JPS62121452A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat developable photosensitive material capable of obtaining an image high in density and free from fog by incorporating a polymer having repeating units derived from a monomer represented by the formula: Q-X. CONSTITUTION:The heat-developable photosensitive material provided with a layer containing photosensitive silver halide on a support contains the repeating units derived from the monomer represented by the formula: Q-X in which Q is an ethylenically unsaturated group or a group having the ethylenically unsaturated group, and X is the residue of a photographic inhibitor. A preferable inhibitor is a compound having an N-containing heterocyclic ring with an -SM group, especially, a compound represented by formula (I) in which R<1> is H, alkyl, or aryl, and M is H, an alkali metal, ammonium, or organic amine residue.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a heat-developable photosensitive material on which an image is formed by heat development, and more particularly to a heat-developable photosensitive material containing a novel inhibitor for suppressing fog during heat development.

[Background of the invention]

Regarding heat-developable photosensitive materials whose development process can be carried out by heat treatment, for example, Japanese Patent Publication No. 43-4921 and No. 43-4
There is a description in Japanese Patent No. 924, which discloses a photosensitive material comprising an organic silver salt, silver halide, and a reducing agent. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Patent Nos. 3,531,286 and 3,7
No. 61゜270 and No. 3,764.328 disclose heat-developable color photosensitive materials in which a color image is formed by a reaction between an oxidized product of an aromatic primary amine developing agent and a coupler. ing. Further, Research Disclosure Nos. 15108 and 15127 disclose heat-developable color photosensitive materials in which a color image is formed by a reaction between an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent and a coupler. However, in these methods, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem that the color image becomes cloudy. To solve this problem, there is a method of removing the silver image by liquid processing or transferring only the dye to another layer, such as an image receiving sheet having an image receiving layer, but it is necessary to distinguish between unreacted materials and the dye. The problem is that it is not easy to transfer only the dye. In addition, as described in Research Disclosure No. 16966, an organic imino silver salt having a dye part is used, and the imino group is liberated in the exposed area by heat development, and a color image is formed on the image receiving layer as a transfer paper using a solvent. A color photosensitive material is disclosed. However, with this method, it is difficult to suppress the release of dye in areas that are not exposed to light.
This has the problem that a clear color image cannot be obtained. Also, JP-A-52-105821, JP-A No. 52-1058
No. 22, No. 56-50328, U.S. Patent No. 4,
No. 235,957, Research Disclosure No. 14448, Research Disclosure No. 15227, Research Disclosure No. 18137, and the like disclose heat-developable color photosensitive materials in which a dull color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Also, U.S. Patent Nos. 3,180,732 and 3,98
No. 5,565 and No. 4,022,617, as well as Research Disclosure No. 12533, disclose heat-developable color photosensitive materials that utilize leuco dyes to form color images. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, JP-A-57-179840, JP-A No. 57-186
No. 744, No. 123533, No. 59-12431, No. 59-124339, No. 59-166954,
Publications such as No. 59-159159, No. 59-181345, and No. 59-229556 disclose heat-developable color photosensitive materials that release or form diffusible dyes by heat development to obtain transferred color images. However, these prior art techniques have the highest concentration (D
There is a disadvantage that increasing the fog (D m1n) increases, and if an inhibitor used in ordinary conventional photographic materials is used to suppress fog, it will not have a suppressing effect and will actually increase the fog. There are drawbacks such as increasing D max or decreasing D max and sensitivity at the same time, and there is a strong desire to develop an inhibitor that can be used in heat-developable photosensitive materials.

[Purpose of the invention]

An object of the present invention is to solve the problems of the above-mentioned photothermographic materials. That is, an object of the present invention is to provide a photothermographic material containing a novel inhibitor. Another object of the present invention is to provide a heat-developable photosensitive material capable of obtaining high-density and fog-free images. Another object of the present invention is to provide a photothermographic material having improved shelf life.

[Structure of the invention]

As a result of intensive research to achieve the above object, the present inventors have developed a heat-developable photosensitive material having a layer containing photosensitive silver halide on a support, from a monomer represented by the following general formula (1). It has been found that the above objects of the present invention can be achieved by a heat-developable photosensitive material containing a polymer having induced repeating units. General Formula (1) In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X represents a residue of a photographic inhibitor. Although the mechanism of action of the above-mentioned polymer in the present invention is not clear, inhibitors that are effective in conventional silver halide photographic materials generally cause a significant increase in fog or a decrease in sensitivity in heat-developable materials. The effect of the present invention is surprising compared to the results obtained.

[Specific structure of the invention]

In the general formula (1), Q is an ethylenically unsaturated group or
or a group that removes an ethylenically unsaturated group.
Alternatively, it is represented by the following general formula (2). −・General formula (2) In the formula, ! E is a hydrogen atom -r-, a carboxy group or an alkyl group
represents a methyl group (e.g. methyl group, edyl μ, etc.);
The alkyl group may have a substituent, and the substituent is
For example, [Igen atom-f'-1 (e.g., fluorine atom
, chlorine atom, etc.), carboxyl group, etc. Carboxyl group and substituent carboxyl group represented by R
Syl groups may form salts. J and J2 are respectively
represents a divalent bonding group, and this divalent bonding group is
For example, -N II CO-1, -CON II-1-COO-
1-OC0-1-s c o-1-COS-1-〇-1
-8-1-s o -1-SO2-, etc. xI and
and X represent divalent hydrocarbons and @ group, respectively;
Examples of hydrocarbon groups include alkylene groups and arylene groups.
group, acylkylene group, alkylenearylene group or arylene group
A rylene alkylene group is mentioned, and as an alkylene group,
For example, methylene group, ethylene group, propylene group, etc.
The arylene group is, for example, a phenylene group.
etc., and the aralkylene group is phenylmethylene
The alkylene arylene group is, for example,
, methylene phenylene group, etc., and arylene alkylene group
Examples of the group include phenylene methylene group, etc.
. k +121+m++ (2t and m2 are O or
represents l. Photographic inhibitor represented by X in the general formula (1)
As a residue, for example, the basic silver halide photography edition of photographic engineering (Japanese
Edited by the Photographic Society, Coronasha) 354 pages, Chemistry of Photography (Sasai
Author: Akira, Photo Kogyo Publishing), pp. 168-169, or The Center
Ollie of Photographic Process (T,H
, edited by James, Matsuku Millan Publishing), pp. 396-399.
Conventional halogenation as described
A photographic inhibitor (or anti-fogging agent) in silver photographic materials.
It is the residue of an organic compound known as
or the solubility product of the silver salt of that compound in water at 25°C.
(pKsp) is a residue of an organic compound of 10 or more. Examples of preferable photographic inhibitors include the following:
can be lost. (R1 and R2 are each hydrogen atom, alkyl group, or alkyl group)
M represents a hydrogen atom, an alkali metal atom, a
Does not represent ammonium groups or organic amine residues. ] [R1 represents an alkyl group, an aryl group, or a hydrogen atom
, M have the same meaning as M in general formula (3). ]R"
H (R' represents a hydrogen atom, an alkyl group, an aryl group or
, R2 and R3 are each hydrogen atom, alkyl group, aryl
group or nitro group, R2 and R3 are bonded to form a 5-membered or nitro group.
may form a 6-membered ring. ]CRI is an alkyl group,
represents an aryl group or a hydrogen atom, and R2 and R3 each represent
Represents a hydrogen atom, alkyl group, aryl group or nitro group
and R2 and R3 combine to form a 5- or 6-membered ring.
Good too. ] [Y represents -N-, -0- or -S-
, R1 represents an alkyl group, a ring group, or a hydrogen atom
, M have the same meaning as M in general formula (3). ], R1 and
R4 each represents an alkyl group, an aryl group or a hydrogen atom;
and R2 and R3 are each a hydrogen atom, an alkyl group, or an aryl group.
represents a 5-membered group or a nitro group, and R1 and R3 are bonded together.
Alternatively, a 6-membered ring may be formed. ] f [Y is Y in general formula (8), R1 and R2 are in general formula (8)
), and M is M in general formula (3), respectively.
are synonymous. ] (R' and R2 are each hydrogen atom, alkyl group, aryl
group, nitro group or halogen atom, and R1 and R2 are
They may be combined to form a 5- or 6-membered ring. ] RI (RISR! and R3 are an alkyl group, an amino group, an atom group, respectively)
alkoxy group, thioalkoxy group, -SM (M is the general formula (
It is synonymous with M in 3). ), hydroxyl group or hydrogen atom
represents a child. ] (R', R'', rt', rt' and R5 are each hydrogen
Atom, alkyl group, aryl group, R6-NH-(R8 is
Represents a hydrogen atom, an alkyl group, or an aryl group. )-S
M (M has the same meaning as M in general formula (3)), alkyl
Represents a thio group, hydroxyl group or alkoxy group. ] J (R', I'j 'Jt 3 and R4 are each represented by the general formula (1
It has the same meaning as R1-R5 in 2). ] (RI and R2 each represent an alkyl group or a hydrogen atom
. ] [R1 and R2 may each be bonded to form a 5- or 6-membered ring. ] R1 and R1 may be combined to form a 5- or 6-membered ring. Y is 10 -, -S- or -N (R' is a hydrogen atom or
or represents an alkyl group. ). ] or alki
represents a group. ). ] R2 each represents an alkyl group, an aryl group, or a hydrogen atom, and R1 and R2 may be combined to form a 5- or 6-membered ring. 〕teeth
Represents a counter-anion. ] A particularly preferred photographic inhibitor is -SM (S is the general formula (3)
It is synonymous with M. ) having a nitrogen-containing heterocycle
It is a compound represented by general formula (4) or general formula (9).
More preferred are compounds such as The monomerization represented by the general formula (1) of the present invention will be described below.
Although typical examples of compounds are shown below, the present invention is not limited to these.
It's not something you can do. (m-1) (m-2) (m-3
) (m-4) (m-5)
(m -6) (m-7) (m-8) II3 (m-L'O) +12 ” UtlL;Ntl II
111I
Q (m-13)
(m-14) (m-19) (m-22) (m-2
3) (m -24) (m
-25)U
0(m-26)
(m -27) (m-28) (
m -29)6++, coon Synthesis examples of exemplary monomers of the present invention are shown below. Synthesis example-1 1-(p-methacrylamidophenyl)-1,2,3
゜Synthesis of 4-tetrazole-5-thiol (m-1). 30 g of I-(p-aminophenyl)-1,2,3,4
-tetrazole-5-thiol in 300m&aacute;
Toryl and 20m(!) dissolved in a pirin solution, and added to this solution.
