JPS62136644A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat developable photosensitive material which has a high max. density and fogs less by using a polymer having the repeating unit derived from the monomer expressed by specified formula for a dye donative material and incorporating silver iodide at a specific rate into photosensitive silver halide. CONSTITUTION:The dye donative material of the heat developable photosensitive having at least the photosensitive silver halide, dye donative material, reducing agent, and binder on a base is the polymer having the repeating unit derived from the monomer expressed by formula I or formula II and having >=30,000 weight average mol. wt. and the photosensitive silver halide is incorporated therein so as to be incorporated at 4-40mol% content of silver iodide. The weight average mol. wt. of the dye donative material polymer is preferably 30,000-5,000,000, more preferably 100,000-2,000,000. The effect of improving the thermal fogging is low if the content of the silver iodide is less than <=4mol% and the photosensitive function is low when the content exceeds 40mol%. The heat developable photosensitive having the small thermal fogging is thus obtd.

Description

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

The present invention relates to a heat-developable photosensitive material, and more particularly, to a heat-developable photosensitive material with high maximum density and low fog.

[Prior art 1] Compared with the conventional wet method, a method in which the developing process for obtaining a color image is performed by dry heat treatment has advantages in terms of processing time, durability, and pollution concerns.
It has many shaku. Therefore, many proposals regarding such heat-developable color photosensitive materials have been made in recent years;
No. 57-198458, No. 57-207250, No. 58-40551, No. 58-58543, No. 5
No. 8'-79247, Japanese Patent Application No. 122590-1980,
No. 57-132884, No. 57-17923 (No. 3,
No. 57-229G71, No. 57-229G74, No. 57-229675, No. 58-3: [No. 63, No. 58
-33364, 58-34083, JP-A-58-
No. n0537, No. 58-12 (No. 533, No. 58-1)
There are No. 49046 and No. 58-14947. The basic composition of the heat-developable color photosensitive materials according to these proposals consists of a photosensitive element and an image receiving element, and the photosensitive element basically contains an organic silver salt, a photosensitive silver halide, a developer (reducing agent),
It consists of a dye-providing compound and a binder. That is, optical information is given to the photosensitive silver halide by image exposure, and during thermal development, dissolution physical development according to the optical information occurs between the organic silver salt and the photosensitive silver halide under the action of a developer. An image-forming dye is released or formed by reacting the developer, which may or may not have acted, with the dye-providing compound. The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image. Since heat-developable photosensitive materials are developed using heat, there is a possibility that thermal fogging may occur in all reaction processes, and this is one of the problems that must be solved in the design of photothermographic materials. In response, many thermal fog inhibitors have been proposed to reduce thermal fog. For example, U.S. Patent No. 3.589,
Mercury compound No. 903, West German Patent No. 2,402,161
N-halogen compound of No. ff1Z, 500. ,50
peroxide of No. 8, ionic compounds of No. 12,017,907, baladium compounds of U.S. Patent No. 4,102,312, sulfinic acids of Japanese Patent Publication No. 53-28417,
Research Dischrono+ -No. 1 (i9077
, flucaptotriazole of IG9079, 1.2.4-) riazole of U.S. Pat. No. 4,137,079, and the like. However, these thermal antifoggants are harmful to the human body or have a small antifoggant effect, and so far no effective antifoggant has been found. The present inventors have proposed that a photothermographic material with low fog can be obtained when the weight average molecular weight of the polymeric dye-providing substance is within a specific range. (The name of the invention filed on August 19, 1985 is "thermally developable photosensitive material.") Although its fog reduction effect is significant, it has not yet reached the goal of a heat developable photosensitive material. OBJECTS OF THE INVENTION Therefore, an object of the present invention is to provide a heat-developable photosensitive material with low thermal fog.

