength, and
New heat-developable image recording materials with excellent rapid processing
Is. [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 recording materials. this
According to heat-developable image recording materials, solution-type processing chemicals
Heat development processing that does not require harshness and is simpler and does not damage the environment
The system can be supplied to customers. Similar demands in the field of general image forming materials
However, medical diagnostic images are particularly required to be finely depicted.
Therefore, high image quality with excellent sharpness and graininess is required.
In particular, cold black images are preferred from the viewpoint of ease of diagnosis.
There are signs. Currently, inkjet printers, electrophotography
Various hard copy systems using pigments and dyes
Although distributed as a general image forming system, medical images
There is no satisfactory image output system. On the other hand, a thermal image 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 heat-developable image recording material generally has a touch.
Active amount of photocatalyst (eg silver halide), reducing agent,
Reducible silver salt (eg reducible organic silver salt), required
To control the color tone of the silver
It has a photosensitive layer dispersed in the lix. Heat-developed image
The image recording material has a high temperature (for example, 80 ° C. or higher) after image exposure.
With a silver salt (which functions as an oxidizing agent) that can be heated and reduced to
A black silver image is formed by the redox reaction with the reducing agent.
To do. The redox reaction is the silver halide generated by exposure.
The latent image is promoted by the catalytic action. Therefore, black
A silver image is formed in the exposed area. US Patent 2910377
Disclosure in a number of documents, including No. 43-4924
Has been. Reduction for use in these heat-developable image recording materials
Possible silver salts are relatively stable to light,
Exposed photocatalyst (eg latent image of photosensitive silver halide) and
Heated to 80 ° C or higher in the presence of reducing agent
In some cases, silver salts that form silver images are conventionally used. This
Non-photosensitive reducible silver salts such as
06-130543, 08-314078, 09-127643, 10-62
Paragraph Nos. 0048 to 0049 of No. 899, JP-A-10-94074
No. 10-94075, European Patent Publication No. 073684A1
Page 8, line 24 to page 19, line 37, European Patent
No. 0962812A1, No. 100004930A2, JP-A-11-349591
JP, 2000-7683, 2000-72711, 2000-112057
No. 2000-155383 and the like. Organic acid silver
Salts, in particular (carbon number 10-30, preferably 15-28
Silver salt of long chain aliphatic carboxylic acid is used as an example
Are silver behenate, silver arachidate, silver stearate,
Silver formate, silver laurate, silver caproate, myristic
List silver oxide, silver palmitate, and mixtures of these
You can. In addition, US Pat.
A silver salt of sulfonic acid is disclosed in JP-A 52-137321.
A silver complex of a torazole derivative is disclosed in JP-A-53-11614.
No. 4 and JP-A-58-118638 include triazole derivatives.
A silver complex of a conductor is disclosed. JP 2000-292 A
881 includes, for example, methacrylic acid / styrene copolymer
Use polymer silver salts in environments with limited silver potential.
And a technique for improving the storage stability at high humidity is disclosed.
The The heat-developable image recording material is photosensitive as described above.
All chemicals necessary for development are incorporated into the material.
Simply by applying heat without using a processing solution,
It has a feature that an image can be formed. one
On the other hand, reducible silver salt that supplies silver to AgX with a latent image
Is generally a bulky organic compound.
Therefore, the film thickness of the photosensitive layer is the same as that of conventional silver halide photographic materials.
It is about 10 times thicker than that.
It was a problem in terms of strength reduction. Also by heat development processing
Therefore, further thinning is desired in terms of rapid processing.
It was. In addition, photosensitive materials are exposed to light by not using processing solutions.
Silver halide and reducible silver salts remain on storage
Image storability against light and heat
It was. [0007] SUMMARY OF THE INVENTION The object of the present invention is to
To provide a heat-developable image recording material that solves this problem
It is in. That is, the object of the present invention is to improve film strength and rapid processing.
Heat-developable image recording material with excellent image storage properties
Is to provide. [0008] The object of the present invention is to provide the following structure.
This is achieved by thermal development image processing. 1. On one side of the support, at least one type of photosensitive
Reduction for silver halides, non-photosensitive organic silver salts, silver ions
A heat-developable image recording material containing an agent and a binder.
As the non-photosensitive organic silver salt, the following general formula (1)
Thermal current characterized by using a silver salt of the polymer represented
Image image recording material. General formula (1) [0009] [Chemical 3] In the general formula (1): A represents the following general formula (2)
A repeating unit derived from a monomer A represented by
Is an ethylene other than monomer A represented by the following general formula (2)
Table shows repeating units derived from the unsaturated monomer B
Derived from vinyl ether monomers or alkenes
Containing at least one repeating unit. General formula (2) [0011] [Formula 4] In general formula (2): R¹And R²The hydrogen field
Represents a child or a methyl group, R^ThreeAnd R^FourRespectively
Independently, a hydrogen atom or a straight chain optionally having a substituent
Or represents a branched alkyl group. However, R^ThreeAnd R^FourLess
At least one represents a hydrogen atom. m is 20-60 mol
% And n are 40 to 80 mol%. Where m + n =
100 mol%. 2. The polymer represented by the general formula (1) is a monomer A and
2. The alternating copolymer of B, wherein
Thermally developed image recording material. 3. The molecular weight of the polymer represented by the general formula (1) is 1.0
1 or above, characterized by being not more than 00,000
2. The heat-developable image recording material according to 2. 4). The total film thickness on the image forming layer side of the heat-developable image recording material is 3
1 to above, characterized in that it is not less than μm and not more than 22 μm.
4. The heat-developable image recording material according to any one of 3 above. 5). The heat development time of the heat development image recording material is 24 seconds or less.
The heat present as described in any one of 1 to 4 above,
Image image recording material. 6). The binder is a polymer latex
The heat-developable image recording according to any one of 1 to 5 above
material. 7). The binder has a glass transition temperature of -20 ° C to 8 ° C.
Any one of 1 to 6 above, wherein the temperature is 0 ° C
A heat-developable image recording material. [0013] DETAILED DESCRIPTION OF THE INVENTION The present invention is described in further detail below.
To do. The heat-developable image recording material of the present invention has a support,
1 type of photosensitive silver halide, non-photosensitive organic silver salt,
Thermal current with reducing agent and binder for silver ion
An image image recording material, the non-photosensitive organic silver salt,
Use the silver salt of the polymer represented by the general formula (1)
It is characterized by. In general formula (1), A represents the above general formula (2).
A repeating unit derived from a monomer A represented by
Is ethylenic other than monomer A represented by formula (2)
Represents a repeating unit derived from unsaturated monomer B;
Derived from vinyl ether monomer or alkene
Contains at least one repeating unit. m and n are
Represents the ratio (mol%) of repeating units A and B, m is
20-60 mol%, preferably 30-60, n is 40
~ 80 mol%, preferably 40-70 mol%
The Here, m + n = 100 mol%. A is a plurality of types of modules represented by the general formula (1).
Even the total of repeating units derived from Nomer A
good. B is similarly derived from multiple types of monomers B
The total number of repeating units may be used. R in the above general formula (2)¹And R²It
Each independently represents a hydrogen atom or a methyl group, R^ThreeAnd
And R^FourEach independently have a hydrogen atom or a substituent.
Represents a linear or branched alkyl group which may be substituted. However
And R^ThreeAnd R^FourAt least one of represents a hydrogen atom.
The linear or branched alkyl group has 1 to 30 carbon atoms.
preferable. The carbon number does not include the carbon atom of the substituent.
Yes. The same applies hereinafter. Optionally on an alkyl group
Examples of the substituent include an alkoxy group, a thioalkoxy group,
Rogen substituents, nitro groups, hydroxyl groups, etc.
However, the present invention is not limited to these. one
As the monomer A represented by the general formula (2), for example, male
Inic acid, monobutyl maleate, monomethyrate maleate
Cybutyl, 1,2-dimethylmaleic acid, 1,2-dimethyl
Til maleic acid mono-2-ethylhexyl, fumaric acid, fumar
Monomethyl citrate, citraconic acid, citraconic acid monooctane
Although chill etc. are mentioned, this invention is limited to these.