While stirring, add 16 m of methacrylic acid chloride (dropwise).
did. After the dropwise addition, after stirring for 1 hour in the chamber layer, 10% of sodium hydroxide was added.
% aqueous solution and stirred for a while, then diluted with dilute hydrochloric acid.
29.4 g of white (target product) precipitated as (yield 72
%) was obtained. Synthesis example-2 1-(p-vinylhensyl)-1,2,3,4-tetra
Synthesis of sol-5-thiol (m-5). 76g of vinylbenol chloride was added to 300mρ of
Dissolved in chloroformamide (D M r' ), and this solution
56 g of potassium thionate and 28 g of sodium iodide.
After heating and stirring at 150°C for 30 minutes,
Most of the MF was distilled off under reduced pressure. Remaining 750m (2nd e)
Extract with water, filter and concentrate to obtain 30g of liquid (vinyl vinyl).
(Norisodionanate) was obtained. 15g of this pendyl isodiocyanate was added to 6.2g of acetic acid.
200ml of water containing sodium dilide (add to 2 with stirring)
Then, it was refluxed for 3 hours. After cooling this reaction solution, it was made acidic with dilute hydrochloric acid.
7 g (34%) of the desired product was obtained as white crystals. Synthesis example-3 5-methacrylamide benzotriazole (m-17
) composition. 26.8g of 5-aminobenzotriazole in 300m(
! of acetonitrile and 40 mQ of pyridine,
6.5 g of methacrylic acid chloride was added dropwise. Concentrate this liquid and add 20% of 10% aqueous sodium hydroxide solution.
0mN! After stirring for 30 minutes, neutralize with dilute hydrochloric acid.
, 27.3 g (6.7%) of precipitated solids were obtained. Derived from the monomer represented by the general formula (1) of the present invention
Polymers having repeating units represented by the general formula (1
) repeating unit consisting of only one type of monomer
It is a so-called homopolymer of the general formula (1)
A copolymer that combines two or more monomers represented by
-, but preferably other copolymerizable ethyl
Consisting of one or more types of comonomers that grow lenically unsaturated groups
It is a copolymer. Monomer and copolymer represented by the above general formula (1) of the present invention
A copolymer containing the above-mentioned ethylenically unsaturated group that can form a polymer.
Acrylic acid ester, methacrylic acid ester
Stell, vinyl esters, olefins, styrenes
, crotonate esters, itaconic acid noesters,
Leic acid diesters, fumaric acid diesters, acrylic acid diesters
Ruamides, allyl compounds, vinyl ethers, vinyl
Ketones, vinyl heterocyclic compounds, glycidyl esters
, unsaturated nitriles, polyfunctional monomers, various unsaturated acids, etc.
can be mentioned. More specifically, these comonomers are
Examples of lylic acid esters include methyl acrylate and ethyl acrylate.
acrylate, n~propyl acrylate, isopropyl acrylate
Pyracrylate, n-butyl acrylate, isobutyl acrylate
acrylate, 5eC-butyl acrylate, ter
t-butyl acrylate, amyl acrylate, hequin
acrylate, 2-ethylhexyl acrylate,
Cutyl acrylate, tert-octyl acrylate
, 2-chloroethyl acrylate, 2-bromoethyl acrylate
Acrylate, 4-chlorobutyl acrylate, cyanoe
Tyl acrylate, 2-acetoxyethyl acrylate
, dimethylaminoethyl acrylate, benzyl acrylate
rate, methoxybenzyl acrylate, 2 to chloro
Xyl acrylate, cyclohexyl acrylate, fluorine
Rufuryl acrylate, tetrahydrofurfuryl acrylate
rate, phenyl acrylate, 5-hydroxypentyl
acrylate, 2,2-dimethyl-3-hydroxypropylene
Lopylacrylate, 2-methoxyethyl acrylate
, 3-methoxybutyl acrylate, 2-ethoxyethyl
acrylate, 2-iso-propoxy acrylate
, 2-butoxyethyl acrylate, 2-(2-methoxy
ethyl acrylate, 2-(2-butoxy)
ethoxy)ethyl acrylate, ω-methoxypolyethyl
Ren glycol acrylate (number of added moles n = 9), l
-bromo-2-methoxyethyl acrylate, 1.1-
Dichloro-2-ethoxyethyl acrylate etc.
It will be done. Examples of methacrylic acid esters include methyl methacrylate.
Le-1, ethyl methacrylate, n-propyl methacrylate
rylate, isopropyl methacrylate, n-butyl methacrylate
tacrylate, isobutyl methacrylate, 5ec-butyl
Tyl methacrylate, tert-butyl methacrylate
, amyl methacrylate, hensimethacrylate, sik
lohexyl methacrylate, hensyl methacrylate,
Chlorobenzyl methacrylate, octyl acrylate
, sulfopropyl methacrylate, N-ethyl-N-ph
Phenylaminoethyl methacrylate, 2-(3-phenylaminoethyl methacrylate)
Lubrovir Okino) Ethyl methacrylate, Dimedylua
Minophenoxyethyl methacrylate, furfuryl meth
acrylate, tetrahydrofurfuryl methacrylate,
Phenyl methacrylate, talesyl methacrylate, sodium
Phthyl methacrylate, 2-hydroxyethyl methacrylate
rate, 4-hydroxybutyl methacrylate, trie
tyrene glycol monomethacrylate, dipropylene
Recall monomethacrylate, 2-methoxyethyl methacrylate
acrylate, 3-methoxybutyl methacrylate, 2-
Acetoxyethyl methacrylate, 2-acetoacetoxy
ethyl methacrylate, 2-ethoxyethyl methacrylate
rate, 2-iso-propoxyethyl methacrylate
, 2-butoxyethyl acrylate, 2-(2-methoxy
noethoxy)ethyl methacrylate, 2-(2-ethoxy)
Noethoxy)ethyl methacrylate, 2-(2-butoxy)
ethoxy)ethyl methacrylate, ω-methoxy poly
Ethylene glycol methacrylate (number of moles added n-
6), allyl methacrylate, dimethyl methacrylate
Minoethyl methyl chloride salt, etc. may be mentioned.
Ru. Examples of vinyl esters include vinyl acetate, vinyl
Nilb-a bionate, vinyl butyrate, vinyl imida
Sol, vinyl caproate, vinyl chloroacetate
, vinyl methoxy acetate, vinyl phenyl acetate
vinyl benzoate, vinyl salicylate, etc.
Ru. Examples of olefins include dicyclopentane
, ethylene, propylene, l-butene, 1-pentene,
Vinyl chloride, vinylidene chloride, isoprene, chloroprene
butadiene, 2,3-dimethylbutadiene, etc.
can be done. Examples of styrenes include styrene and methylstyrene.
trimethylstyrene, trimethylstyrene, ethylstyrene
Styrene, isopropylstyrene, chloromethylstyrene
, methquinostyrene, acetoquinostyrene, chlorstyrene
Ren, nochlorostyrene, promstyrene, vinyl rest
Examples include fragrant methyl ester. Examples of crotonate esters include butyl crotonate.
, hexyl crotonate, etc. In addition, as itaconic acid diesters, for example, itaconic acid diesters include itaconic acid diesters.
Dimethyl acid, diethyl itaconate, dibdel itaconate
Examples include. Examples of maleic acid esters include maleic acid
diezyl, dimethyl maleate, dibdel maleate, etc.
Can you name any? Examples of fumaric acid diesters include fumaric acid diesters.
Chil, dimethyl fumarate, dibdel fumarate, etc.
It will be done. Examples of other comonomers include:
Ru. Acrylamides, e.g. acrylamide, mejilua
Acrylamide, ethyl acrylamide, propylacrylamide
ruamide, butylacrylamide, tert-butyl acrylamide
Acrylamide, cyclohexyl acrylamide, benzene
lyacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, trimethylaminoethyl
Acrylamide, phenylacrylamide, dimethylacrylamide
Acrylamide, diethylacrylamide, β-cyanoe
tylacrylamide, N-(2-acetoacetoxyethyl
) Acrylamide, etc.: Methacrylamides, such as methacrylamide, methacrylamide, etc.
methacrylamide, ethyl methacrylamide, propylene
methacrylamide, butyl methacrylamide, jer
t-Butylmethacrylamide, chlorohexylmethacrylamide
Ruamide, Benzylmethacrylamide, Hydroquinomethi
methacrylamide, methoxyethyl methacrylamide
, dimethylaminoethyl methacrylamide, phenylmethacrylamide
tacrylamide, diethylacrylamide, diethyla
Acrylamide, β-noanoethyl methacrylamide, N
-(2-acetoacetoxyethyl)methacrylamide
Allyl compounds, such as allyl acetate, allyl caproate
, allyl laurate, allyl benzoate, etc. Vinyl ethers, such as methyl vinyl ether, vinyl ether, etc.
Chyl vinyl ether, hexyl vinyl ether, methoxy
ethyl vinyl ether, dimethylaminoethyl vinyl
Ethers, etc.; Vinyl ketones, such as vinyl ketone, phenyl
Rubinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinyl ketone, etc.
Nylimidazole, N-vinyloxazolidone, N-vinyl
Nyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate
and glycidyl acrylate. Unsaturated nitriles, e.g. acrylonitrile, methacrylate
Rylonitrile etc.: Polyfunctional monomers, e.g. novinylbenzene, styrene
Bisacrylamide, ethylene glycol no methacrylate
In addition, acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc.
monoalkyl itaconate, e.g.
monomethyl itaconate, monobutyl itaconate
Lunato: Monoalkyl maleate, e.g. monomethylate maleate
monoethyl maleate, monobutyl maleate, etc.
: Citraconic acid styrene sulfonic acid, vinyl benzyl sulfate
Phonic acid, vinyl sulfonic acid, acryloyloxyalkyl
sulfonic acid, e.g. acryloyloxymethyl sulfonic acid
phonic acid, acryloyloxymethylsulfonic acid, acrylic
loyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl sulfonic acid, e.g.
tacryloyloxymethylsulfonic acid, methacryloyl
Oxyethylsulfonic acid, methacryloyloxypropyl
rusulfonic acid, etc.; acrylamide alkyl sulfonic acid
, for example, 2-acrylamido-2-methylethanesulfate
Fonic acid, 2-acrylamido-2-methylpropanesul
Phonic acid, 2-acrylamido-2-methylbutanesulfonate
methacrylamide alkyl sulfonic acids, such as 2-methacrylamidoalkylsulfonic acids;
tacrylamide-2-methylethanesulfonic acid, 2-methyl
tacrylamide-2-methylpropanesulfonic acid, 2-
Niacryloyloxyalkyl phosphates such as methacrylamide-2-methylbutanesulfonic acid, e.g.