[Structure of the invention]

The above objects of the invention are achieved by the following. That is, the heat-developable photosensitive material of the present invention has a small amount of
Photosensitive silver halide, dye donor, reducing agent and
In the heat-developable photosensitive material having a binder and a binder, the color
The element donor substance is represented by the following general formula [1] or [2]
Weight average fraction with repeating units derived from monomers
A polymer having a molecular weight of 30,000 or more, and having the above-mentioned
The photosensitive silver halide has a silver iodide content of 4 mol% to 40 mol
%. General formula (1) (]Q?-fXI-cp General formula (2) (QhCp2-1X)rrDy
e In the formula, Q is an ethylenically unsaturated group or an ethylenically unsaturated group.
represents a group having a Japanese group, and CI' + and l/Cp2 are each
Reacts with the oxidized form of the reducing agent to form a diffusible dye or
is a right-handed group that releases, X represents a divalent bonding group, and the X
is bound to the active site of CI+1 and auto)2, and II
represents O or 1, Dye represents a diffusible dye residue
. The present invention will be explained in detail below. Said dye 0 used in the present invention (weight average of donor material polymer)
The molecular weight is preferably aooooo to 5,000,000.
, more preferably 100,000 to 2,000,000.
Ru. In the present invention, the weight average molecular weight is determined by the GPC method (Delpa
-measuring by chromatography method)
The following six measurement methods are shown below. GPC: IILc-802^ (manufactured by Toyo Soda) Color
Mu: 1"SK gel (manufactured by Toyo Shindatsu) CMI
I (exclusion limit molecule ff14X10', column dimension 7
．． 51X 60 (hm) 1 bottle Solvent: TIIF flow, jl: 1+nQ/rain Power ram temperature: 38℃ Detector: UV-8+nodel [[(Toyo
Detection wavelength 254 old
Create a line. In the present invention, represented by general formula [1] or [2]
If the monomer remains unreacted in the polymer of the present invention,
This residual amount is less than 5ffl% of the polymer.
It is preferable that the amount of
be. The remaining amount of such monomers can also be measured by the above GPC method.
Can be determined. In the above general formulas [1] and [2], represented by q
ethylenically unsaturated group I;
The group is preferably a group represented by the following general formula [3].
Ru. [3] In the formula, R is a hydrogen atom, a carboxyl group, or an alkyl group.
Represents a kill group (e.g. methyl group, ethyl group, etc.), and this
The alkyl group may have a substituent, and as a substituent
is, for example, a halogen atom (e.g. fluorine atom, chlorine atom)
4! ? ), carboxyl group, etc. represented by R
The carboxyl group of the substituent and the carboxyl group of the substituent are salts.
may be formed. J, and V J 2 each represent a divalent bonding group, and this
As the divalent bonding group, for example, -old lC0-1-CO
Nn-1-COO-1-0CO-1-SCO-1-CO
5-1-0-1-S-1-SO-1-SO,- etc.
. X and x2 each represent a divalent hydrocarbon group,
Examples of divalent hydrocarbon groups include alkylene groups and aryl groups.
-lene group, aralkylene group, alkylenearylene group or
or arylene alkylene group, and alkylene group
For example, methylene group, ethylene group, propylene group, etc.
Examples of arylene groups include phenyl groups, etc.
lene group, etc., and phenylmethylene group as an aralkyl group.
lene group, etc., and examples of alkylenearylene groups include
For example, methylene phenylene group, etc.
As the kylene group, for example, phenylene methylene group etc.
be. k s '1 + , +Il + , Q 2 and
and m2 each represent 0 or 1. In addition, CP and l/Cp2 are each so-called coupler residue.
A group represented by the following general formula is preferable. Margin below: white. [6] [7] In formula [・I] to formula [3], n+, 1 and
, lL3 and IL4 are each a hydrogen atom,
F, Al-1′ group, cycloalkyl group, aryl group,
acyl group, alkyloxycarbonyl group, aryl group
Xycarbonyl group, alkylsulfonyl group, aryls
sulfonyl group, carbamoyl group, sulfamoyl group, acyl
ruoxy group, amino group, alkoxy group, aryloxy group
group, cyano group, 1nreido group, al-tru f...1 group
, ``no-arylthio group, carboxy group, sulfo group or
represents a ring residue, which is further hydroxyl group, carboxyl group, etc.
xy, ru group, sulfo group, flukoxy cyano group, 21
・Mouth group, alkyl group, aryl group, aryloxy group,
Acyloxy group, acyl group, sulfamo-r group, cal
Substituted with bamoyl group, imide group, halogen atom, etc.