It is not a thing. The monomer A is used alone.
Can be used, or two or more can be used in combination.
It can also be used. In the above general formula (1), as described above.
And B is an ethylene other than the monomer A represented by the general formula (2).
A repeating unit derived from a renically unsaturated monomer B
Derived from vinyl ether monomer or alkene
Containing at least one repeating unit. Below is a convenience store
Detailed explanation of ruether monomer. In the present invention,
What is vinyl ether monomer?₂= CH-O-skeleton
It is a general term for vinyl monomers. One preferred vinyl ether monomer
And having a linear or branched alkyl group having 1 to 30 carbon atoms.
Alkyl vinyl ether or cycloalkyl
And vinyl ethers. For example, methyl vinyl ether
Ether, ethyl vinyl ether, n-propyl vinyl ether
-Tel, isopropyl vinyl ether, n-butyl vinyl
Ether, isobutyl vinyl ether, tert-butyl ether
Til vinyl ether, n-pentyl vinyl ether, n
-Hexyl vinyl ether, n-octyl vinyl ether
, N-dodecyl vinyl ether, n-eicosyl vinyl
Ether, 2-ethylhexyl vinyl ether, cycl
Specific examples of preferred are hexyl vinyl ether and the like.
Can be mentioned. Among them, straight chain alkyl having 4 to 20 carbon atoms
More preferred are alkyl vinyl ethers having groups, examples
For example, n-butyl vinyl ether, n-hexyl vinyl ether
-Tel, n-octyl vinyl ether, n-dodecylbi
Nyl ether, n-eicosyl vinyl ether, etc.
A more preferable example is given. Linear or branched alkoxy having 1 to 30 carbon atoms
Also preferred are alkoxyalkyl vinyl ethers with thio groups.
A kind of new vinyl ether monomer, such as
Siloxyethyl vinyl ether, eicosyloxye
Til vinyl ether, butoxybutyl vinyl ether,
Hexyloxybutyl vinyl ether, 2-ethylhexyl
Specific examples in which siloxybutyl vinyl ether is preferred
It is mentioned. Among them, straight-chain Al having 4 to 20 carbon atoms
Alkoxyalkyl vinyl ether having a alkoxy group
More preferably, for example, butoxybutyl vinyl ether,
Dodecyloxyethyl vinyl ether, eicosyloxy
As a more preferable specific example, such as ciethyl vinyl ether
Is mentioned. The alkyl group and the alkoxy group are hydride.
It may have a substituent such as a roxyl group, for example, 2-
Hydroxyethyl vinyl ether, 3-hydroxypro
Pyrvinyl ether, 2-hydroxypropyl vinyl ether
Ether, 4-hydroxybutyl vinyl ether, 3-hydroxy
Droxybutyl vinyl ether, 5-hydroxy pliers
Ruvinyl ether, 6-hydroxyhexyl vinyl ether
And hydroxyl group-containing vinyl ethers such as tellurium. Also preferred vinyl ether monomers and
And CH₂= CH-O-Rf (Rf contains a fluorine atom)
An alkyl group or an alkoxyalkyl group)
Fluoroalkyl vinyl ethers and fluores represented
Examples include lower alkoxyalkyl vinyl ethers.
Specifically, fluorobutyl vinyl ether, fluorobut
Toxiethyl vinyl ether and the like can be mentioned. The vinyl ether monomer has the specific examples described above.
It is not limited to examples. Monomer B is one kind
Can be used alone, or two or more
Can be used in combination. Next, ethylenically unsaturated monomer B
The alkene is described in detail below. 4-30 carbon atoms
A straight-chain or branched alkene of
Ten, isobutene, 1-hexene, 1-dodecene, 1-
Preferred examples include octadecene and 1-eicosene.
It is mentioned. Among these, straight-chain aluminum having 6 to 20 carbon atoms
Ken is more preferred, for example 1-hexene, 1-dodece.
1-octadecene, 1-eicosen, etc. are more preferred
A new example is given. In addition, the following
Safluoropropene, vinylidene fluoride, chlorotrif
Fluoroethylene, 3,3,3-trifluoropropylene
, Fluoroolefins such as tetrafluoroethylene
Can also be suitably used as the monomer B. Echi
Lenically unsaturated monomer B is limited to these specific examples.
It is not something. Monomer B is used alone
Or you can combine two or more
Can be used. Regarding the polymer represented by the general formula (1)
Further explanation will be given. The polymer represented by the general formula (1) is:
A part of the repeating unit B is a monomer group shown below.
Consists of a copolymer that combines monomers selected from
It is also possible to do. Especially the monomers that can be used
Anything that can be polymerized by ordinary radical polymerization
Can be suitably used. Monomer group 1) Diene 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 and the like. 2) α, β-unsaturated carboxylic acid and its
salts Acrylic acid, methacrylic acid, itaconic acid, acrylic acid
Thorium, ammonium methacrylate, potassium itaconate
Umm etc. 3) Derivatives of α, β-unsaturated carboxylic acids 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) Esters of unsaturated polycarboxylic acids Dimethyl maleate, dibutyl maleate, itaconic acid
Dimethyl, dibutyl taconate, butyl crotonate, chloro
Hexyl tonate, diethyl fumarate, dimethyl fumarate
Such. 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-cyclohexanetetramethacrylate
Polypropylene glycol dimethacrylate (poly
Number of moles of oxypropylene added: n = 2 to 100
Things). 3e) Amides of α, β-unsaturated carboxylic acids 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, p-vinyl benzoic acid, p-vinyl
Methyl benzoate, α-methylstyrene, p-chloromethyl
Styrene, vinyl naphthalene, p-methoxystyrene
, P-hydroxymethylstyrene, p-acetoxys
Tylene, p-styrenesulfonic acid, p-styrenesulfone
Sodium salt, potassium p-styrenesulfinate
Salt, p-aminomethylstyrene, p-divinylbenze
4-vinylbenzoic acid-2-acryloylethyls
Tell 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) 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 be used or a combination of two or more
You can also Poly of the present invention represented by the general formula (1)
The monomer is preferably an alternating copolymer of monomers A and B.
Preferably, monomer B is vinyl ether monomer
And at least one of alkene. Polymer represented by the general formula (1) of the present invention
Although the manufacturing method is not particularly limited, for example
Cationic polymerization or radical polymerization using vinyl group
Or a polymerization method such as anionic polymerization.
Dical polymerization is preferred. The polymerization initiator will be described in detail below.
As a polymerization initiator for radical polymerization, radical thermal polymerization
Known compounds such as initiators and radical photopolymerization initiators
Can be used, especially radical thermal polymerization initiation
It is preferable to use an agent. Where radical thermal gravity
The initiator is polymerized by heating above the decomposition temperature.
It is a compound that generates radicals that initiate the reaction.
Examples of such radical thermal polymerization initiators include:
Acetyl peroxide, benzoyl peroxide, etc.
Diacyl peroxide; methyl ethyl ketone per
Ketones such as oxide and cyclohexanone peroxide
Peroxide; hydrogen peroxide, tert-butyl hydride
Peroxide, cumene hydroperoxide, etc.
Idoperoxide; di-tert-butylperoxy
Side, dicumyl peroxide, dilauroyl peru
Dialkyl peroxides such as oxides;
Tilperoxyacetate, tert-butylperoxy
Peroxyesters such as cypivalate; Azobisiso
Azo such as butyronitrile and azobisisovaleronitrile
Compounds; ammonium persulfate, sodium persulfate,
Examples include persulfates such as potassium persulfate. like this
One radical thermal polymerization initiator can be used alone.
Can be used, or use in combination of two or more
Can. The radical polymerization method is described in detail below.
To do. The radical polymerization method is limited to specific radical polymerization
Not emulsion polymerization method, suspension polymerization method, bulk polymerization
Method, solution polymerization method, etc.