Cryloyloxyethyl phosphate, 3-acryloyl
methacryloyloxyalkyl phosphate, e.g.
Methacryloyloxyethyl phosphate, 3-meth
Cryloyloxypropyl-2-phosphate, etc.; 3-aryloxy-2-hydroxypropyl having two hydrophilic groups;
Examples include sodium lopanesulfonate. these
The acid may be a salt of an alkali metal (e.g., Na.K, etc.) or ammonium ion.
. Further, as other comonomers, U.S. Pat.
No. 459,790, No. 3,438,708, No. 3
゜554.987, same No. 4.215,195, same No.
No. 4,247,673, Japanese Patent Application Publication No. 57-205735
Using crosslinking monomers described in the report specifications, etc.
I can do it. Examples of such crosslinking monomers include N
-(2-acetoacetoxyethyl)acrylamide, N
-(2-(2-acetoacetoxyethoxy)ethyl)a
Examples include crylamide. Moreover, the monomer shown in the above (1) of the present invention and the above comonomer
When forming a copolymer with a polymer, preferably the above-mentioned
The weight ratio of the repeating unit consisting of the monomer shown in (1) is
It may contain 10 to 90% by weight of the total polymer.
more preferably 30 to 70% by weight M%.
be. Polymer couplers are generally produced using emulsion polymerization or solution polymerization.
is polymerized by the method and is represented by the general formula (1) according to the present invention.
The present invention has a repeating unit derived from a monomer that
Bright polymers can also be polymerized in a similar manner. milk
For the chemical polymerization method, see U.S. Patent No. 4,080,211.
, No. 3,370,952;
Regarding the method of dispersing latin in the form of latex in aqueous solution.
is described in U.S. Patent No. 3.451.820.
A method can be used. These methods are used to form homopolymers and copolymers.
In the latter case, the comonomer is a 4-fold comonomer.
Nomar? -Also on A2〈-In the case of tight polymerization, it is fixed in the normal state.
It also acts as a solvent for the monomer. Emulsifiers used in emulsion polymerization include surfactants.
These include sexing agents, polymeric protective colloids, and copolymer emulsifiers.
It will be done. As the surfactant, surfactants known in the field can be used.
ionic activators, nonionic activators, cationic activators and both
and sexual activators. Examples of anionic activators include soaps, dodecyl bene
Sodium Zensulfonate, Sodium Lauryl Sulfate,
Sodium dioctyl sulfosuccinate, nonionic activator
Examples include sulfates of. Examples of nonionic activators include polyoxyethylene nonionic
Luphenyleyachil, polyoxyethylene stearic acid
Ester, polyoxyethylene sorbitan monolauryl
Acid ester, polyoxyethylene-polyoxypropylene
Examples include block copolymers and the like. Also cationic activity
Examples of agents include alkylpyridium salts and tertiary amines.
etc. Examples of amphoteric activators include dimethylalkyl beta
Examples include ines, alkylglycines, and the like. Also high
Child protective colloids include polyvinyl alcohol and hydroxide.
Examples include roxyethylcellulose. These protections
Colloids may be used alone as emulsifiers or may be used in other
It may be used in combination with other surfactants. These activities
Regarding the types of agents and their effects, please refer to Be1g1sch
e Chemische 1industrie, 28.
16-20 (1963). Lipophilic polymers synthesized by the melt KJL polymerization method etc.
To disperse gelatin in a latex form in an aqueous solution,
After dissolving the lipophilic polymer in an organic solvent,
With the help of a dispersant in an aqueous gelatin solution, ultrasonic waves,
Disperse into latex using a Lloyd mill, etc. lipophilic po
Dispersing the remer in the form of latex in an aqueous gelatin solution
The method is described in U.S. Pat. No. 3,451,820.
has been done. Ester is an organic solvent that dissolves lipophilic polymers.
such as methyl acetate, ethyl acetate, propyl acetate, etc.
Alcohols, ketones, halogenated hydrocarbons, ethers
It is possible to use the following methods. In addition, these organic solvents may be used alone or in combination of two or more.
It can be used in conjunction with In producing the polymer according to the present invention,
The solvent used is one that dissolves the monomer and the resulting polymer well.
It is desirable that the polymer has low reactivity with the polymerization initiator.
. Specifically, water, toluene, alcohol (e.g. meth)
nol, ethanol, 1so-propertool, tert
-butanol, etc.), acetone, methyl ethyl ketone,
Trahydrofuran, dioxane, ethyl acetate, dimethyl
Formamide, dimethyl sulfoxide, acetonitrile
, methylene chloride, etc., and these solvents
They may be used alone or in combination of two or more. The polymerization temperature depends on the type of polymerization initiator, the type of solvent used, etc.
Although it needs to be taken into account, it is usually in the range of 30 to 120℃.
Ru. Used in emulsion polymerization method and solution polymerization method of the polymer of the present invention
Examples of polymerization initiators that can be used include those shown below.
. Examples of water-soluble polymerization initiators include potassium persulfate and persulfate.
Persulfates such as ammonium sulfate and sodium persulfate,
Sodium 4,4'-azobis-4-cyanovalerate, 2
．． 2°-azobis(2-amidinopropane) hydrochloride, etc.
Water-soluble azo compounds and hydrogen peroxide can be used. It is also used as a lipophilic polymerization initiator for solution polymerization.
For example, azobisisobutyronitrile, 2.2°-a
Zobis-(2,4-dimethylvaleronitrile) 2.2°
-Azobis(4-methoxy-2,4-dimethylvaleroni)
trill), 1. l゛-azobis(cyclohexanone-1
-carbonitrile), 2,2'-azobisisocyanobutyric
Acid, 2.2'-dimethyl azobisisobutyrate, 1°1°-
Azobis (cyclohexanone-1-carbonitrile),
Azo compounds such as 4,4°-azobis-4-cyanovaleric acid
, benzoyl peroxide, lauryl peroxide
, chlorobenzyl peroxide, diisobrobyl peroxide
Oxydicarbonate, di-t-butyl peroxide
Peroxides such as Which of these is better?
The preferred ones are benzoyl peroxide and chloroben.
Zil peroxide, lauryl peroxide, etc.
can be done. These polymerization initiators are suitable for emulsion polymerization and solution polymerization.
In the range of 0.01 to 10% by weight based on the total amount of monomers.
preferably in the range of 0.1 to 5%
can be done. - Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization, may also be used.
Methods such as polymerization and bulk polymerization can also be applied. That is,
In the present invention, represented by the general formula (1) of the present invention,
Homopolymers of monomers, combinations of two or more of the monomers
or a copolymer comprising the monomer and at least one other
A copolymerizable comonomer of species is used as a copolymerization component.
It encompasses all of the polymers and through its synthesis process
is not limited. Also, certain types of monomers represented by the above general formula (1)
In the polymerization reaction of monomers, especially monomers having -SH groups,
After protecting the -SH group with an acetyl group etc., the polymerization reaction is carried out.
and then deprotecting the group by hydrolysis.
, the polymer of the invention may be obtained. The polymer according to the present invention is represented by the general formula (1).
m &
Contains 10 to 95% (more preferably 30 to 80%) in t%
ff copolymers are preferred. Next, specific representative examples of the polymer of the present invention are shown in Table-1.
However, it is not limited to gore. , Table 1 (Note) BA: Butyl acrylate E^: Ethyl acrylate
Acrylate St: Styrene vP: Vinylpyrrolidone MMA:
Methyl methacrylate M^: Methyl acrylate A synthesis example of the polymer of the present invention is shown below. Synthesis Example-I Synthesis of P-1 5 g of monomer (m-1) and 5 g of butyl acrylate
to 100 mQ of trimethylformamide (DMF)
Dissolve and heat to 80°C while degassing through nitrogen gas.
Ta. While maintaining this temperature, azobisisobutyronitrile
After adding 250 mg of azole and reacting for 2 hours, azo
Add 250 mg of bisisobutyronitrile and further
The reaction was carried out at 80°C for 2 hours. After cooling this reaction solution, pour it into IQ cold water and precipitate solids.
was filtered out. This solid was dissolved and extracted in ethyl acetate, and sulfuric acid
Dry with magnesium, filter and remove ethyl acetate.
8.3 g of a yellow target product was obtained.
(Molecular weight 4,300) Synthesis example 2P-7 Synthesis exemplified monomer (m-5) 6.5g was added to 10g of acetonitrile.
Dissolved in 0 mQ and added 5 m of pyridine. To this solution
2.4g of acetyl chloride was added dropwise and heated for 2 hours after dropping.
After heating under reflux, concentrate, pour into ice water, and filter out the precipitated solids.
, and dried to obtain an acedelylated monomer. This acetylated monomer 6, Og and butyl acrylic
Dissolve 5.0g of rate in DMF' of 11On+f2,
It was heated to 80° C. while degassing through nitrogen gas. While maintaining this temperature, azobisisobutyronitrile 4
00 mg was added and reacted for 4 hours. After cooling this reaction solution, it was poured into 1 g of cold water, and the precipitated particles were
The body was filtered. This solid was redissolved in DMF' and 10%
Add 20ml of aqueous sodium hydroxide solution and stir for 2 hours.
After stirring, pour it into the water in step 1a again, neutralize it with dilute sulfuric acid, and then
The body was filtered and dried to obtain 7.9 g of the desired product. Other polymers can also be synthesized according to the above synthesis example.
can. The polymers of the present invention may be used alone or in combination of two or more.
May be used together. The amount used is not limited, and the amount used is not limited.
The type of marker, whether it is used alone or in combination of two or more types, or whether the main
The photographic constituent layer of the light-sensitive material of the invention is a single layer or a multilayer of two or more layers.
The amount to be used can be determined depending on the halogen
Preferably from 0.01 to 500 g per mole of
Preferably it is 0.1g to long. Containing the polymer of the present invention in a photographic constituent layer of a heat-developable photosensitive material
Any method can be used, for example, using a low boiling point solvent (methane).
alcohol, ethanol, ethyl acetate, etc.) or high boiling point solvents (
Dibutyl phthalate, dioctyl phthalate, trictyl phthalate
Dissolved in resin (such as resin phosphate) and then dispersed with ultrasonic waves.
or an aqueous alkaline solution (e.g. sodium hydroxide).
10% aqueous solution, etc.), then dissolve it in a mineral acid (e.g., hydrochloric acid).
or nitric acid, etc.), or use an appropriate
Aqueous solutions of polymers (e.g. polyvinyl butyral, polymers)
(such as ribinylpyrrolidone), and other compounds (such as pigments)
(donor substance) in a low-boiling point solvent or a high-boiling point solvent,
May be subjected to ultrasonic dispersion. Next, the photosensitive silver halide used in the present invention will be explained.