It's okay. For the purpose of these Ilt dust, (CpI and C1)2
In Cp2, the IM substituent -
is an ethylenically unsaturated group represented by Q, or ethylene
It is a group that contains a sexually unsaturated group. Also, in general formulas [I] and [2], J5 is represented by X.
The divalent bonding group represented by the following general formulas [14] to [38]
] is preferable. General formula (1=l) General formula [15]゛1“
+6 General formula [1G] General formula [17] ta General formula [18] General formula [19] -N1.
IC0N1. l-It. -Nll5O2(C)- 1per-Nll5O2Nll-[ts -8-(C)- +1 ta General formula [4] General formula [B] -s6UI L
”l I□0 shield C0
In the 0LI general formula [2n] -N=N formula (lll) to [22], lt and 1(. each represent a water bladder atom or an alkyl group (e.g. methyl group, ethyl group).
(chill group, etc.), and ■ represents 0, ■ or 2. General formula [B] General formula [2G] General formula (27
) General formula [28] General formula [29]
General formula [30] General formula [3I]
General formula [32] i General formula [33] General formula [
34〇 General formula [35] General formula [3G] General formula [
:373 General formula [38] Formula [5] or Formula
In [38], 几7 is ki ## beak water su (atomic, halogen
atom, alkyl group, cycloalkyl group, aryl group,
Acyl group, alkyloxycarbonyl group, arylox
Cycarbonyl group, alkylsulfonyl group, arylsulfonyl group
Honyl group, carbamoyl group, sulfamoyl group, acyl group
Oxy group, amide 7 group, alkoxy group, aryloxy group
, sia/group, ureido group, alkylthio group, aryl group
O group, carboxy group, sulfo group, PJJ element m'M group, etc.
In other words, this is even more water rj! ! group, carboxyl group,
Sulfo group, alkoxy group, sia/group, nitro group, alkyl
group, aryl group, aryloxy group, acyloxy group
, acyl group, sulfamoyl group, carbamoyl group, imide
It may be substituted with a do group, a halogen atom, etc. 1) yc is eliminated when Cp2 reacts with the oxidized form of the reducing agent.
The color chart does not show any residue. As dye residues, azo dyes,
Azomethine color JC% anthraquinone dye, Naf I/Kino
dyes, styryl dyes, nitro dyes, quinoline dyes,
Examples include residues of talocyanine pigments, such as yellow
, as magenta and cyan pigments, the following general formula [3
9] to [73] are pregnant. (Yellow) General formula [39] General formula [=IO':1!
(. General formula [=lI] General formula [-12:]-
General formula - [n5] General formula [46] 〇 General formula [47] General formula [48] General formula [
49] General formula [father] LIO [9 General formula [55] General formula [56] General formula [
57] General formula [58] General formula [59]
General formula [60] (cyan) General formula [61] General formula [62] General formula [
63] General formula [64] General formula [65]
General formula [66] General formula [67]
General formula [68] General formula [69] General
Formula [70] General formula [71] General formula [72]
] General formula [73] It. Alkyl group, cycloalkyl group, aralkyl group, alkyl group
xy group, aryloxy group, aryl group, acylami 7
group, acyl group, sia/M, hydroxyl & argyl sulfo
nylamino group, sulfonylamino group, alkyl
Sulfonyl group, hydroxyalkyl group, cyanoalkyl group
group, alkoxycar4ζnylalkyl group, alkoxy
Alkyl represents aryl A gysialkyl group, nitro group, halo
Gen atom, sulfamoyl group, N-[L sulfamo・'
carbamoyl group, N-substituted carbamoyl group, sulfur group, carbamoyl group, N-substituted carbamoyl group,
Famido group, N-I! Substituted sulfamide group, hydroxya
alkoxy group, alfukidialkoxy group, carboxyl group
, 7 ami groups, 7 substituted ami groups, alkyl Chi A black N, ? Li
ruthio group, hydroxamic acid group, imide citron, sulfo group
Phosphate group, 7It & ammonium group, ureido group, complex
Represents 3 substituents selected from ring groups, etc. Further, as another preferable dye, the following general formula [74
] and [75], the chelatable pigment is
Can be mentioned. General formula (74) General formula [75] Formula [74]
] and [75], Y is at least one ring
is composed of 5 to 7 atoms (e.g.
benzene ring, naphthalene ring) or m-ring (e.g. pyridine ring)
form ring, pyrazole ring, pyrazolotriazole ring)
represents the atomic group necessary to
At least one adjacent position of the carbon atom is (a) a nitrogen atom
or (l)) nitrogen (atoms, acid atoms or sulfur)
is a carbon atom substituted with an atom, and Y2 is at least 1
An aromatic ring in which one ring is composed of 5 to 7 radicals T.