Is a typical radical polymerization method for solution polymerization
This will be described more specifically. In the general formula (1) of the present invention,
The polymer represented is preferably an alternating copolymer
For example, a maleic anhydride derivative and the monomer B are
It is suitably used for synthesizing an alternating copolymer. An organic solvent is used for solution polymerization.
There is a need to. Examples of such an organic solvent include the present invention.
Can be selected within the range that does not impair the purpose and effect of
Usually, the boiling point under atmospheric pressure is in the range of 50-200 ° C.
Is an organic compound that dissolves each component uniformly.
The organic compound to be formed is preferred. Examples of preferred organic solvents
Alcohols such as isopropanol and butanol
, Dibutyl ether, ethylene glycol dimethyl ether
Ethers such as ether, tetrahydrofuran and dioxane
, Acetone, methyl ethyl ketone, methyl isobutyl
Ketones, ketones such as cyclohexanone, ethyl acetate,
S such as butyl acetate, amyl acetate, γ-butyrolactone
Aromatic carbonization of tellurium, benzene, toluene, xylene, etc.
Hydrogen is mentioned. In addition, these organic solvents are 1 type.
Can be used alone or in combination of two or more
is there. Use water in combination with the above organic solvent.
Is possible. Also, the 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, before the start of solution polymerization, place with inert gas.
It is preferable to perform a replacement operation. As an inert gas
Nitrogen gas is preferably used. The mass average molecular weight will be described in detail below.
The The mass average of the polymer represented by the general formula (1) of the present invention
The average molecular weight should be less than 1,000,000
That's right. This is because the mass average molecular weight is 1,000,000.
If it is larger, the handleability becomes worse, and the polymers shown below
This is because the silver chloride rate cannot be increased in the silver chloride step.
Therefore, the mass average of the polymer represented by the general formula (1)
It is more preferable that the average molecular weight is 1,000,000 or less
That's right. Such mass average molecular weight is determined by gel permeation.
Polyester by using chromatography (GPC)
Replacement of ethylene oxide or polyethylene glycol
It can be measured as an arithmetic value. In the following, it is preferably used in the present invention.
Specific examples of the polymer represented by the general formula (1)
However, the present invention is not limited to these specific examples.
Yes. Here, the numerical value indicating the composition ratio of each monomer is a mole percentage.
The molecular weight indicates the average molecular weight. [0041] [Chemical formula 5] [0042] [Chemical 6]A synthesis example of the polymer P-1 will be described below. [Synthesis example of polymer P-1] Stirrer, monomer supply
500m with bath, thermometer, cooling pipe, nitrogen gas introduction pipe
l flask with 150 g of ethyl acetate, maleic anhydride
Add 48.95g and 50g of butyl vinyl ether.
Introduce raw gas and keep the temperature inside the flask at 60 ° C while stirring.
And heated. Next, 2, dissolved in 20 g of ethyl acetate
Add 0.41 g solution of 2'-azobisisobutyronitrile.
Agitated at the same temperature for 5.5 hours, butyl vinyl ether
/ A maleic anhydride copolymer solution was obtained. To the above reaction solution
Add in 2 liters of xanthine and collect the precipitate that forms.
Dry under reduced pressure for 8 hours at ℃, butyl vinyl ether /
95 g of maleic anhydride copolymer was obtained. Stirrer, mono
Equipped with water supply tank, thermometer, cooling pipe, nitrogen gas introduction pipe
In a 1000 ml flask, 10 g of the obtained copolymer,
Contains 180 g of distilled water and 15 ml of tert-butyl alcohol
Nitrogen gas was introduced and the flask internal temperature was adjusted to 7 with stirring.
Heated to 5 ° C. Next, 10g of sodium hydroxide was distilled.
Add an aqueous solution dissolved in 100 ml of water and stir at 75 ° C. for 1 hour.
Stir. After treating the reaction solution with nitric acid, methanol
Add to 0.5 liter and collect the precipitate formed,
And dried under reduced pressure for 8 hours to obtain 95 g of polymer P-1.
It was. The polymer silver salt used in the present invention is not known.
It may be manufactured by any synthetic method.
Laboratory Chemistry Course 4th edition, volume 22, p.43-43, 193-2
Refer to page 27 and the literature described in them.
Then, those skilled in the art can prepare it easily. Production of polymer silver salt used in the present invention and
In the dispersion method, a known method can be applied.
The For example, the above-mentioned JP-A-10-62899, European Patent Publication No. 08
03763A1, European Patent Publication No. 0962812A1, JP-A-11-34959
No. 1, JP 2000-7683, 2000-72711, Japanese Patent Application No. 11-348
No. 228-30, No. 11-203413, No. 2000-90093, No. 2000
-195621, 2000-191226, 2000-213813, 200
You can refer to 0-214155, 2000-191226, etc.
Yes. When the polymer silver salt of the present invention is used, a heat-developable image is obtained.
The total film thickness on the image forming layer side of the image recording material is 3 μm or more and 22
Although it can be designed with a size of μm or less, it is 3 μm or more and 20 μm or less
Is preferably 3 μm or more and 14 μm or less.
More preferably, it is 3 μm or more and 10 μm or less.
Is preferred. In the present invention, a non-photosensitive organic silver salt is used.
The silver salt of the polymer represented by the above general formula (1)
Other organic silver salts, such as silver salts of higher fatty acids, are used in the present invention.
Can be used as long as the achievement of the target is not hindered. Main departure
In order to realize the light effect, it is represented by the general formula (1).
A non-photosensitive organic silver salt other than the silver salt of the polymer is represented by the general formula (2)
Even when used together with the silver salt of the polymer represented by
The silver salt of the polymer of formula (2) is non-photosensitive in the photosensitive material
It must occupy at least 50 mol% of the organic silver salt. The heat-developable image recording material of the present invention has a temperature of 110 ° C.
It is preferable to develop at a heat development temperature of 160 ° C or lower.
Developed at a heat development temperature of 130 ° C. or higher and 150 ° C. or lower.
More preferably. The heat development temperature here is heat
Defined by the surface temperature of the image forming layer side of the developed image recording material
The maximum time that the temperature has been reached has continued for more than 1 second.
Refers to the temperature. The heat-developable image recording material of the present invention has a development time.
Is preferably 3 seconds to 24 seconds, preferably 3 seconds or more
More preferably, it is 15 seconds or less. During development here
The interval is more than the temperature obtained by subtracting 10 ° C from the heat development temperature.
This is the total time the light material has been exposed. Incidentally, a reducible silver salt, that is, non-photosensitive
When photosensitive silver salt is allowed to coexist during mechanical silver salt dispersion, fog
Rises and the sensitivity is significantly reduced.
It is more preferable that substantially no silver salt is contained. The present invention
Then, the amount of photosensitive silver salt in the aqueous dispersion of reducible silver salt
Is 0.1 m per 1 mol of reducible silver salt in the solution.
ol% or less, do not actively add photosensitive silver salt
Yes. In the present invention, a reducible silver salt aqueous dispersion and
Producing photosensitive material by mixing photosensitive silver salt water dispersion
The ratio of reducible silver salt to photosensitive silver salt
The ratio (molar ratio) can be selected according to the purpose, but reducible silver
The ratio of the photosensitive silver salt to the salt is in the range of 1 to 30 mol%.
Preferably 3 to 20 mol%, in particular 5 to 15 mol%
A range is preferred. Two or more types of reducible silver when mixed
Mix the salt water dispersion and two or more photosensitive silver salt water dispersions.
That is preferably used for adjusting photographic characteristics
Is the law. The reducible silver salt of the present invention is used in the desired amount
Yes, but 0.1 to 5 g / m as the amount of silver²Is preferred,
More preferably 1 to 3 g / m²It is. (Description of Reducing Agent) Thermal Development Image Recording of the Present Invention
The material preferably contains a reducing agent for the reducible silver salt.