Ru. The heat-developable color photosensitive material of the present invention includes the dye of the present invention as described above.
Contains photosensitive silver halide along with a donating polymer. As the photosensitive silver halide used in the present invention, chloride
Silver, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
Single jet method and double jet method in the field of photographic technology
The adjustment can be made by any method such as, but in the present invention,
If so, use the usual preparation method for silver halide gelatin emulsions.
Therefore, the prepared light-sensitive silver halide emulsion has favorable results.
give. The photosensitive silver halide emulsion can be prepared by any person in the field of photographic technology.
It may also be chemically sensitized using a method. Such sensitization methods include
Gold sensitization, sulfur sensitization, gold-sulfur sensitization, reduction sensitization, etc.
Here are some methods. Even if the silver halide in the above photosensitive emulsion is coarse grain,
Fine particles may be used, but the preferred particle size is
The diameter is about 0.001 μm to about 1.5 μm, more preferably
Preferably, it is about 0.01 μm to about 0.5 μm. The photosensitive silver halide emulsion prepared as above was prepared in this invention.
Most preferred for heat-developable photosensitive layers, which are the constituent layers of bright photosensitive materials.
can be applied appropriately. In the present invention, as another method for preparing photosensitive silver halide,
The photosensitive silver salt-forming component is allowed to coexist with the organic silver salt described below.
, forming a photosensitive silver halide in a part of the organic silver salt.
You can also do it. Photosensitive silver salt formation used in this preparation method
As a component, an inorganic halide, for example, expressed as MXn.
halides (where M is an H atom, N H, a group
or represents a metal atom, and X is CQs B r or I
, n is 1 when M is an H atom or an NH4 group, and n is 1 when M is a gold atom.
When it is a genus atom, its valence is indicated. As a metal atom,
thium, sodium, potassium, rubidium, cesium
, steel, gold, beryllium, magnesium, calcium, steel
Trontium, barium, zinc, cadmium, mercury, aluminum
Luminium, indium, lanthanum, ruthenium, tali
aluminum, germanium, tin, lead, antimony, bismuth,
Chromium, molybdenum, tungsten, manganese, zinc
aluminum, iron, cobalt, nickel, rhodium, palladium,
Examples include osmium, iridium, platinum, and cerium.
Ru. ), halogen-containing metal complexes (e.g. K2PtCCs
. tPtBre, HAu C124, (NH4)t
IrCL2e, (NH4), 3 1r Cf2e. (NH,), Ru C128, (NH,)3Ru
CQ8. (Nl!,)3 Rh CQ8゜(NH4)
3 RhBre, etc.), onium halide, (e.g. Te
Tramethylammonium bromide, trimethylphenylene
ammonium bromide, cetylethyldimethylammonium
Monium bromide, 3-methylthiazolium bromide
As trimethylbenzylammonium bromide
Quaternary ammonium halide, tetraethyl phosphor
Quaternary phosphonium halide such as nium bromide
Benzylethylmethylsulfonium bromide!
- Tertiary sulfonyl compounds such as ethylthiazolium bromide
halogenated hydrocarbons (e.g. iodine), halogenated hydrocarbons (e.g. iodine),
doform, bromoform, carbon tetrabromide, 2-bromo-2
-methylpropane, etc.), N-halogen compounds (N-chloro
rosuccinimide, N-bromosuccinimide, N-bromosuccinimide
lomophthalic acid imide, N-bromoacetamide, N-io
Dosuccinimide, N-bromophthalazinone, N-chloride
Lorophthalazinone, N-bromoacetanilide, N,N
-dibromobenzenesulfonamide, N-bromo-N-
Methylbenzenesulfonamide, 1,3-dibromo-4
, 4-dimethylhydantoin, etc.), other halogen-containing
compounds (e.g. triphenylmedyl chloride, triphenyl bromide)
Nylmethyl, 2-bromobutyric acid, 2-bromoethanol, etc.
) etc. can be given. These photosensitive silver halide and photosensitive silver salt forming components are
, can be used in combination in various ways, and the amount used depends on the color
0.002 per mole of monomer unit of element donating substance
It is preferably from mol to 10 mol, more preferably
The amount is 0.2 mol to 2.0 mol. The thermal color photosensitive material of the present invention has the dye-providing property of the present invention.
It is sufficient if it has at least one layer containing a polymer.
However, each layer is sensitive to blue light, green light, and red light,
Namely, heat-developable blue-sensitive layer, heat-developable green-sensitive layer, heat-developable red-sensitivity layer.
The optical layer can also have a multilayer structure. Also same color feeling
Separating the photosensitive layer into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer)
It can also be provided separately. In the above cases, each blue-sensitive silver halide emulsion used
, green-sensitive silver halide emulsion, red-sensitive silver halide emulsion
The agent is prepared by adding various spectral sensitizing dyes to the above-mentioned silver 10-genide emulsion.
It can be obtained by adding Typical spectral sensitizing dyes used in the present invention include, for example:
For example, cyanine, merocyanine, complex (trinuclear or
(4 nuclear) cyanine, holopolar cyanine, styryl
, hemicyanine, oxonol, etc. Siani
Thiazoline, oxazoline, vilor
pyridine, oxazole, thiazole, selenazole
It is more preferable to use a substance with a basic nucleus such as imidazole or imidazole.
Delicious. Such nuclei include alkyl groups, alkylene groups, and hydrogen groups.
Droxyalkyl group, sulfoalkyl group, carboxyl group
alkyl group, aminoalkyl group or fused carbocyclic or
has an enamine group that can form a heterocyclic ring.
You can stay there. It may also be symmetrical or asymmetrical, and
Alkyl group, phenyl group, ena chain in chin chain, polymethine chain
It may have a min group or a heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine pigments include, for example, thiophyl
Dantoin nucleus, rhodanine nucleus, oxazolidine cough, bal
Biruric acid nucleus, thiazolinthion nucleus, malononitrile nucleus
, may have an acidic nucleus such as a pyrazolone nucleus. this
These acidic nuclei further contain alkyl groups, alkylene groups, and phenyl groups.
group, carboxyl alkyl group, sulfoalkyl group, hydro
xyalkyl group, alkoxyalkyl group, alkylami
may be substituted with a ring group or a heterocyclic nucleus. If necessary, these dyes may be used in combination.
. Furthermore, ascorbic acid derivatives, azaindene cadmium
salts, organic sulfonic acids, etc., such as U.S. Pat.
Described in the specifications of No. 390 and No. 2,937,089.
Contains supersensitizing additives that do not absorb visible light, such as
can be used. The amount of these dyes added is silver halide or silver halide.
per mole of forming component I x 10-' mole-1 mole
Ru. More preferably, LX 10-' mol to IX 10
−'Mole. Further, in the present invention, it is preferable to add an organic silver salt.
stomach. In the heat-developable photosensitive material of the present invention, sensitivity may be adjusted as required.
Various organic silver salts are used to increase the
I can be there. As an organic silver salt used with the heat-developable photosensitive material of the present invention,
These are Special Publications No. 43-4921 and No. 44-26582.
, No. 45-18416, No. 45-12700, No. 4
No. 5-22185, JP-A No. 49-52626, No. 52
-31728, 52-137321, 52-1
No. 41222, No. 53-36224 and No. 53-3
No. 7610 and U.S. Patent No. 3,330,6
No. 33, No. 3,794,496, No. 4,105,
No. 451, No. 4,123.274, No. 4,168
．． Fats as described in the specifications of No. 98Q etc.
Silver salts of group carboxylic acids, e.g. silver laurate, myristicin
Silver acid, silver palmitate, silver stearate, arachidonic acid
Silver, silver behenate, α-(1-phenyltetrazolethio)
) Silver aromatic carboxylates such as silver acetate, e.g. silver benzoate
, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 45
-12700, 45-18416, 45-22
No. 185, JP-A-52-31728, JP-A No. 52-137
No. 321, JP-A-58-118638, JP-A No. 58-11
Imino groups as described in various publications such as No. 8639
silver salts, such as silver benzotriazole, 5-acetamide
Dobenzotriazole silver, 5-nitrobenzotriazole
silver, 5-chlorobenzotriazole silver, 5-methoxy
Benzotriazole silver, 4-sulfobenzotriazole
Silver, 4-hydroxybenzotriazole silver, 5-amino
Benzotriazole silver, 5-methylsulfobenzotriazole
Sol silver, 5-carboxybenzotriazole silver, imi
dazole silver, benzimidazole silver, 6-nidropenz
imidazole silver, pyrazole silver, urazole silver, 1.2
．． 4-triazole silver, IH-tetrazole silver, 3-a
Mino-5-benzylthio-1,2,4-triazole silver
, silver saccharin, silver phthalazinone, silver butarimide, etc.
, other 2-mercaptobenzoxazole silver, Merca
silver putoxadiazole, 2-mercaptobenzothiazo
silver, 2-mercaptobenzimidazole silver, 3-mercaptobenzimidazole silver,
Lucapto-4-phenyl-1,2,4-1 lyazole silver
, 4-hydroxy-6-methyl-1,3,3a,7-thi
Trazaindene silver and 5-methyl-7-hydroxy-
1,2,3,4,6-pentazaindene silver, etc.
It will be done. Among the above organic silver salts, imino group silver salts are preferred;
Especially silver salts of benzotriazole derivatives, more preferably
Silver salts of sulfobenzotriazole derivatives are preferred. The organic silver salt used in the present invention may be used alone or in combination of two or more kinds.
It may be used in combination, and the isolated product may be used in an appropriate manner.
It may be used by dispersing it in a binder, or
Prepare the silver salt in a suitable binder and use it directly without isolation.
It may be used for any purpose. The usage of the organic silver salt is 1 mole per unit of dye-providing substance monomer.
The amount is preferably 0.1 to 5 mol per mol, more preferably 0.1 to 5 mol per mol.
Preferably, it is 0.3 to 3 mol. The reducing agent used in the heat-developable photosensitive material of the present invention is
It is possible to use materials commonly used in the field of photosensitive materials.
For example, U.S. Pat. No. 3,531,286;
No. 761,270 and No. 3,764,328
, also 11D No. 12146, same No.
15108, No. 15127, and JP-A No. 15127
p-)Unilene diamine described in Publication No.-27132 etc.
and p-aminophenol-based developing agents,
Roamidophenols and sulfonamidophenols
Examples include hydrazone-based color developing agents and hydrazone-based color developing agents.