(e.g. benzene ring, naphthalene ring) or heterocycle (e.g.
pyridine ring, pyrazole ring, pyrazolotriazole ring
) represents the atomic group necessary to form
・Chemical groups (e.g. amide 7 group, water rn group, carboxyl group,
(alkoxy group, thiofurkoxy group). l(,1
and [tl, is 1] (synonymous with tto~lL+3 in j.
Ru. The four dye groups are temporarily capable of restoring color during heat development or transfer.
It may also be in the form of a short wave ratio. A more preferable form of the compound represented by general formula (1) is
As expressed by the following general formulas [7G] to [80]
It is a compound. -・General formula (7(i) and [77], 'It,
are alkyl groups each having a substituent and C may be
group or a back-ring residue, [L2 and It are each
each hydrogen atom (, f: each may have a substituent
Represents an alkyl group, aryl group or carbocyclic residue, 1
(, is a hydrogen atom or an alkyl n having a substituent
5, Xlj: nitrogen-containing heterocycle which may have a substituent
Represents the atomic group necessary to form a residue, J, Su3, V
n2 each represents a divalent bonding group, and YI represents a divalent hydrocarbon m
j+k wo F2 L, Y21. t-(22)o2
cOOHT (fl 392 divalent hydrocarbon group
represents, ZljJ nib Z2 respectively alkylenez, 1;
1) is a hydrogen atom, Nn. 71i or monovalent metal
Represents an atom, ni, view, product, II ls n2 are each O*
or 1. General formula [78] ++ , -<:()<:H(x>NH-8,2(n,i
(Jλ,, C-Cl+2 In the general formula [78], 1t1 represents an alkyl group,
1 (2 is aru; 1-luno, (or represents an aryl group,
1(, represents 2 filli hydrocarbon group 2, ■L represents a
Represents an alkyl group or a hydrogen atom, and J is a divalent bonding group 3
I, g represents O or 13, and Ill represents O or l.
vinegar. General formula [78] A "In the general formula [78], Q is an ethylenically unsaturated group or
Is it an ethylenically unsaturated group? represents a group with Z is an N atom
together with nitrogen-containing heterocyclic residues (polymerizable ethylenic
Atoms necessary to form a plan (which may have unsaturated bonds)
Represents group 3, Rt is an alkyl tv group, a') ” group
, argylami 7 groups, 7nilino groups, ryodylami 7 groups or
is a ureido group, and Ar is an aryl group or a carbocyclic group.
Represents a residue, nA "In the general formula [79], 1 (1 is a hydrogen atom, the number of carbon atoms is 1
~lt lower alkyl groups or chlorine atoms, n
2 and 1 (, are each substituted or unsubstituted alkylene
group, arylene group or aralkylene group;
The kylene group may be linear or branched. X is -CON
Represents H- or 1000-, Y is -0-5-S-1
-SO-1-SO2-1-CONI-1- or -CO
represents O-, Ar is unsubstituted or substituted phenyl Jl
Also showing fangs, I? 4 is R1 [substitution or substituted aniline]
%1%
m and n do not each represent 0 or l. General formula [80] Y-C1l-Q 100 (X1M In general formula [80], X is a benzene ring or
Represents the atomic group necessary to form a ren ring. The benzene ring or naphthalene ring formed here is a substituent
It may have. Y represents oxygen atom or sulfur base-F
I, Q is an ethylenically unsaturated group or ethylenically unsaturated
Represents a group having a group, M is a hydrogen atom, a Nn4 group, or
Represents a monovalent metal atom. Specific examples of the compound represented by general formula [I] are shown below.
However, the present invention is not limited thereto. 1ゝ, hereafter go to Kamaichi N [IC0C= ClI2 CI3 l1 M -7 CI-1゜M -9 M -12 1=1 M -13 il (-n1 il (:00n C00
II Below are specific examples of compounds represented by general formula [2].