Good. Reducing agent for reducible silver salt
Any substance (preferably an organic substance) that reduces to metallic silver.
It may be. Such a reducing agent is disclosed in JP-A-11-65021.
No. 0043 to 0045 and European Patent Publication No. 0803684A
Recorded on page 7, line 34 to page 18, line 12 of issue 1
It is listed. In the present invention, the reducing agent is hinder.
Preferred are phenolic reducing agents and bisphenol reducing agents.
More preferably, the compound represented by the following general formula (R) is more preferred.
That's right. [0054] [Chemical 7] (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 X¹Each independently represents 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,
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 preferred. R¹³But with 1 to 8 carbon atoms
In the case of a primary or secondary alkyl group, R¹²and
R ¹²'Is preferably a methyl group. R¹³Of 1 to 8 carbon atoms
As the secondary or secondary alkyl group, methyl group, ethyl
Group, propyl group, and isopropyl group are more preferable.
More preferred are a ru group, an ethyl group and a propyl group. R¹¹, R
¹¹', R¹²And R¹²When all of 'are methyl groups
R¹³Is preferably a secondary alkyl group
Yes. In this case R¹³As the secondary alkyl group,
Pyr, isobutyl and 1-ethylpentyl groups are preferred
An isopropyl group is more preferable. The compounds represented by the general formula (R) of the present invention are as follows:
Although the specific example of the reducing agent of this invention including a compound is shown,
The present invention is not limited to these. [0064] [Chemical 8][0065] [Chemical 9][0066] 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 contained with respect to 1 mol of silver on the surface having
Preferably 10 to 40 mol%
Further preferred. The reducing agent should be included in the image forming layer.
Is preferred. 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. At that time, the protective colloid
(For example, polyvinyl alcohol), surfactant (eg
For example, 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). (Explanation of Development Accelerator) Thermally developed image of the present invention
In recording materials, Japanese Patent Application No. 11-73951 is disclosed as a development accelerator.
Phenol derivatives represented by the formula (A) described in the book are preferred.
Used. (Explanation of Hydrogen Bonding Compound) In the present invention
When the reducing agent has an aromatic hydroxyl group (—OH),
Especially in the case of the aforementioned bisphenols, these groups and
Non-reducing with groups capable of forming hydrogen bonds
It is preferable to use a compound in combination. Hydroxyl or amino
Examples of groups that form hydrogen bonds with groups include phosphoryl groups and
Ruxoxide group, sulfonyl group, carbonyl group, amide
Group, ester group, urethane group, ureido group, tertiary amino
Group, nitrogen-containing aromatic group and the like. Preferred among them
Are phosphoryl group, sulfoxide group, amide group (however,
> N—H group, and> N—Ra (Ra is other than H
Blocked). ), Urethane group
(However,> N—H group 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). [0072] 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}Examples of the alkyl group of
Methyl group, ethyl group, butyl group, octyl group, dodecyl
Group, isopropyl group, t-butyl group, t-amyl group, t
-Octyl group, cyclohexyl group, 1-methylcyclohexyl
Xyl, benzyl, phenethyl, 2-phenoxy
A propyl group etc. are mentioned. Examples of aryl groups include
For example, phenyl group, cresyl group, xylyl group, naphthyl
Group, 4-t-butylphenyl group, 4-t-octylphene
Nyl group, 4-anisidyl group, 3,5-dichlorophenyl
Groups and the like. As an alkoxy group, for example,
Toxi group, ethoxy group, butoxy group, octyloxy
Group, 2-ethylhexyloxy group, 3,5,5-trime
Tylhexyloxy group, dodecyloxy group, cyclohexyl
Siloxy group, 4-methylcyclohexyloxy group,
Nyloxy group and the like. As an aryloxy group
For example, phenoxy group, cresyloxy group, isop
Lopyrphenoxy group, 4-t-butylphenoxy group, na
Examples thereof include a ftoxy group and a biphenyloxy group. Ami
Examples of the group include dimethylamino group and diethylamino group.
Group, dibutylamino group, dioctylamino group, N-methyl
Tyl-N-hexylamino group, dicyclohexylamino
Group, diphenylamino group, N-methyl-N-phenyla
And a mino group. 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. [0076] Embedded image [0077] 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 liquid and used in a light-sensitive material.
The compound of the general formula (D) is a phenolic hydroxide in the solution state.
Compound having hydrogen group and / or amino group and hydrogen bonding complex
A reducing agent and a compound of the general formula (D)
Depending on the combination, it may be isolated in the crystalline state as a complex.
You can. The crystal powder isolated in this way
Use as a fine particle dispersion gives stable performance
This is particularly preferable. Further, the reducing agent and the general formula (D)
Mix the compound with powder and use a suitable dispersant to sand.
The method of complexing at the time of dispersion with a lineder mill is also preferred.
Can be used. The compound of general formula (D) is reduced
To be used in the range of 1 to 200 mol% with respect to the agent
Preferably, more preferably in the range of 10 to 150 mol%
More preferably, it is used in the range of 30 to 100 mol%.
To do. (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 proportion of silver halide grains
50% or more of the surface is preferable, 65% or more is more preferable
80% or more is more preferable. Of Miller index [100]
The ratio is the absorption of the [111] face and the [100] face in the adsorption of the sensitizing dye.
T.Tani; J. Imaging Sci., 29, 165 (19
1985). 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 exists in a form, but it is mixed with water.
Easy to soften and suitable for silver halide emulsion precipitation operations
Sodium ion, potassium ion, rubidium ion
Alkali, cesium ions and lithium ions
Metal ion, ammonium ion, alkylammonium
Ions (eg, tetramethylammonium ion,
Traethylammonium ion, tetrapropylammo
Nium ion, tetra (n-butyl) ammonium ion
Are preferred. The hexacyano metal complex is miscible with water in addition to water.
Suitable organic solvents (eg alcohols, ethers)
, Glycols, ketones, esters, amides
Etc.) and mixed with gelatin aqueous solution
be able to. The addition amount of the hexacyano metal complex is about 1 mol 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
These silver salts of hexacyanoiron (II) are less soluble than AgI.
Because of its salt, it can prevent re-dissolution by fine particles.
To produce silver halide grains with small grain size
It 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-Fe atom), silver salt emulsion desalting method,
Regarding chemical sensitization, JP-A No. 11-84574, paragraph number 0046-
0050, Japanese Patent Laid-Open No. 11-65021, paragraph numbers 0025 to 0031, Japanese Patent Laid-Open No. 11-65021
-119374 paragraph numbers 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. As sensitizing dyes applicable to the present invention,
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 preferred 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 flow rate of addition 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 described in Chapter 8 etc.
There is a way to use. (Description of Binder) The reducible of the present invention
In addition to the latex of the present invention, the binder of the silver salt-containing layer is
Any polymer can be used in combination, suitable binder
Is transparent or translucent, generally colorless, and is free from natural resins and polymers.
Limers and copolymers, synthetic resins and polymers and copoly
, Other film-forming media, eg gelatin
Rubbers, poly (vinyl alcohol) s, hydroxy
Siethylcelluloses, cellulose acetates, cells
Loose acetate butyrate, poly (vinyl pyrrolide)
), Casein, starch, poly (acrylic acid),
Poly (methyl methacrylic acid) s, poly (vinyl chloride)
, Poly (methacrylic acid), styrene-maleic anhydride
Acid copolymers, styrene-acrylonitrile copolymers
, Styrene-butadiene copolymers, poly (vinyl alcohol)
Cetals) such as poly (vinyl formal) and
Poly (vinyl butyral)), poly (esters), poly
Ri (urethane), phenoxy resin, poly (vinyl chloride)
Den), poly (epoxide), poly (carbonate)
G), poly (vinyl acetate) s, poly (olefin)
, Cellulose esters, and poly (amides).
The binder is coated from water or an organic solvent or emulsion.
A cover may be formed. In the present invention, a layer containing a reducible silver salt
The glass transition temperature of the binder that can be used together is 10 ° C or higher
80 ° C. or less (hereinafter referred to as a high Tg binder)
Yes), preferably 20 ° C. to 70 ° C.