Ru. Also, U.S. Patent No. 3,342.599, U.S. Patent No. 3.71
No. 9,492, JP-A-53-135628, JP-A No. 54-
Color developing agent breaker described in No. 79035 etc.
Zers etc. can also be used to advantage. As a particularly preferable y-base agent, JP-A No. 56446133
Represented by the following general formula (20) described in the specification
Examples include reducing agents. General formula (20) %Formula% In the formula, R1 and R2 are hydrogen atoms or substituents *
YT l-7t, , 1: i1. i+ iJf
, Ii:j −7−14+r 1 ~20(
bY 'P 1. 1-11~4) Alki
rtl and R1 are ring-closed to form a heterocycle.
You may. R3, n 4, rt 5 and J: and R6
is a hydrogen atom, a halogen atom, a hydroxy group, an amino group,
Alkoxy group, acylamido group, sulfonamide group,
Carbon which may have a lukyl sulfonamide group or a substituent
an alkyl group having 1 to 30 (preferably 1 to 4) elementary atoms;
and R3 and R1 and R5 and R'' are respectively closed rings.
may be used to form a heterocycle. M is an alkali metal atom,
ammonium group, nitrogen-containing organic base or quaternary nitrogen atom
Represents a compound containing The nitrogen-containing organic base in the above general formula (20) is an inorganic acid.
an organic compound containing a basic nitrogen atom that can form a salt with
Amine compounds are particularly important organic bases.
Can be mentioned. And as a chain amine compound, it is a primary
Amines, secondary amines, tertiary amines, etc. are also cyclic
The amine compound is a typical heterocyclic organic base.
Examples include well-known pyridine, quinoline, piperidine,
Examples include dazole. In addition, hydroxylamine,
Compounds such as hydrazine and amidine can be used as chain amines.
It is useful. In addition, as salts of nitrogen-containing organic bases, the above
Inorganic acid salts of organic bases (e.g. hydrochlorides, sulfates, nitrates)
acid salts, etc.) are preferably used. On the other hand, the bipedal general formula (20) contains quaternary nitrogen.
As a compound, a substituted compound having a tetravalent covalent bond is used.
Examples include salts and hydroxides. Next, the preferable reducing agent represented by the general formula (20) is
A specific example is shown below. (rt-1) (R-2) (n -3) (R-4) Shirko (R-5) (R-6) (R-7) (R-8) (R-9) Shi (R-10) C11゜(R-11) し11゜(r(-12) (R-13) (R-14) NH. (R-15) (R-16) (rt -17) ( R-18) (R-19) (R-20) (R-21) (R-22) C, H. (R-23) The reducing agent represented by the above general formula (20) can be prepared by a known method.
, e.g. TI ouben -W ey I, M
ethoden derOrganischen C
bemie, BandX r/2.645zu03 pages
It can be synthesized according to the method described in . Other reducing agents as described below can also be used.
. For example, phenols (e.g. p-phenylphenol)
, p-methoxyphenol, 2.6-C-Lcrt-B
Chill-p-cresol, N-methyl-p-aminopheno
), sulfonamidophenols [e.g.
benzenesulfonamidophenol, 2benzenesulfone
Amidophenol, 2゜6-dichloro-4-benzene
Sulfonamidophenol, 2,6-dipromo 4-(p
-1-luenesulfonamide) phenol, or
Polyhydroxybenzenes (e.g. hydroquinone, t
ert -butylhydroquinone, 2,6-dimethyl ha
Hydroquinone, Chlorohydroquinone, Carboxyhydroquinone
Droquinone, catechol, 3-carboxycatechol, etc.
), naphthols (e.g. α-naphthol, β-naphthol)
ol, 4-aminonaphthol, 4-methquinonaphthol
etc.), hydroxybinaphthyls and methylene bisnaph
Tolls [e.g. 1. l'-dihydroquine-2,2'-
Binaphthyl, 6,6'-dibromo-2,2'-dihydro
xy-1,1'-hinamethyl, 6,6-sinitro2
, 2'-dihydroquine-1,1'-binaphthyl, 4.4
'-Diftquine-1,I'-dihydroquine-2,2'-
Binaphthyl, bis(2-hydroquine-1-naphthyl)methane
Tan, etc., methylene bisphenols [e.g. 1.1=
Bis(2-hydroxo-3,5-dimethylphenyl)-
3,5,5-trimethylhexane, 1,1-bis(2-
Hydroxy-3-tert-butyl-5-methylphenylene
) Methane, 1. l-bis(2-hydroxy-3,5-
di-tert-butylphenyl)methane, 2,6-methy
Renbis(2-hydroxy-3-tert-butyl-5
-methylphenyl)-4-methylphenol, α-phenylene
Nyl-α,α-bis(2-hydroquine-3,5-di-t
ert-butylphenyl)methane, α-phenyl-α
α-bis(')-? ni-mouth car ゛no q-tert-butyl
-5-methylphenyl)methane,
Droxy-3,5-dimethylphenyl)-2-methylpropylene
Lopan, 1,1,5,5-tetrakis (2-hydroquine)
-3,5-methylphenyl)-2,4-ethylbenc
2,2-his(4-hydroxy-3,5-dimethyl
phenyl)propane, 2,2-bis(4-hydroquine-
3-Methyl-5-tert-butylphenyl)propane
, 2,2-bis(4-hydroxy-3,5-diter)
t-butylphinyl) propane, etc. 1, ascorbic acids
, 3-pyrazolidones, ascorbic acids, 3-pyrazo
Lydones, pyrazolones, hydrazones and paraphrases
Examples include nylene diamines. These reducing agents may be used alone or in combination.
You can also do it. The use of reducing agent m depends on the photosensitive halo used.
Types of silver genide, types of organic acid silver salts, and other additions
Although it depends on the type of agent, it is usually a dye donor monomer.
It is in the range of 0.05 to 10 mol per 1 mol, which is preferable.
Preferably, it is 0.1 to 5 mol. As a binder used in the heat-developable photosensitive material of the present invention
is polyvinyl butyral, polyvinyl acetate, ethylcetate
Lulose, polymethyl methacrylate, cellulose acetate
Tate butyrate, polyvinyl alcohol, polyvinyl
Synthesis of pyrrolidone, gelatin, phthalated gelatin, etc.
Or use one or more natural polymer substances in combination
be able to. In particular, gelatin or its derivatives and polyester
Hydrophilic polymers such as vinyl pyrrolidone and polyvinyl alcohol
It is preferable to use it together with a reamer, more preferably a special
The following binder described in Application No. 58-104249
- is. This binder consists of gelatin and vinylpyrrolidone polymerization.
It includes the body. Vinyl pyrrolidone polymer is vinyl
Polyvinylpyrrolidone, a homopolymer of pyrrolidone.
It may be present, or it may be copolymerized with vinylpyrrolidone.
copolymer with one or more monomers (kraft copolymer)
Including coalescence. ). These polymers
It can be used regardless of the degree of polymerization. polyvinylpylene
Lolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight i, ooo~4
00,000. Copolymerized with vinylpyrrolidone
Other possible monomers include acrylic acid, methacrylic acid
(meth)acrylic acids such as acids and their alkyl esters;
Esters, vinyl alcohols, vinyl imidazoles
, (meth)acrylamides, vinyl carbinols,
Examples include vinyl monomers such as vinyl alkyl ethers.
However, at least 20% (wt%) of the composition ratio
The same) is preferably polyvinylpyrrolidone. A preferred example of such a copolymer has a molecular weight of 5,000.
~400.000. Gelatin can be produced by lime treatment or acid treatment.
Also, ossein gelatin, pickskin gelatin,
Idgelatin or esterification of these, phenylcarba
Moylated modified gelatin may also be used. In the above binder, gelatin is 10 to 90%.
It is preferably 20 to 60%, and more preferably 20 to 60%.
, preferably 5 to 90% of the polymer of the present invention
, more preferably 10 to 80%. The binder may contain other polymeric substances,
Gelatin and molecular weight1. QQ (1-400.0 (IQ)
Polyvinylpyrrolidone and one or more other polymeric substances
mixture with gelatin and molecules f45,000-400
゜000 vinylpyrrolidone copolymer and one or more other
Mixtures with the above polymeric substances are preferred. Other used
Polyvinyl alcohol, polyacrylic
Rylamide, polymethacrylamide, polyvinyl butyra
polyethylene glycol, polyethylene glycol, polyethylene glycol
Proteins such as esters or cellulose derivatives
natural products such as starch, polysaccharides such as gum arabic, etc.
One example is quality. These range from 0 to 85%, preferably from 0 to 85%.
It may be contained in an amount of 70%. Note that the vinylpyrrolidone polymer mentioned above is a crosslinked polymer.
However, in this case, crosslinking is performed after coating on the support.
(including the case where the crosslinking reaction progresses due to natural standing)
) is preferred. The amount of binder used is usually 0.0 per m” of support.
05g to 100g, preferably 001g to 40g
It is. In addition, the binder is a dye-donating substance monomer.
It is preferable to use 0.1g to 10g per 1g unit.
and more preferably 0.25 to 4 g. In the heat-developable photosensitive material of the present invention, a dye-providing substance is added.
It is preferable to add
is a preferred embodiment. The dye-donating substance of the present invention is particularly suitable for forming diffusible dyes.
It is preferable that the Dye donor that can be preferably used in the present invention
Explain quality. Halogens are used as dye-donating substances.
Involved in the reduction reaction of silver oxide and/or q-silver salt, and the reaction
Any material that can form a diffusible pigment as a function of
Depending on the form of the reaction, a negative type that acts on a positive function
dye-donor (i.e. negative-working silver halide)
(forms a negative dye image when
Positive-acting dye-donors (i.e., negative-acting halo)
(forms a Bong dye image when using silver genide)
Can be classified. Negative dye-donor substances include:
are categorized. Each dye-providing substance will be further explained. As the reducing dye releasing compound, for example, general formula (21)
Examples include compounds represented by: General formula (21) % formula % In the formula, Car represents reduction of silver halide and/or organic silver salt.
A reducing substrate (so-called
carrier) and Dye is a diffusible dye residue.
. Specific examples of the above-mentioned reducible dye-releasing compounds include JP-A No. 5
No. 7-179840, No. 58-116537, No. 59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
No. 59-123837, No. 59-165054
, those described in the same specification publication No. 59465055 etc.
Examples include the following compounds. Exemplary dye-donating substances oc,,n,. As another reduced dye releasing compound, for example, general formula (22)
Examples include compounds represented by: ^2 In the formula, A and A are hydrogen atoms and hydroxyl groups, respectively.
or represents an amino group, and Dye is represented by the general formula (21)
It is synonymous with Dye. Compound represented by general formula (22)
A specific example of the product is shown in JP-A-59-124329.