However, the present invention is not limited thereto. IJ Nl-18 The unit represented by the general formula [1] or [2] of the present invention
Polymers with repeating units derived from needles are
vl[single-needle body represented by general formula [1] or [2]
The so-called homopolymer is a repeating unit consisting of only one type of
- even if it is represented by the above general formula [1] or [2]
It is a copolymer that combines two or more types of monoanal bodies.
and other copolymerizable ethylenically unsaturated groups.
A copolymer consisting of one or more comonomers having
There may be. The unit represented by the general formula [1] or [2] of the present invention
The above ethylenically unsaturated group capable of forming a copolymer with the host
Examples of comonomers having
Taacrylic acid esters, vinyl esters, olefins
, styrenes, crotonate esters, diethyl itaconic acid
Steles, maleic acid diesters, fumaric acid diesters
compounds, acrylamides, allyl compounds, vinyl ethers
vinyl ketones, vinyl heterocyclic compounds, gurinji
esters, unsaturated nitriles, polyfunctional monomers, etc.
These comonomers can include species such as unsaturated acids, etc.
- To be more specific, acrylic esters
Examples include methyl acrylate, ethyl acrylate,
n-propyl acrylate, isobutyl acrylate,
n-butyl acrylate, isobutyl acrylate, S
ec-butyl acrylate, tert-butyl acrylate
rylate, amyl acrylate, hexyl acrylate
, 2-ethylhexyl acrylate, octyl acrylate
tert, tert-octyl acrylate, 2-cut
Loloethyl acrylate, 2-bromoethyl acrylate
4-chlorobutyl acrylate, cyanethyl acrylate
rylate, 2-acetoxyethyl acrylate, dimethylate
Ruaminoethyl acrylate, benzyl acrylate,
To methoxybenzyl acrylate-1,2-chlorocyclo
xyl acrylate-1, /chlorohexyl acrylate,
Furfuryl acrylate, tetrahydrofurfuryl acrylate
Li-V-l-, phenyl acrylate, 5-hydroxybenzene
methyl acrylate-1,2,2-dimethyl-3-hydro
Ki/globyl acrylate, 2-methquine ethyl acrylate
rate, 3-methoxybutyl acrylate-1,2-method
xyethyl acrylate, 2-1so-propoxyacrylate
Relay-1, 2-butoxyethyl acrylate, 2-(
2-Methoquinethoxy)ethyl acrylate (・, 2-(
2-ptoxy/ethoxy)ethyl acrylate, ω-meth
Ki7 Polyethylene glycol acrylate 1” C added mole
number n = 9), 1-bromo 2-methoxyethyl acrylate
1,1-dichloro-2-nitoxyethyl acrylate
For example, Examples of methacrylic acid esters include methyl methacrylate.
Leh!・, ethyl methacrylate, n-probyl methacrylate
rylate, isobutyl acrylate, ■-butylmethac
rylate, inbutyl methacrylate, 5eC-butyl
Methacrylate, Lert-butyl methacrylate, a
Mil methacrylate, hexyl methacrylate, ncro
Hequinyl methacrylate, benzyl methacrylate,
lorobenzyl methacrylate, octyl methacrylate-1
・, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate-1-12-(3-ph)
phenylpropyloxy)ethyl methacrylate, dimethy
Ruaminophenoxyethyl methacrylate-1・, Furufuri
methacrylate, tetrahydrofurfuryl methacrylate
-1・, phenyl methacrylate, Kunzil methacrylate
Naphthyl methacrylate-1,2-hydroxyethyl
methacrylate, 4-hydroquine butyl methacrylate
G, triethylene glycol monomethacrylate,
Ropylene glycol monomethacrylate, 2-methoxy
Ethyl methacrylate, 3-methoxybutyl methacrylate
-1.,2-acetoxyethyl methacrylate-1.,2-
Acetoacetoxyethyl methacrylate, 2-ethoxy
Ethyl methacrylate, 2-1so-propoxyethyl
Methacrylate-1-12-butoxyethyl methacrylate
, 2-(2-methoxystyrene/)ethyl methacrylate
2-(2-(7-hydroxy)ethyl methacrylate)
2-(2-butoquinol)ethyl methacrylate
1., ω-methoxy/polyethylene glycol methacrylate
(subdivided molar c!1.n = 61, allylmetac
Relay-1・, dimethylaminoethylmethyl methacrylate
Examples include chloride salt. Examples of vinyl esters include vinyl acetate, vinyl
Nilprobionate, Vinyl Butyrate, Vinyl Inobu
Thyrate, vinyl caproate, vinyl chloroacetate
, vinyl methoxy acetate, vinyl phenylacetate
vinyl benzoate, vinyl salicylate, etc.