More preferably, the temperature is 23 ° C. or higher and 65 ° C. or lower.
Good. 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) (by J. Brandrup, E.H.Immergut
(Wiley-Interscience, 1989)) was adopted. [0104] Two or more binders may be used as required.
May be used. Also, the glass transition temperature is 20 ° C or higher
In combination with a glass transition temperature of less than 20 ° 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, a 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. Note 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. Further, “equilibrium water content at 25 ° C. and 60% RH”
Rate "is an equilibrium state 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. 25 of the binder polymer used in the present invention.
The equilibrium water content at 60 ° C RH is 2% or less.
Is preferable, but more preferably 0.01% or more and 1.5.
% Or less, more preferably 0.02% or more and 1% or less
Good. The binder used in the present invention is an aqueous solvent.
Dispersible polymers are particularly preferred. Distributed vine
As an example, a water-insoluble hydrophobic polymer particle
The dispersed latex and polymer molecules
May be dispersed in the form of micelles.
Deviation is also preferred. The average particle size of the dispersed particles is 1 to 50000
nm, more preferably in the range of about 5 to 1000 nm.
Good. There are no particular restrictions on the particle size distribution of the dispersed particles.
Even a wide particle size distribution has a monodisperse particle size distribution.
One thing may be sufficient. In the present invention, a polymer dispersible in an aqueous solvent.
Remers include acrylic polymers, poly (esthetics)
), Rubbers (eg SBR resin), poly (urethane)
, Poly (vinyl chloride), poly (vinyl acetate), poly
Li (vinylidene chloride), poly (olefin), etc.
An aqueous polymer can be preferably used. These
Polymers that are branched even with linear polymers
Or a cross-linked polymer or a single mono
A so-called homopolymer obtained by polymerizing mer may be used.
A copolymer obtained by polymerizing at least one kind of monomer may be used. Copo
In the case of a remer, even if it is a random copolymer,
It may be a remmer. These polymers have a number average molecular weight
5,000 to 1,000,000, preferably 10,000
~ 200000 is good. If the molecular weight is too small, emulsion
The mechanical strength of the layer is insufficient.
Is bad and not preferred. (Specific Examples of Latex) Preferred Polymer
Specific examples of latex include the following:
it can. In the following description, polymer is used as raw material monomer
The numbers in parentheses are mol%, and the molecular weight is number average molecular weight.
It is. When polyfunctional monomer is used, a cross-linked structure is created.
Because the concept of molecular weight is not applicable, it is described as crosslinkability.
The molecular weight is omitted from the description. Tg is the glass transition temperature
Represent. 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
(Quantity 40,000, Tg 59 ° C) Q-3; -St (50) -Bu (47) -MAA (3)-latex (crosslinkable, Tg-
(17 ℃) Q-4; -St (68) -Bu (29) -AA (3)-latex (crosslinkable, Tg17
℃) Q-5; -St (71) -Bu (26) -AA (3)-latex (crosslinkable, Tg24
℃) Q-6; -St (70) -Bu (27) -IA (3)-latex (crosslinkable) Q-7; -St (75) -Bu (24) -AA (1)-latex (crosslinkable, Tg29
℃) Q-8; Latex (crosslinked) 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 (crosslinkability,
(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
Of copolymer and butadiene monomer units
The total content is preferably 60 to 99%. Preferred molecule
The range of the amount is the same as described above. Styrenes 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, Nipo
l Examples include Lx416. The 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, more preferably 1 / 5-4 / 1 is preferred.
Yes. Further, 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 in the image forming layer of the present invention is
0.2-30 g / m², More preferably 1-15 g / m²
The range of is preferable. The image-forming layer of the present invention is cross-linked
Cross-linking agent, surfactant for improving coating properties, etc.
May be. (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
(Number is%). (Description of antifogging agent)
Antifoggant, stabilizer and stabilizer precursor
Paragraph No. 0070 of Kaihei 10-62899, European Patent Publication No. 080376
4A1 page 20 line 57 to page 21 line 7
Of the compounds described in JP-A-9-281637 and 9-329864.
I can get lost. Further, the fog prevention preferably used in the present invention.
Stopper is an organic halide, and these are special
The patent described in paragraph Nos. 0111 to 0112 of Kaihei 11-65021
What is shown. In particular, Japanese Patent Application No. 11-87297
An organic halogen compound represented by the formula (P) of JP-A-10-3399
An organic polyhalogen compound represented by the general formula (II) of No. 34,
The organic polyhalogen compounds described in Japanese Patent Application No. 11-205330
preferable. (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 above 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. [0129] Embedded image[0130] 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 antifoggants to photosensitive materials
Includes the method described in the method for containing a reducing agent, and
Also added 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 6317 and Japanese Patent Application No. 2000-187298.
Phthalazinones (including phthalazinone and phthalazinone derivatives)
Or metal salts such as 4- (1-naphthyl) phthalazinone, 6-
Chlorophthalazinone, 5,7-dimethoxyphthalazinone and
2,3-dihydro-1,4-phthalazinedione); phthalazino
And phthalic acids (e.g., phthalic acid, 4-methylphthalate)
Acid, 4-nitrophthalic acid, diammonium phthalate, lid
Sodium rurate, potassium phthalate and tetrachloro
In combination with phthalic anhydride; phthalazines (phthalazi
, Phthalazine derivatives or metal salts; for example 4- (1-na
Butyl) phthalazine, 6-isopropylphthalazine, 6-t-
Butyl phthalazine, 6-chlorophthalazine, 5,7-dimethoxy
Phthalazine and 2,3-dihydrophthalazine);
A combination of gins and phthalic acids is preferred, especially phthalates
A combination of gins and phthalic acids is preferred. (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 Laid-Open 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 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. (Explanation of Layer Structure) Thermally developed image in the present invention
The surface of the image recording material is used for the purpose of preventing adhesion of the image forming layer.
A protective layer can be provided. The surface protective layer may be a single layer
In addition, a plurality of layers may be used. For the surface protective layer,
Kaihei 11-65021 paragraph number 0119-0120, Japanese Patent Application 2000-171936
In the issue. Binder for surface protective layer of the present invention
Preferred as gelatin is polyvinyl alcohol
It is also preferable to use (PVA) in combination.
As gelatin, inert gelatin (eg Nitta Gelachi)
750), phthalated gelatin (eg Nitta Gelatin 801)
Etc. can be used. As PVA, JP 2000
-171936, paragraphs 0009 to 0020
PVA-105 of fully saponified product, P of partially saponified product
VA-205, PVA-335, modified polyvinyl alcohol
MP-203 (product name made by Kuraray Co., Ltd.)
Etc. are preferred. Protective layer (per layer)
Livinyl alcohol coating amount (support 1m²Win)
0.3 to 4.0 g / m²Is preferred, 0.3-2.
0g / m²Is 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. 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 a monolayer on the support.
Consists of more layers. Return if it consists of one layer
Possible silver salts, photosensitive silver halides, reducing agents and binders
Color tones, coating aids, etc.
Optional additional materials, such as adjuvants. More than two layers
The first image forming layer (usually adjacent to the support).
Reducible silver salt and photosensitive silver halide
Including the second imaging layer or some other in both layers
Ingredients must be included. Multicolor photosensitive photothermographic material
The composition of the material includes a combination of these two layers for each color
And is described in US Pat. No. 4,708,928.
Thus, all components may be contained in a single layer. Many
In the case of a dye multicolor photosensitive photothermographic material, each emulsion layer
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 separate from each other
The The photosensitive layer of the present invention has a color tone improved, laser
Viewpoints to prevent interference fringes and exposure to radiation during exposure
To various dyes and pigments (for example, C.I.Pigment Blue 60, C.I.
I. Pigment Blue 64, C.I. Pigment Blue 15: 6)
be able to. For these, WO98 / 36322, JP
10-268465, 11-338098, etc.