Ru. As a coupled dye-releasing compound, the following general formula (
23) can be mentioned. General formula (23) % formula % In the formula, Cp reacts with the oxidized form of the c base agent to form a diffusible dye.
organic groups that can be released (so-called coupler residues)
, J is a divalent bonding group, and the oxidized form of the reducing agent
The reaction cleaves the bond between Cp+ and J. i is O or
1) ye is defined by general formula (21)
It is synonymous with . Also, apl is a coupled dye-releasing type
Substituted with various ballast groups to make the compound non-diffusible
is preferably used as a ballast group.
Depending on the form of the photosensitive material used, the number of carbon atoms is 8 or more, 1-(like
(preferably 122 or more) organic groups, or sulfo groups,
Hydrophilic groups such as carboxyl groups, or 8 or more (more preferably
(preferably 122 or more) carbon atoms, sulfo groups, carbo
It is a group that also contains a hydrophilic group such as a xyl group. Another particularly preferred ballast] 1 (in which polymer chains are
can be mentioned. ” - as a specific example of the compound represented by the general formula (23)
JP-A-57-186744, JP-A No. 57-1225
No. 96, No. 57-160698, No. 59174834
No. 57224883, No. 59-159159,
It is described in Japanese Patent Application No. 59-104901, and for example,
The following compounds may be mentioned. ,7 ＼Hereafter, the rest below
White Exemplary Dye Donor 0C113 SO. As the coupling dye-forming compound, the following general formula (2
Examples include compounds shown in 4). General formula (24) % formula %:) In the formula, Cpt is the reaction (coupling reaction) with the oxidized form of the reducing agent.
organic groups (response) that can form diffusible dyes (
is a so-called coupler residue), and X represents a divalent bonding group.
and Q represent a ballast group. The color formed as a coupler residue represented by Cpt
The molecular weight is preferably 700 or less for the diffusivity of the element,
More preferably it is 500 or less. In addition, the ballast group of Q is the ballast group defined by general formula (23).
The same ballast group as the last group is preferable, especially 8 or more (
more preferably 12 or more carbon atoms, a sulfo group,
A group having a hydrophilic group such as a ruboxy group is preferable,
Furthermore, polymer chains are more preferred. This polymer chain
Coupling dye-forming compounds having the following general
Repeat derived from the monomer represented by formula (25)
Polymers having units are preferred. General formula (25) % formula % In the formula, Cpt and X are as defined in general formula (24).
are synonymous, and Y is an alkylene group, an arylene group, or an arylene group.
represents a lekylene group, Z represents a divalent organic group, and
Ethylenically unsaturated group or group having an ethylenically unsaturated group
represents. Coupling colors represented by general formulas (24) and (25)
Specific examples of elementary-forming compounds include JP-A-59-1243
No. 39, No. 59-181345, patent application No. 58-109
No. 293, No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
It is described in each specification etc. of No. 7, for example, the following compounds
Things can be mentioned. Exemplary dye-donor substances ■ C,611s+ ■ 0H CHI 1 0CIIC141b* 0OH C-self-Hco5 Valve 1 Volima, - ■ C1l. CIl, C00N l @ CM. In the above general formulas (23), '(24) and (25),
For coupler residues defined as cpl or Cp,
To explain in more detail, a group represented by the following general formula is preferable.
stomach. In the formula, R11R1, R3 and R4 are each a hydrogen atom,
Halogen atom, alkyl group, cycloalkyl group, aryl
group, acyl group, alkyloxycarbonyl group, aryl group, acyl group, alkyloxycarbonyl group,
oxycarbonyl group, alkylsulfonyl group, aryl
sulfonyl group, carbamoyl group, sulfamoyl group,
Acyloxy group, amino group, alkoxy group, aryloxy group
xy group, cyano group, ureido group, alkylthio group, ali
ruthio group, carboxyl group, sulfo group or heterocyclic residue
and these further include hydroxyl, carboxyl, and carbonyl groups.
Rupho group, alkokene group, cyano group, nitro group, alkyl
group, aryl group, aryloxy group, acyloxy group,
Acyl group, sulfamoyl group, carbamoyl group, imide
It may be substituted with a group, a halogen atom, etc. these
The substituents are selected depending on the purpose of CpI and Cps,
As mentioned above, in <CpI, one of the substituents is a ballast group.
It is preferable that the color formed in Cpt is
In order to improve the diffusivity of the element, the molecular weight is preferably 700 or less.
It is preferable that the substituents are selected such that the number of substituents is less than or equal to 500.
Delicious. For example, as a dye-donating substance for the bottom type, the general formula (
There is an oxidizable dye-releasing compound represented by 26). General formula (26) In the formula, w+ is a quinone ring (with no substituents on this ring).
represents the atomic group necessary to form R
5 represents an alkyl group or a hydrogen atom, B is -N-C R7 square (in the formula, Re represents an alkyl group or a hydrogen atom, and R?
Represents an oxygen atom or -N-. ) or -SO, -
, r represents O or l, and Dye is the general formula (21).
Synonymous with defined. Specific examples of this compound are
Kaisho No. 59-166954, Kaisho No. 59-154445, etc.
For example, the following compounds are listed in the specifications of
. Exemplary dye-donor substance CR3 Another positive dye-donor substance is represented by the following general formula (27)
When oxidized, the pigment is released as represented by the compound represented by
There are compounds that cause you to lose your abilities. General formula (27) In the formula, W2 is a benzene ring (which may have a substituent on the ring).
represents the atomic group necessary to form R5, B,
r and Dye are the same as defined in general formula (26).
It is righteousness. A specific example of this compound is JP-A-59-1243.
No. 29, No. 59-154445, etc.,
For example, there are the following compounds. Exemplary dye-donor substance OCR
Examples include compounds represented by 28). In the above formula, W! , R6 and Dye are represented by the general formula (27
) has the same meaning as defined in ). of this compound
Specific examples are described in JP-A-59-154445, etc.
For example, there are the following compounds. Exemplary dye-providing substance [phase] General formula (21), (22), (26), (27) above
and a diffusible dye represented by Dye in (28)
The residues will be described in further detail. As a residue of diffusible dye
The molecular weight is preferably 800 or less due to the diffusivity of the dye.
It is preferably 600 or less, and an azo dye,
Azomethine dye, anthraquinone dye, naphthoquinone color
element, styryl dye, nitro dye, quinoline dye, carbo
Examples include residues such as nyl dyes and phthalocyanine dyes. These dye residues can create multiple colors during thermal development or transfer.
It may also be in a temporary shortwave form. In addition, these pigment residues
For the purpose of increasing the light resistance of images, for example,
-4111765, described in 5G-12433'7
A preferred form of chelatable dye residues is
be. These dye-providing substances may be used alone or in combination of two or more.
The above may also be used together. The amount used is not limited, and the amount used is not limited.
The type of substance used, whether it is used alone or in combination of two or more, or
The photographic constituent layer of the light-sensitive material of the present invention may be a single layer or two or more layers.
The decision can be made depending on whether there are multiple layers, etc., but for example, the amount used
is 0.005g to 50g per 1m', preferably 0.
1g to 10g can be used. The above dye-providing compound is added to the photographic constituent layer of a heat-developable photosensitive material.
The method of inclusion is arbitrary, for example, using a low boiling point solvent (medium).
(tanol, ethanol, ethyl acetate, etc.) or high boiling point solutions
media (dibutyl phthalate, dioctyl phthalate, tri-
Ultrasonic dispersion after dissolving in cleansyl phosphate, etc.)
or alkaline aqueous solution (e.g. sodium hydroxide).
After dissolving in a mineral acid (e.g. 10% aqueous solution of
Neutralize with hydrochloric acid or nitric acid, or use an appropriate
Aqueous solutions of suitable polymers (e.g. gelatin, polyvinyl
butilade, polyvinylpyrrolidone, etc.)
It can be used after being dispersed using a vacuum cleaner. As a binder used in the heat-developable photosensitive material of the present invention
is polyvinyl butyral, polyvinyl acetate, ethylcetate
Lulose, polymethyl methacrylate, cellulose acetate
Tate butyrate, polyvinyl alcohol, polyvinyl
Synthesis of pyrrolidone, gelatin, phthalated gelatin, etc.
Or use one or more natural polymer substances in combination
be able to. In particular, gelatin or its derivatives and polyester
Hydrophilic polymers such as vinyl pyrrolidone and polyvinyl alcohol
It is preferable to use it together with a reamer, more preferably a special
The following binder described in Application No. 58-104249
- is. This binder consists of gelatin and vinylpyrrolidone polymerization.
It includes the body. Vinyl pyrrolidone polymer is vinyl
Polyvinylpyrrolidone, a homopolymer of pyrrolidone.
It may be present, or it may be copolymerized with vinylpyrrolidone.
copolymer with one or more monomers (kraft copolymer)
Including coalescence. ). These polymers
It can be used regardless of the degree of polymerization. polyvinylpylene
Lolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 4.
00,000. Copolymerized with vinylpyrrolidone
Other possible monomers include acrylic acid, methacrylic acid
Acrylic acid and its alkyl ester (meth)acrylic acid
Esters, vinyl alcohols, vinyl imidazoles
, (meth)acrylamides, vinyl carbinols,
Examples include vinyl monomers such as vinyl alkyl ethers.
However, at least 20% (wt%) of the composition ratio
The same) is preferably polyvinylpyrrolidone. A preferred example of such a copolymer has a molecular weight of 5,000.
~400.000. Gelatin can be produced by lime treatment or acid treatment.
Also, ossein gelatin, pickskin gelatin,
Idgelatin or esterification of these, phenylcarba
Moylated modified gelatin may also be used. In the above binder, gelatin is 10 to 90%.
It is preferably 20 to 60%, and more preferably 20 to 60%.
, preferably 5 to 90% of the polymer of the present invention
, more preferably 10 to 80%. The binder may contain other polymeric substances,
Gelatin and polyester with a molecular weight of 1,000 to 400,000
combination of vinylpyrrolidone and one or more other polymeric substances
Mixture, gelatin and molecular weight 5,000-400,00
0 vinylpyrrolidone copolymer and one or more other high
Mixtures with molecular substances are preferred. Other polymeric materials used include polyvinyl alcohol.
polyacrylamide, polymethacrylamide, polyester
Rivinyl butyral, polyethylene glycol, polyester
Tylene glycol ester or cellulose derivative
proteins such as, and polysaccharides such as starch and gum arabic.