It will be done. Examples of olefins include dicyclopentadiene.
, ethylene, clopine, 1-butene, 1-pentene,
Vinyl chloride, vinylidene chloride, isoprene, chloroprene
7.2.3-dimethylbutadiene, etc.
can be done. Examples of styrenes include styrene and methylstyrene.
dimethylstyrene, trimethylstyrene, ethylstyrene
Styrene, Improvylstyrene, Chlormethylstyrene
, methoxystyrene, acetoxystyrene, chlorstyrene
Ren, dichlorstyrene/bromstyrene, vinyl rest
Examples include fragrant methyl ester. Examples of crotonate esters include butyl crotonate.
, hequinyl crotonic acid, and the like. In addition, as itaconic acid diesters, for example, itaconic acid diesters include itaconic acid diesters.
dimethyl itaconate, diethyl itaconate, diptylphate itaconate
Examples include. As maleic acid diesters, for example, maleic acid
Diethyl, dimethyl maleate, diptyl maleate, etc.
Which can be mentioned. Examples of fumaric acid diester include fumaric acid diester.
Chill, dimethyl fumarate, diptyl fumarate, etc.
It will be done. Examples of other comonomers include:
Ru. Acrylamides, e.g. acrylamide, methyl acetate
Acrylamide, ethyl acrylamide, propylacrylamide
Leramide, Butylacrylamide, Lert-Butylacrylamide
Acrylamide, cyclohexyl acrylamide, benzene
lyacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, dimethylamine ethyl
Acrylamide, phenylacrylamide, dimethylacrylamide
Acrylamide, diethylacrylamide, β-7 anoe
tylacrylamide, N-(2-acetoacetoquinethyl
methacrylamide, etc.; methacrylamide, e.g.
methacrylamide, ethyl methacrylamide, propylene
butyl methacrylamide, butyl methacrylamide, tc self
-Butyl methacrylamide, 7 chlorohexyl methacryl
Amide, benzyl methacrylamide, hydroquine methyl
methacrylamide, methoxyethyl methacrylamide,
Dimethylaminoethyl methacrylamide, phenylmeth
Acrylamide, dimethylmethacrylamide, diethylmethacrylamide
tacrylamide, β-cyanethyl methacrylamide,
N-(2-acetoacetoxyethyl methacrylamide)
Allyl compounds, such as allyl acetate, allyl caproate
, allyl laurate, allyl benzoate, etc.; vinyl ethers, ψrieba, methyl vinyl ether,
Phthyl vinyl ether, hexyl vinyl ether, meth
xyethyl vinyl ether, dimethylaminoethyl vinyl
Vinyl ketones, such as methyl vinyl ketone, phenyl ether, etc.
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
unsaturated nitriles, glycidyl methacrylate, etc.
For example, acrylonitrile, methacrylate, etc.
etc.; polyfunctional polymers, such as divinylbenzene, methyl
bisacrylamide, ethylene glycol dimethacrylate
rate etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, male
monoalkyl itaconate, e.g.
monomethyl itaconate, monoethyl itaconate, motsuputi itaconate
such as maleic acid monoalkynodi, e.g.
Monomethyl maleate, monoethyl maleate, monomethyl maleate
Butyl, etc.; citraconic acid, stich. Rensulfonic acid,
Vinyl benzyl sulfonic acid, vinyl sulfonic acid, acrylic
loyloxyalkyl sulfonic acids, e.g. acryloyl
oxymethylsulfonic acid, acryloyloxyethyl
Sulfonic acid, acryloyloxypropylsulfonic acid
methacryloyloxyalkyl sulfonic acid, e.g.