The In the 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. The heat-developable image recording material is generally used for the photosensitive layer.
In addition, it has a non-photosensitive layer. Is the non-photosensitive layer its arrangement?
(1) Provided on the photosensitive layer (on the side farther from the support)
(2) a protective layer between the plurality of photosensitive layers or with the photosensitive layer.
Intermediate layer provided between protective layers, (3) photosensitive layer and support
(4) Opposite side of photosensitive layer
Can be categorized as a back layer. The filter layer
It is provided in the photosensitive material as the layer (1) or (2).
The antihalation layer shall be the layer (3) or (4)
Provided in the photosensitive material. The antihalation layer is disclosed in JP-A-11.
No. -65021, paragraph numbers 0123 to 0124, JP-A-11-223898, 9
-230531, 10-36695, 10-104779, 11-23145
No. 7, 11-352625, 11-352626, etc.
The Antihalation layer has absorption at exposure wavelength
Containing antihalation dyes. Exposure wavelength is infrared
If it is in the range, an infrared absorbing dye may be used.
In some cases, a dye having no absorption in the visible region is preferred. Visible
Prevents halation using dyes that absorb in the region
In some cases, the dye color does not substantially remain after image formation.
It is preferable to remove the color by heat of heat development.
It is preferable to use a means, and in particular, heat decolorization in the non-photosensitive layer
Add dye and base precursor to anti-halation
It is preferable to function as an active layer. To these technologies
This is described in JP-A-11-231457. The amount of decoloring dye added depends on the use of the dye.
Determine. In general, light measured at the target wavelength
Use in an amount where the chemical concentration (absorbance) exceeds 0.1. Optical
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 if 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, silver tone and aging of image are changed.
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 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
Degree of stardust failure (one of the coating surface defects, the matting agent is the emulsion layer)
As long as it is in a range that does not cause a breakdown
Good, but Beck smoothness of 30 to 2000 seconds is preferred
In particular, it is preferably 40 seconds or more and 1500 seconds or less. Be
The smoothness of the paper is determined by Japanese Industrial Standard (JIS) P8119
And smoothness test using Beck tester for paperboard and TA
It can be easily obtained by the PPI standard method T479. 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. In the 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. The 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 hardener is added as a solution and the solution
The timing of addition to the protective layer coating solution is from 180 minutes before application.
Immediately before, preferably 60 minutes to 10 seconds before, mixing method
And the mixing conditions as long as the effects of the present invention are sufficiently exhibited.
There are no particular restrictions on the location. As a 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 No. 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-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. What 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 shown in Fig. 427 on the same book.
It is in ure 11b.1. In addition, if desired, pages 399-536
Paged method, U.S. Pat.No. 2,761,791 and British patent
Two or more layers by the method described in No. 837,095
The 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 fluid has a shear rate of 0.1S.^-1Viscosity at 400 mPa
· S to 100,000 mPa · s is preferable,
More preferably, it is 500 mPa · s or more and 20,000.
mPa · s or less. Also, shear rate 1000S^-1In
1 mPa · s to 200 mPa · s is preferable
More preferably, 5 mPa · s or more and 80 mP
a · 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.
Heat-developed image-developable image-recorded material that has been exposed to JWise development
Is done. The preferred development temperature is 80 to 250 ° C.
More preferably, it is 100-140 degreeC. During development
The interval is preferably 1 to 60 seconds, more preferably 5 to 30 seconds.
Preferably, 10 to 20 seconds are particularly preferable. As a thermal development method, a plate heater 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 side 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, pages 39-55.
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 [0171] 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
-Intrinsic viscosity (IV, Intrinsic Visc
osity) is 0.66 (phenol / tetrachloroethane = 6/4
(Measured at 25 ° C in (mass ratio)) polyethylene terephthalate
(PET) was obtained. 4 hours at 130 ° C after pelletizing
Dry for a while, melt at 300 ° C, then extrude from a T-die and quench rapidly
However, the thickness is not yet extended so that the film thickness after heat setting is 175 μm.
A stretched film was created. 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. (Preparation of 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 10% solution 5.4g     (Average number of ethylene oxide = 8.5)   MP-1000 (polymer fine particle, average particle size 0.4μm) 0.91g by Soken Chemical Co., Ltd.   935ml distilled water [0176] 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-20 g                      Triazine sodium salt 8% aqueous solution   10% 1% aqueous solution of sodium laurylbenzenesulfonate   Distilled water 854ml [0177] 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   Distilled water 80 5ml << Coating of undercoat layer >> The above-mentioned thickness of 175 μm
Both sides of biaxially stretched polyethylene terephthalate support
After applying the above corona discharge treatment to each, one side (photosensitive
Layer coating) with a wire bar.
The coating amount is 6.6ml / m²Apply to (per side)
And dry for 5 minutes at 180 ° C, then backside (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
Group precursor compound 11 (chemical structure will be shown later
64g, diphenylsulfone 28g and Kao
Surfactant Demol N 10g made by Co., Ltd. mixed with 220ml distilled water
And mix the mixture with a sand mill (1/4 Gallon sand grinder
-Bead dispersion using Mill, Imex Co., Ltd.
Of a base precursor compound having an average particle size of 0.2 μm
A fine particle dispersion (a) was obtained. (Preparation of dye solid fine particle dispersion) Cyanine
9.6 g of dye compound 13 (chemical structure will be summarized later)
And p-dodecylbenzene sodium sulfonate 5.8 g
Mix with 305 ml of distilled water and mix the mixture with a sand mill (1/4 Gallo
n Sand grinder mill, manufactured by Imex Co., Ltd.
Disperse beads and fine dye solid particles with an average particle size of 0.2μm
A 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, blue dye compound 14 (chemical structure will be summarized later
0.2g, yellow dye compound 15 (the chemical structure is
3.9g) and 844ml water to prevent halation
A stopping layer coating solution was prepared. (Preparation of back surface protective layer coating solution)
Incubate at 40 ° C and flow gelatin 40g, liquid paraffin emulsion.
1.5g as moving paraffin, 35m benzoisothiazolinone
g, 1mol / L caustic 6.8g, t-octylphenoxyethoxy
Sodium ethanesulfonate 0.5g, polystyrene
Sodium phonate 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 (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 ℃,
Diluted solution A and odor by adding distilled water to 22.22 g of acid silver and diluting to 95.4 ml
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
A silver halide emulsion 1 was prepared by adding a molar amount. The grains in the prepared silver halide emulsion are:
Average sphere equivalent diameter 0.042μm, sphere equivalent diameter variation coefficient 20%
Silver iodobromide grains uniformly containing 3.5 mol% of copper. grain
The child size is the average of 1000 particles using an electron microscope.
Asked. The [100] face ratio of this particle is
80% using the method. << Preparation of silver halide emulsion 2 >> Halogenation
In the preparation of silver emulsion 1, the liquid temperature at the time of grain formation was 30 ° C to 47 ° C.
In Solution B, 15.9 g of potassium bromide 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
Spectral sensitization and chemical sensitization in the same way as Emulsion 1 except that
Sensation and 5-methyl-2-mercaptoben ヅ imidazole, 1-
Phenyl-2-heptyl-5-mercapto-1,3,4-triazol
The silver halide emulsion 2 was obtained. halogen
The emulsion grains of silver halide emulsion 2 have an average equivalent sphere diameter of 0.080 μm and spheres
Pure silver bromide cubic grains with an equivalent diameter variation coefficient of 20%. << Preparation of silver halide emulsion 3 >> Halogenation
In the preparation of silver emulsion 1, the liquid temperature at the time of grain formation is 30 ° C.
The silver halide emulsion 3 was prepared in the same manner except that
Made. In addition, as with the silver halide emulsion 1, precipitation /
Desalting / washing / dispersion was performed. Spectral sensitizing dye A and spectral sensitization
Solid dispersion (gelatin aqueous solution) with a molar ratio of dye B of 1: 1
Sensitizing dye A and sensitizing dye B per mole of silver
6 × 10 as the sum of^-3Mol, tellurium sensitizer 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
So that the content of silver was 38.2 g as silver. (Preparation of non-photosensitive organic silver salt dispersion) : Preparation of reducible silver salt dispersions A to C << 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
The solid content is filtered off and the conductivity of filtered water is 30 μS / cm.