Natural substances such as These are 0-85%,
Preferably, it may be contained in an amount of 0 to 70%. The vinyl pyrrolidone polymer mentioned above is a crosslinked polymer.
However, in this case, crosslinking is performed after coating on the support.
(including the case where the crosslinking reaction progresses due to natural standing)
) is preferred. The amount of binder used is usually 0.0 per 1 m of support.
05g to 100g, preferably 0.01g to 40g
It is g. In addition, the binder is a dye-donating substance monomer.
It is preferable to use 0.1g to 10g per 1g of unit.
and more preferably 0.25 to 4 g. The support used in the heat-developable photosensitive material of the present invention includes:
For example, polyethylene film, cellulose acetate film
film and polyethylene terephthalate film,
Synthetic plastic films such as polyvinyl chloride, and
True base paper, printing paper, baryta paper and resin coated paper
Examples include paper supports such as . In particular, various heat solvents are added to the heat-developable photosensitive material of the present invention.
It is preferable that The thermal solvent of the present invention refers to thermal development and
/ or any substance that promotes thermal transfer, preferably
is solid, semi-solid, or liquid at room temperature and cannot be heated.
A substance that is dissolved or solvated in the binder by
and preferably urea derivatives (e.g. dimethylurea,
diethylurea, phenylurea, etc.), amide derivatives,
(e.g. acetamide, benzamide, etc.), polyhydric alkaline
Coles (e.g. 1,5-bentanediol, 1.6
-bentanediol, 1,2-cyclohexanediol
, pentaerythritol, trimethylrolethane, etc.)
, or polyethylene glycols. be familiar with
As a specific example, it is described in Japanese Patent Application No. 511-104249.
It is. These thermal solvents can be used alone or in combination of two or more.
May be used. In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention also includes
Various additives can be added as required. For example, as a development accelerator, U.S. Patent No. 3,220,8
No. 40, No. 3.521.285, No. 4,012,
No. 260, No. 4.060, 420, No. 4.088
, No. 496, No. 4,207,392 Specifications, n D
No. 15733, No. 15734, No.
o, 15776, JP-A-56-130745, JP-A No. 56
- Urea and guaninoumt described in No. 132332 etc.
Alkali release agents such as rechloroacetate, Special Publication 1972-
Organic acids described in US Pat. No. 12,700, US Pat. No. 3,667.9
-Co-, -8Offi-, -8o- groups described in No. 59
a non-aqueous polar solvent compound having U.S. Pat. No. 3,438,
No. 776: fii! Melt Former-1 U.S. Patent No.
No. 3,666.477, described in JP-A-51-19525.
There are polyalkylene glycols listed above. Also color toning agent
For example, JP-A-46-4928, JP-A-46-6
No. 077, No. 49-5019, No. 49-5020,
No. 49-91215, No. 49-107727, No. 5
No. 0-2524, No. 50-67132, No. 50-67
No. 641, No. 50-114217, No. 52-3372
No. 2, No. 52-99813, No. 53-1020, No. 53-1020, No. 52-99813, No. 53-1020, No.
No. 53-55115, No. 53-76020, No. 53-
No. 125014, No. 54-156523, No. 54-1
No. 56524, No. 54-156525, No. 54-15
No. 6526, No. 55-4060, No. 55-4061
, Publications such as No. 55-32015 and West German Patent No. 2
, No. 140,406, No. 2,147,063, No. 2
, 220,618, U.S. Pat. No. 3,080,254
, No. 3,847,612, No. 3,782,941
No. 3.994,732, No. 4,123,28
2, No. 4.201,582, etc.
The compounds phthalazinone, phthalimide, and
Lazolone, quinazolinone, N-hydroxynaphthalimide
Benzoxazine, Naphthoxazinedione, 2.
3-1hydro-phthalazinedione, 2,3-dihydro-
1,3-oxazine-2,4-dione, oxypyridine
, aminopyridine, hydroxyquinoline, aminoquinoli
ion, isocarbostyryl, sulfonamide, 2H-1,
3-Benzothiazine-2,4-(3H)dione, benzo
triazine, mercaptotriazole, dimercaptote
Trazapentalene, phthalic acid, naphthalic acid, phthalamide
and imidazole, and one or more of these and imida
Mixtures with sol compounds, as well as phthalic acid, naphthalic acid, etc.
at least one acid or acid anhydride and phthalazine
A mixture of compounds, including phthalazine and maleic acid
, combinations of itaconic acid, quinolinic acid, gentisic acid, etc.
can be mentioned. Also, JP-A-58-189628, JP-A-58-1934
3-amino-5-mercapto described in Publication No. 60
-1゜2.4-triazoles, 3-acylamino-5
-Mercapto-1,2,4-triazoles are also effective°
It is. Also, as a stabilizer, especially a printout prevention agent after processing.
They may be used simultaneously, for example, JP-A No. 48-45228.
, No. 50-119624, No. 50-120328,
Halogenated hydrocarbon water described in Publication No. 53-46020 etc.
elements, specifically tetrabromobutane, tribromoeta
nor, 2-bromo-2-tolylacetamide, 2-butyl
lomo-2-tolylsulfonylacetamide, 2-trib
lomomethylsulfonylbenzothiazole, 2,4-bis
(tribromomethyl)-6-methyltriazine, etc.
can be lost. Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
No. 50-77034, sulfur-containing
A post-treatment may be carried out using the compound. Furthermore, U.S. Patent No. 3,301,678;
506゜444, same No. 3.824.103, same No. 3
, 844.7 layer number isothiuronium series described in each specification
Stabilizer Precursor, also U.S. Patent No. 3,66
No. 9,670, No. 4,012,260, No. 4.0
Activators described in Specification No. 60,420, etc.
It may also contain a stabilizer precursor and the like. Also, sucrose, NH4Fe(SO1)t' 12Ht
A water release agent such as O may be used.
Supply water and perform heat development as in No. 6-132332.
Good too. In addition to the above ingredients, the photosensitive material of the present invention further includes ingredients as necessary.
spectral brightening dyes, antihalation dyes, fluorescent whitening dyes,
Additives, hardeners, antistatic agents, plasticizers, spreading agents, etc.
agents, coating aids, etc. are added. The heat-developable photosensitive material of the present invention basically has (1
) photosensitive silver halide, (2) reducing agent, (3) the present invention.
containing a polymer, (4) an organic silver salt, and (5) a binder.
It is preferable to have. (6) Pigment as needed
Preferably, it contains a donor substance. However, these are not necessarily contained in a single photographic constituent layer.
(+), (2), (3), (4)
and (5) in one photosensitive layer.
Contain (6) and (5) in other layers adjacent to the photosensitive layer.
+f 2 or more even if they are in a state where they can react with each other, such as tightening
It may be contained separately in the photographic constituent layers. Furthermore, the inhibitor of the present invention can be used for thermal development that forms images only with silver.
Of course, it is also effective for image-sensitive materials (dry silver).
Ru. In addition, the photosensitive layer may be two layers, such as a high-sensitivity layer and a low-sensitivity layer.
It may be divided into more parts, and furthermore, the color sensitivity can be set differently.
It may have one or more photosensitive layers, or an overcoat.
layer, subbing layer, backing layer, interlayer, or filter layer.
It may have various photographic constituent layers such as layers. The heat-developable photosensitive layer of the photosensitive material of the present invention and, if necessary,
Protective layer, intermediate layer, undercoat layer, back layer,
For other photographic constituent layers, prepare respective coating solutions and immerse
method, air knife method, curtain coating method or U.S. patent no.
Various hopper coating methods described in No. 3,681,294, etc.
Photosensitive materials can be created by coating using the coating method of
Ru. Further, if necessary, U.S. Pat. No. 2,761,791 and
and the method described in British Patent No. 837,095.
Therefore, two or more layers can be applied simultaneously.
Ru. The above-mentioned material used in the photographic constituent layer of the heat-developable photosensitive material of the present invention
The components are coated onto the support and the thickness of the coating is l after drying.
~1. , 000 μm is preferable, more preferably 3 to 000 μm.
It is 20 μm. After the heat-developable photosensitive material of the present invention is imagewise exposed as it is,
Usually 80°C to 200°C, preferably 120°C to 17
at a temperature range of 0°C for 1 second to 180 seconds, preferably
Color development is achieved simply by heating for 1.5 seconds to 120 seconds.
Ru. Also, if necessary, attach water-impermeable material to the
It may be developed or heated at a temperature of 706C to 180C before exposure.
Preheating may be carried out in the range of Various exposure means can be used for the heat-developable photosensitive material according to the present invention.
I can be there. A latent image is an image of radiation including visible light.
Obtained by exposure to light. Generally normal color print
light sources used for, e.g. tungsten lamps, mercury lamps
, xenon lamp, laser beam, CRT beam, etc. as a light source
It can be used as The heating means is a method that can be applied to ordinary heat-developable photosensitive materials.
All available, e.g. heated block or pre
contact with a heated roller or drum.
or pass through a high temperature atmosphere, or
By using heating or furthermore, in the photosensitive material of the present invention,
has a conductive layer in the image-receiving layer (element) for thermal transfer, and
Joule heat generated by a strong magnetic field can also be used.
Ru. There are no particular restrictions on the heating pattern;
How to reheat after preheating
continuously at high temperatures for short periods of time or at low temperatures for long periods of time.
Rise, fall, repeat, and even discontinuous heating possible
However, a simple pattern is preferable. Also, exposure and
A method in which heat proceeds simultaneously may also be used. The heat-developable photosensitive material of the present invention releases or forms a diffusible dye.
When containing a dye-providing substance, an image-receiving layer is used.
There is a need. In the present invention, the photographic constituent layers are imagewise exposed and thermally developed.
an image-receiving layer that receives the diffusible dye that is generated in an image-wise manner by
If so, use what is commonly used in this field.
For example, paper, cloth, plastic, etc. can be used.
Preferably, a mordant or dye-receiving agent is added to the support.
An image-receiving layer containing a compound with this ability is used.
It will be done. As a particularly preferable image receiving layer, Japanese Patent Application No. 58-97907
Layer made of polyvinyl chloride and patent application No. 1983-
From polycarbonate and plasticizer described in No. 128600
There are several layers. The image-receiving layer may be provided on the same support as the above-mentioned photographic constituent layers.
In this case, after the dye is transferred, it is removed from the photographic constituent layers.
It may have a structure that allows it to be removed, or it may be provided on separate supports.
There are no particular restrictions on its formation (using Moi's technology).
I can do many things. [Example] Examples of the present invention are shown below.