, methacryloyloxymethylsulfonic acid, methacryloyl
yloxyethylsulfonic acid, methacryloyloxyp
Sodium lopylsulfonate; acrylamide alkyl sulfonate
acid, e.g., 2-acrylamido-2-methylethane
sulfonic acid, 2-acrylamido-2-methylpropane
sulfonic acid, 2-acrylamido-2-methylbutane
Sulfonic acid, etc.; methacrylamide alkyl sulfonic acid
, for example, 2-methacrylamido-2-methylethane
Sulfonic acid, 2-methacrylamido-2-methylpropane
Sulfonic acid, 2-methacrylamido-2-methylbutane
Sodium sulfonate; acryloyl oxy-7 alkyl phosphite
Acryloyloxyethyl phosphate, side light, acryloyloxyethyl phosphate
, 3-acryloyl oxinglovir-2-phosphate
etc.; methacryloyloxyalkyl phosphates, e.g.
For example, methacryloyloxyethyl psulfate-1, 3
-Methacryloyl oquinprovir-2-phosphe-1.
etc.; 3-aryloki/-2-hydro having two hydrophilic groups
Storium xypropane sulfonate and other substances are exposed. These acids include alkali gold (e.g. Na, etc.)
) or a salt of ammonium ion. Further, as other comonomers, U.S. Patent No. 314
5L790, 3.438,708, 3.5
No. 54,987, No. 4,215.195, No. 4,
No. 247,873, Japanese Unexamined Patent Publication No. 57-205735
It is possible to use crosslinking monomers listed in the specifications etc.
can. Examples of such crosslinking monomers include
N-(2-7ceto7cetoxyethyl)acrylic acid
Mido, N-(2-(2-7set),
A copolymer is formed by the monomer and nl [mentioned comonomer].
is preferably represented by the above general formula [1] or [2].
The repeating unit consisting of the single unit that is
Rimmer processing 0 to 9) contains 0 weight 1i%, and
Even more preferable: 3υ~70 weight scales are included.
. Generally, polymer couplers are produced using 7L polymerization method or solution polymerization method.
Polymerized legally, the general formula [1] or according to the present invention
or the repeating unit derived from the unitary unit shown in [2].
The dye-coupling material polymer of the present invention having
can be polymerized with Regarding the emulsion polymerization method, please refer to the United States
Patent No. 1I, 081J, 2n, Patent No. 3.37
(J, No. 952) also describes lipophilic polymers dissolved in gelatin water.
For information on how to disperse it in latex form in a liquid, please refer to the U.S.
Using the method described in Patent No. 3.451.82υ
I can be there. These methods are used to form homopolymers and copolymers.
In the latter case, the comonomer is a liquid comonomer.
In the case of emulsion polymerization, it is usually a fixed monomer.
It also acts as a solvent for the body. 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, dode/ruben
Sodium Zensulfonate, Sodium Lauryl Sulfate,
Dioctylsulfosuccinic rll sodium, nonionic active
Examples include sulfates of sexual agents. Examples of nonionic activators include polyoxyethylene nonionic
Luphenyl ether, polyoxyethylene stearic acid
Ester, polyoxyethylene sorbitan monolauryl
Acid ester, polyoxyethylene-polyoxy7propylene
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 agents and their functions, [le1gisc
l+eCI+cmiscl+e fdustrie
, 28.16-2Q (1963).
Ru. Gela is a lipophilic polymer synthesized by solution polymerization method etc.
In order to disperse Chin in the form of latex in an aqueous solution, first the parent
After dissolving the oil-based polymer in an organic solvent, it is added to gelatin.
With the help of a dispersant in an aqueous solution of chlorine, ultrasonic
Disperse in a latte-like manner using a domil etc. lipophilic poly
Dispersing the polymer in the form of latex in an aqueous gelatin solution
The method is described in U.S. Pat. No. 3,451.820.
It is. As an organic solvent for dissolving lipophilic polymers,
, esters such as methyl acetate, ethyl acetate, acetate
Lopil, etc., alcohols, ketones, halogenated hydrocarbons
Elements, ethers, etc. can be used. Also these
Organic solvents may be used alone or in combination of two or more.
I can do it. In producing the dye-providing substance polymer according to the present invention,
Therefore, the solvent used for polymerization is the monomer and the color produced.
It is a good solvent for the donor polymer and has a strong reaction with the polymerization initiator.