Washed with water until Thus, a fatty acid silver salt was obtained. Obtained
Keep the solid content as a wet cake without drying.
Tubed. The morphology of the obtained silver behenate particles B 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%. The above
The flaky silver salt particles are defined as follows. Silver salt grain
Observing the particles with an electron microscope, the shape of the organic acid silver salt particles is rectangular
Approximating the body, and from the shortest side of this cuboid, a,
When b and c (c may be the same as b), short
It calculates with the numerical value a and b which is the most, and calculates x from the following formula. x = b / a In this way, x is obtained for about 200 particles,
When the average value x (average) is given, x (average) ≧ 1.5
Those satisfying the above relationship are made flakes. Wet cake equivalent to 100 g of dry solid content
In contrast, polyvinyl alcohol (trade name: PVA-21
7, average polymerization degree about 1700) 7.4 g and water,
Preliminarily disperse with homomixer after setting the total amount to 385 g
did. Next, the pre-dispersed stock solution is applied to a disperser (trade name: My
Black Fluidizer M-110S-EH, Micro Full
Idex International Corporation
Manufactured by G10Z Interaction Chamber)
Was adjusted to 175.0 MPa, treated three times, and behenic acid.
A silver dispersion was obtained. For the cooling operation, a serpentine heat exchanger is
Installed on the front and rear sides of the cooling chamber, respectively,
The dispersion temperature was set to 18 ° C. by adjusting the degree. : Reducible polymer silver salt dispersions D to P
Preparation of Similar to the preparation of reducible silver salt dispersion A, the COG used in
Behenic acid manufactured by NIS DEUTSCHLAND GmbH (product name EDENOR C22-8
Carboxylic acid compounds (general formulas) listed in Table 1 against 5JP GW
(1) polymers P-4, 8, 11 and acrylic acid /
2-ethylhexyl acrylate random copolymer)
An amount of equimolar amounts of carboxyl groups, 423 ml of distilled water,
49.2 ml of 5 mol / liter-NaOH aqueous solution, t
ert-butanol (120 ml) was mixed and 1 at 75 ° C.
The reaction was stirred for an hour. Separately, 40.4 g of silver nitrate in water
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.
The total amount of the previous sodium salt solution and the total aqueous silver nitrate solution
Add the amount at a constant flow rate over 62 minutes 10 seconds and 60 minutes respectively.
Added. At this time, 7 minutes and 20 seconds after the start of addition of the aqueous silver nitrate solution
Only the aqueous silver nitrate solution should be added between
Start adding sodium salt solution and finish adding silver nitrate aqueous solution.
9 minutes and 30 seconds after completion, only sodium salt solution is added
I did it. At this time, the temperature in the reaction vessel is 30 ° C.
The external temperature was controlled so that the liquid temperature was constant.
Also, the sodium salt solution addition system piping is steam
The temperature is maintained by the race, and the liquid temperature at the outlet of the addition nozzle tip is
The steam opening was adjusted to 75 ° C. Glass
The piping of the silver acid aqueous solution addition system circulates cold water outside the double pipe.
It was kept warm by ringing. Addition of sodium salt solution
The position and the addition position of the silver nitrate aqueous solution are centered around the stirring axis.
And a height that prevents contact with the reaction solution.
Prepared. After completing the addition of the sodium salt solution
The mixture was left stirring at temperature for 20 minutes, and the temperature was lowered to 25 ° C. That
After that, the solid content is separated by suction filtration, and the solid content is transferred to the filtered water.
The water was washed until the degree reached 30 μS / cm. Poly
Mar silver salt was obtained. Do not dry the resulting solids.
Stored as an et cake. Wet cake equivalent to 100 g of dry solid content
In contrast, polyvinyl alcohol (trade name: PVA-21
7, average polymerization degree about 1700) 7.4 g and water,
Preliminarily disperse with homomixer after setting the total amount to 385 g
did. Next, the pre-dispersed stock solution is applied to a disperser (trade name: My
Black Fluidizer M-110S-EH, Micro Full
Idex International Corporation
Manufactured by G10Z Interaction Chamber)
Is adjusted to 175.0 MPa and treated three times to obtain a polymer.
A silver salt dispersion was obtained. Cooling operation is performed with a serpentine heat exchanger.
Attach before and after the traction chamber,
The dispersion temperature was set to 18 ° C. by adjusting the temperature. (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)
Tilphenol) and triphenylphosphine oxide
1: 1 complex) 10 kg, triphenylphosphine oxide 0.
12Kg and modified polyvinyl alcohol (Kuraray Co., Ltd.,
Add 7.2 kg of water to 16 kg of 10% aqueous solution of Poval MP203)
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
Dispersion for 4 hours 30 minutes, and then benzoiso
Add 0.2 g of thiazolinone sodium salt and water to concentrate the reducing agent.
And the reducing agent complex-3 dispersion
Obtained. Reducing agent contained in the reducing agent complex dispersion thus obtained
Complex particles have a median diameter of 0.46 μm and a maximum particle diameter of 1.6 μm or less.
it was under. The resulting reducing agent complex dispersion has a pore size of 3.0 μm.
Filtered with a polypropylene filter of trash, etc.
The 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 having 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) 1
Add 4.28 Kg to prepare a 5% solution of phthalazine compound-1.
Made. (Preparation of aqueous solution of mercapto compound-1)
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 solution) Tg = 23 ° C.
The SBR latex was prepared as follows. Polymerization initiator
As ammonium persulfate, anionic interface as emulsifier
Using activator, 70.5 parts by mass of styrene, butadiene
26.5 parts by mass and 3 parts by mass of acrylic acid are emulsion polymerized
After aging, aging was performed at 80 ° C. for 8 hours. Then 4
Cool to 0 ° C and adjust to pH 7.0 with aqueous ammonia.
In addition, Sanyo Chemical Co., Ltd. sandet BL will be 0.22%
It was added. Next, add 5% aqueous sodium hydroxide.
PH 8.3, and further adjusted to pH 8.4 with aqueous ammonia.
It was prepared as follows. Na used at this time⁺Ion and NH_Four ⁺
The molar ratio of ions was 1: 2.3. In addition, this liquid
1 kg of benzoisothiazoline non sodium salt 7
Add 0.15 ml of a 0.1% aqueous solution and prepare the following SBR latex solution.
Made. SBR latex: -St (70.5) -Bu (26.5) -AA
(3)-Latex Tg23 ℃ Average particle size 0.1 μm, Concentration 43%, Equilibrium moisture content at 25 ℃ 60% RH 0.6%, Ionic conductivity 4.2mS / cm (Ion conductivity is measured by Toa
Industrial Co., Ltd. conductivity meter Using CM-30S, measure latex stock solution (43%) at 25 ° C) pH8.4 SBR latexes with different Tg are styrene, butadiene
The ratio was appropriately changed and prepared in the same manner. (Preparation of coating solution for each constituent layer) << Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-1 >> Return obtained above
Organic silver salt dispersion containing silver salt compound B or H
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 173g, SBR latte in the amount of Table 2
(Tg: 20.5 ° C), 9 g of mercapto compound-1 aqueous solution
Add 158g of silver halide mixed emulsion immediately before coating.
Add and mix well the emulsion layer coating solution as it is.
The solution was sent to the coating die and applied. << Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution-2 >>
Each of the reducible silver salt compounds A to P obtained above is included.
Mu, organic silver salt dispersion 1000g, water 104ml, pigment-1 dispersion 30
g, organic polyhalogen compound-2 dispersion 21 g, organic polyhalogen
Rogen compound-3 dispersion 69g, phthalazine compound-1 solution
173 g of liquid, SBR latex (Tg: 23 ° C) in the amount shown in Table 2, reducing agent
Complex-3 dispersion 258g, mercapto compound-1 solution 9g in order
Next, add silver halide mixed emulsion A110g just before coating.