It is not limited to these. Example-1 [Preparation of 5-methylbenzotriazole silver] 5-methyl
Benzotriazole and silver nitrate in water/ethanol mixed solvent
5-methylbenzotriazole obtained by reacting in
28.8 g of silver and poly-N-vinylpyrrolidone (molecule ff
l 30. QOO) 150mQ of water containing 16g of aluminum
Disperse with a Nabor mill, and set this dispersion to pl (5,5).
[Dye-providing substance dispersion] 35.5 g of the following dye-providing substance (cpm -1),
5.0 g of hydroquinone compound and the polymer of the present invention (P
-1) Dissolve 3.0g in 200ml of ethyl acetate,
Alkanol XC (manufactured by DuPont) 5% by weight aqueous solution 12
4mQ1 phenylcarbamoylated gelatin (Haslow Co., Ltd.)
. Type 1.7819P C) Gelatin containing 30.5g
Mix with 720ml of aqueous solution and use an ultrasonic homogenizer.
After dispersing and distilling off ethyl acetate, 1) H5,5
I completed it to 800mf2. Dye-donating polymer (cpm-1) Hydroquinone compound 1'l11 [Developer solution] 23.3 g of developer (R-11), the following development accelerator 1. l
og. Poly(N-vinylpyrrolidone) (molecular m 30,000
) and 0.5 g of the following fluorosurfactant dissolved in water,
250mf at pH 5.5! Finished. Development accelerator surfactant (m, n = 2 or 3) <Preparation of heat-developable photosensitive material> 12.5 ml of the above-mentioned silver salt dispersion, the above-mentioned dye-providing substance
Dispersion liquid 40. On+17. 12.5 mQ of the developer,
Liethylene glycol 2. Og, 3-methylpentane
-1,3,5-triol2. Og and average particle size 0.1
6mQ of 3μm silver halide emulsion (silver halide
(containing 7.5 x 1O-3 mol) and further
Hardener liquid [tetra(vinylsulfonylmethyl)methane]
and taurine at a ratio of 1:l (weight ratio) to form phenylcarbonate.
Rubamoylated gelatin was dissolved in a 1% aqueous solution and tetra
vinylsulfonylmethyl)methane to 3% by weight.
2.5m (after adding
Photographic polyethylene terephthalate with a thickness of 180 μm
Coating on the film to give silver 1!2.648/m”
and further the phenylcarbamoylated gelatin is added thereon.
and poly(N-vinylpyrrolidone) (molecular weight 30.00
A protective layer consisting of a mixture of photosensitive materials No. 0) and I
was created. After drying the obtained photosensitive material, white exposure of 80QQCMS was performed.
Light was given through the step ueno. Then, separately polysalt as image receiving layer material on baryta paper
Image receiving sheet coated with vinyl chloride (1.2g/a+”)
The image-receiving layer surface and the coated surface of the exposed photosensitive material are overlapped.
Then, perform heat development at 150°C for 1 minute to remove the image-receiving sort.
A magenta transferred image was obtained on the image receiving sheet. Obtained
Maximum reflection density (D max) of the transferred image
Table 2 shows the li (D m1n). Example-2 Types and addition of the polymer of the present invention and comparative inhibitor
Same as Example 1 except that the amount was changed as shown in Table 2.
Photosensitive materials No. 2 to No. 28 were prepared and carried out.
The same exposure and heat development as in Example-1 were carried out, and the results shown in Table-2 were obtained.
Ta. Comparative Example-1 The following comparative inhibitor was used instead of the polymer of the present invention in Example-1.
Example except that agents (A, B, C, D') were added.
The same photosensitive material as in -1 was prepared, and the same exposure as in Example -[ was carried out.
Heat development was performed and the results shown in Table 2 were obtained. Comparative inhibitors (C) (D) Table 2 From the above examples and comparative examples, inhibitors containing the polymer of the present invention
The heat-developable photosensitive materials that contain
D1ro was significantly improved compared to those using known inhibitors.
I know it will be good. Example-3 The dye-providing substance of Example-1 was mixed with the following compounds (cpm-■ and
The procedure was the same as in Example-1 except that the
A photosensitive material was prepared and subjected to the same exposure and thermal development as in Example-1.
The results shown in Table 3 were obtained. cpm-U Ha (weight ratio) cpm-[ From Table 3, the present invention is effective for various dye-providing substances.
It can be seen that it is. Example-4 Undercoated photographic polyethylene with a thickness of 180 μm
The following composition is exposed from the bottom layer on the terephthalate film.
The material was prepared. ■ First photosensitive layer: Example-1) 10 Silver Genide with green color
A photosensitive layer having the same composition as in Example 1 except that silver halide having an average grain size of 0.13 μm was used (however, the amount applied was 215 as in Example 1). ■ Intermediate layer ■, per support tm'', gelatin 0, 8
g, 0.8 g of polyvinylpyrrolidone, 0.4 g of polyethylene glycol, 0.4 g of 3-methylpentane-1,3,5-triol and 0.4 g of the following compound (CD'scahenger). ■ Second photosensitive layer: Silver halide is used as a halo with red sensitivity.
A photosensitive layer having the same composition as the first photosensitive layer except that the dye-providing substance was changed to CPM-II (however, the amount applied was 1/3 of Example-I). ■ Intermediate layer■ ; The following yellow fill is added to the intermediate layer■
Intermediate layer 8 containing a tar dye (0.4g) ■ Third photosensitive layer: silver halide with blue sensitivity
The second photosensitive layer had the same composition except that the dye-providing substance was changed to cpm -[[ in addition to silver generide. ■ Protective layer; same protection as the protective layer described in Example-1
layer. CD'Scavennoya-rII3 Y-filter dye CT11゜This light-sensitive material was treated with 8000CMS of red light and green light, respectively.
Exposure to colored light and blue light caused the same thermal phenomenon as in Example-1.
and transfer of cyan, magenta and yellow dyes respectively.
Photographicity (Dmax and fog) was measured. Display the results -
4. Comparative Example-3 Photosensitive layer of each photosensitive layer of Example-4 excluding the polymer of the present invention
The materials and polymers of the present invention were combined with the comparative inhibitor (A) described above.
A photosensitive material was prepared with a different value, and the same exposure and
Heat development was performed. The results are shown in Table 4. Table 4 From Example 4 and Comparative Example 3, the present invention can produce color images.
When applied to a multilayer photothermographic material that gives D m
It can be seen that in is significantly improved. Example-5 Photosensitive materials of Examples-1, -2 and Comparative Example-1 1°2.3
, 4.17. and 26 under high temperature (50℃) and high humidity.
(relative temperature 80%) for 24 hours, Example-
Perform the same heat development as in step 1, and set D max D min and
Desensitization rate due to exposure [(1-sensitivity after exposure/sensitivity before exposure)
×100%] was calculated. The results are shown in Table-5. From these results, it can be seen that the heat-developable photosensitive material of the present invention
Contains no remer or contains comparative inhibitor.
When stored under high temperature and high humidity, compared to heat-developable photosensitive materials,
The sensitivity D, max and Dmin change little, and the
It can be seen that the storage stability has been improved. Example 6 A photosensitive material and an image receiving material having the following configurations were prepared, and the photosensitive material
8oo from the support side as in Example-4. CMS'7: exposed to light and in close contact with the image receiving material at 150°CI
Thermal development was performed for a minute, and the results shown in Table 6 were obtained. Photosensitivity + 4 ingredients (Written in order from top layer to bottom layer.Amount of each component
indicates the amount per Im2. ) Protective layer Gelatin 0.42g%5ift Q, 36g,
Saffron 10g0 Red sensitive layer; Methylbenzotriazole silver 1.6g. Reducing agent (R-+1) 0.57g, Cpm-rl 0.
8g. 0.58 g of red-sensitive silver halide (see property 1 below) in terms of silver, hydroquinone compound of Example-1
60 mg, gelatin 0.75 g, phthalated gelatin 0.75 g, polyvinyl
Pyrrolidone 0.5g, 3-methy 0.38g, polyethylene
nglycol 1.1g. A I K-X C, C (see Note 3) 80+ng, present invention
Polymer (P-1) 0.52 g, hardener 60 mL Intermediate layer: gelatin 0.5 g, CD' scarf of Example-4
Bennya-04g1 Methylbenzotriazole silver 1.2g, rt! Film agent 20mg0 green feeling
Layer: Cpm -12.3g, green sensitive silver halide (note
2) as silver equivalent: 0.76g meddimethylbenzotriazo
2 g of silver, 0.76 g of reducing agent (R-11),
90 mg of droquinone compound, 1 g of gelatin, 1 phthalate
Latinin 1g 1 Polyvinylpyrrolidone 0.66g, 3
-Methylpentane-1,3,5-triol 0.5g1
Polyethylene glycol 1. J, AIK-X
CO, l1g, polymer of the present invention (P-1) 0.688
% Hardener 80mg0 Intermediate layer: Y-filter dye of Example-4 0.4g, front
CD' scavenger 0.4g, methylbenzotriazole chain 1.2g, Zera
Chin 0.5g, hardener 20mg. Blue-sensitive layer: Cpm-I [11.4g, blue-sensitive halogen
Silver oxide (silver equivalent: 0.97 g, methylbenzotriazole 2
．． 7g, reducing agent 0.97g, the above hydroquinone compound
90 mg 5 gelatin 1.26 g, phthalated gelatin 1.
28g, polyvinylpyrrolidone 0.84g, 3-methy
Lupentane-1,3,5-triol 0.63 g, polyethylene glycol 1.9 g, A I K -X CO, 14 g, present invention
Polymer (P-1) 0.87 g, hardener 0.1 g Gelatin layer: 2.5 g gelatin Support, 180 μm thick polyester with latex subbing
Ethylene phthalate film. Image-receiving material Image-receiving layer: 10 g of polycarbonate 1 0 of the following compound (1)
．． 5g, the following compound (2) 0.5g0 Support: baryta
Paper compound (1) Compound (2)
Note 1 Sensitizing dye Note 2 Sensitizing dye Note 3 AIK-XC Table 6 [Effects of the invention] The thermal phenomenon photosensitive material according to the present invention has high density and improved fogging.
It provides an improved image and also has an improved life support column (sensitivity D).
max and D min). Applicant Konishiroku Photo Industry Co., Ltd. Procedural Amendment December 1, 1986!

Claims (1)

[Scope of Claims] A heat-developable photosensitive material having a layer containing photosensitive silver halide on a support, which contains a polymer having a repeating unit derived from a monomer represented by the following general formula (1). A heat-developable photosensitive material characterized by: General formula (1) QX [wherein Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X represents a residue of a photographic inhibitor. ]