Add and mix emulsion layer coating solution as it is
The solution was fed to the die and applied. << Preparation of Emulsion Surface Intermediate Layer Coating Solution >> Polyvinyl
772g of 10% aqueous solution of alcohol PVA-205 (Kuraray Co., Ltd.)
5.3 g of 20% pigment dispersion, methyl methacrylate / styre
/ Butyl acrylate / hydroxyethyl methacrylate
/ Acrylic acid copolymer (copolymerization mass ratio 64/9/20/5/2)
X 27.5% solution 226g and aerosol OT (American Sai
2 ml of 5% aqueous solution of Anamide), diammonium phthalate
10.5 ml of 20% aqueous solution of um salt, water to a total volume of 880 g
And adjust with NaOH so that the pH is 7.5.
10ml / m as cloth liquid²To the coating die
Liquid. The viscosity of the coating solution is 40 ° C (No. 1 rotor)
-60 rpm) and 21 [mPa · s]. << Preparation of coating liquid for emulsion surface 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 liquid for emulsion layer protective layer second layer >>
Methyl methacrylate is dissolved in water
/ Styrene / Butyl acrylate / Hydroxyethyl meta
Chrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20
/ 5/2) 27.5% latex by weight 102g, fluorinated surface activity
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]. (Preparation of heat-developable image recording material) << Heat development image recording using emulsion layer (photosensitive layer) coating solution-1
Recording material-1 series preparation> Back side of the undercoat support
In addition, the anti-halation layer coating liquid is solid solid dye
Application amount of 0.04g / m²And back side protective layer
The coating amount of gelatin is 1.7g / m²Simultaneous weight to be
The layers were applied and dried to form a back layer. [0211] Emulsion layer from undercoat to reverse side
(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
Apply simultaneous multi-layer coating using the formula to make a sample of heat-developable image recording material.
Made. At this time, the emulsion layer and intermediate layer are
One layer was adjusted to 36 ° C, and the first protective layer was adjusted to 37 ° C. milk
Coating amount of each compound in the agent layer (g / m²) Is as follows. [0212]   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.
It was dried with a drying air having a temperature of 23 to 45 ° C and a wet bulb temperature of 15 to 21 ° C.
After drying, the humidity is adjusted to 40-60% RH at 25 ° C, and the film surface is 70
Heated to ~ 90 ° C. After heating, film surface up to 25 ° C
Cooled down. The matte degree of the heat-developable image recording material thus prepared
Is Beck smoothness, photosensitive layer surface side is 550 seconds, back surface is 130
Second. 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 series of heat-developable image recording materials >> Heat-developable image recording materials
-1 to emulsion layer (photosensitive layer) coating solution-2
Change to the yellow dye compound from the antihalation layer
Except for the product 15, the same as heat-developable image recording material-1
Two series of heat-developable image recording materials were prepared. Emulsion at this time
Coating amount of each compound in the layer (g / m²) Is as follows. [0216]   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 Used in the heat-developable image recording material prepared in Table 2.
Emulsion layer coating solution, coating amount, reducible silver chloride used
The compound, the SBR amount, and the total thickness of the image forming layer are shown. Table 2
In the heat developing material column, for example, “1B”
The heat developing material is an emulsion layer (photosensitive layer) coating solution.
Belongs to 1 series of heat-developable image recording material using 1 and can be reduced
A material using B shown in Table 1 as a simple silver salt compound
Means that it is the second of the materials
To do. The compounds used in the examples of the present invention are shown below.
The academic structure is shown. [0219] Embedded image [0220] Embedded image[0221] Embedded image [0222] Embedded image[0223] Embedded image Regarding the produced recording material (sample),
Measure and evaluate processability and photographic properties by the following methods.
It was. The results are shown in Table 3. ・ Processability evaluation (film quality evaluation) The obtained sample, with an upper blade of a heel angle of 1 ° and a blade edge angle of 89 °,
Use a lower blade with a 0 ° edge angle and a 90 ° edge angle, and fix the lower blade.
The upper blade was cut at 1 m / sec with respect to the lower blade.
Observe both cut surfaces of the cut sample at 100x with an optical microscope
Then, the processability (film quality) was evaluated. Evaluation is below
This was done in four stages. A: No film peeling occurs and the cut surface is smooth ○: No film peeling but rough surface Δ: Film peels off, but peels off after rubbing by hand
There is no problem in practical use. X: Film break-up occurs and it is peeled off by hand. ・ Photographic evaluation 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 under 25 ° C environment
The photographic properties were evaluated after packaging. (Packaging material) PET 10μm / PE 12μm / Aluminum foil 9μm / Ny 15μm / Carbo
Polyethylene 50% containing 3% Oxygen permeability: 0ml / atm · m²・ 25 ℃ ・ day, moisture permeability: 0g
/ atm ・ m²・ 25 ℃ ・ day (Specific photographic evaluation method) Sample (heat-developable image recording material)
Fuji Medical Dry Laser Imager FM
-DPL (660nm semiconductor laser with maximum output of 60mW (IIIB)
For measurement of the density of the image obtained by exposure and thermal development.
More went. In other words, the measurement of photographic properties is sensitivity and fogging.
(Dmin) is measured by the international standard (IS
Status A neutral fill by optical system specified in O-5)
Depending on the concentration. As the sensitivity value, Dmin + 0.2
The inverse logarithm of the exposure amount was taken and indicated by its relative value. Development strip
The case is as follows. Temperature: 135 ° C Time: 12 seconds The sensitivity of the heat-developable image recording material 1B is assumed to be 100, and the relative table
Indicated. [0225] [Table 1] # 1: Acrylic acid / 2-ethylhexylua
Chryrate random copolymer (50/50% by mass) [0227] [Table 2] [0228] [Table 3]From the results of Table 3, the following is clear.
The heat-developable image recording material of the present invention has good processability,
Excellent film strength. The heat-developable image recording material of the present invention
Even if the material is processed in a short time (12 seconds), the sensitivity is good and the
The yellowtail density is small and it is suitable for rapid processing. In particular, relatively
The heat-developable image recording of the present invention also in the development processing at high temperature
The material has a low fog density value and is an excellent photograph.
Maintains performance. Although not shown in Table 3, Table 3
5 days at 50 ° C. and 40% RH
Concentration measurement is performed again after storage.
The degree of change is 0.02 or less, and the image storage stability is practical.
It was also shown that it was quite sufficient. [0230] The heat-developable image recording material of the present invention has a film quality,
Excellent in rapid processing suitability, photographic properties and image storage
In particular, the film for medical diagnosis
And heat-developable image recording material excellent for photoengraving film
Can provide a fee.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Yamanouchi             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H123 AB00 AB01 AB03 AB23 AB25                       BA00 BA14 BB00 BB09 BB39                       CA00 CA22 CB00 CB03

Claims (1)

1. A heat containing at least one photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent for silver ions, and a binder on one side of the support. A heat-developable image recording material, wherein a silver salt of a polymer represented by the following general formula (1) is used as the non-photosensitive organic silver salt. General formula (1) (In the general formula (1): A represents a repeating unit derived from the monomer A represented by the following general formula (2), and B represents an ethylenic group other than the monomer A represented by the following general formula (2). Represents a repeating unit derived from unsaturated monomer B;
It contains at least one repeating unit derived from a vinyl ether monomer or alkene. ) General formula (2) (In general formula (2): R ¹ and R ² are each independently
A hydrogen atom or a methyl group is represented, and R ³ and R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group which may have a substituent. However, at least one of R ³ and R ⁴ is a hydrogen atom. m and n represent the ratio (mol%) of the repeating units A and B, respectively.
m is 20 to 60 mol%, and n is 40 to 80 mol%. Here, m + n = 100 mol%. )