It is desirable to use a material with a rounded response, specifically water, toluene,
Alcohol (e.g. methanol, ethanol, 1so-
7” lovanol, (ert-butanol etc.), acetic acid
Thon, methyl ethyl ketone, te!・Rahydrofuran, di
Oxane, ethyl acetate, dimethylformamide, dimethylene
Rusulfoxide, acetonitrile, methylene chloride, etc.
These solvents can be used alone or in combination of two or more.
It may be used by mixing the above. The polymerization temperature depends on the type of polymerization σ8 initiator, the type of solvent used, etc.
Although it is necessary to take into account the
It is. Emulsion polymerization method and solution polymerization method of dye-providing polymer of the present invention
The following are polymerization initiators that can be used legally:
Can be mentioned. As a water-soluble polymerization G'A initiator, for example, potassium persulfate
, ammonium persulfate, sodium persulfate, etc.
4. Sodium 4'-azobis-4-cyanovalerate
, 2.2'-azobis(2-amidinopropane) hydrochloride
Water-soluble azo compounds such as hydrogen peroxide can be used.
Ru. Also, it is used as a lipophilic polymerization initiator used in solution polymerization method.
is, for example, azobisinobutyronitrile, 2,2'-
Asohisu (2,4-dimethylvaleronitrile), 2.
2'-Azobis(4-methoxy-2,ll-dimethylbase)
leronitrile), 1,1'-azobis(ncrohexano)
-l-carbonitrile), 2,2'-azobisincin
Anobutyric acid, 2.2'-azobisin dimethyl acetate, 1.
1'-Azobis(ncrohexanone-1-tricarbonitrile)
), 4,4'-azobis-4-/anovaleric acid, etc.
Compound, benzoyl peroxide, lauryl peroxide
side, chlorobenzyl peroxide, diisopropylene
peroxydicarbonate, di-t-butyl peroxydicarbonate
Examples include peroxides such as side. these
Among these, preferred are benzoyl peroxide and chloride.
lobenzyl peroxide, lauryl peroxide, etc.
can be mentioned. These polymerization initiators are suitable for emulsion polymerization and solution polymerization.
o, oi~1゜ffi relative to the total amount of monomer
, preferably in the range of 0.1 to 5 times.
You can Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization, may also be used.
, bulk polymerization and other methods can also be applied. That is, books
In the invention, the general formula [1] or [2] of the present invention
A monohedral dye-donating homopolymer represented by
A copolymer consisting of a combination of two or more polymers or the monomer
the facepiece and at least one other polymerizable comonomer.
Includes all copolymers as polymerization components, and
It is not limited by the synthesis process. Hereinafter, specific representative examples of the dye-donating substance polymer of the present invention will be described.
Although it is listed as person-1, it is not limited to this. Table 1 In Table 1, the abbreviations of comonomers are as follows. BA: n-butyl acrylate M A: Methyl acrylate M M: Methyl methacrylate EM Diethyl methacrylate ST: Styrene In addition, the remaining monomer is the unreacted dye-donor monomer.
It is the content rate. Examples of polymerization of the dye-providing substance polymer of the present invention are shown below. Polymerization example 1 Copolymerization poly of monomer M-4 and rope tyl acrylate
Synthesis of mer dye-donating substance (P-1). 30 g of exemplified monomer (M-4) and 20 J of n-butyl acetate
Cleary) dissolved in 500 me of dioxane,
Heating to 85°C while introducing nitrogen gas, 2,2'-
Add 30 (lIg) azobisisobutyronitrile, 5 o'clock
The mixture was heated at 85°C for a while. After the reaction is completed, the reaction solution is heated to 2500 ml.
Pour into 1nl of water, filter out the precipitate, and recycle this solid content.
and 500 me dioxane, 2500 ml
water and filtered out the precipitate. Dry the solid and use the poly
Mar P-1's 48! I got y. Polymerization Example 2 Copolymerization of monomer M-10 and n-butyl acrylate
Synthesis of polymeric dye-donor (P-10). 30.9 of the exemplified monomer (M-10) and 20 g of n-
Butyl acrylate f Dissolved in 250 ml of dioxane
4.4.
'-Azobis-4-cyanovaleric acid was added,
Heated at 80°C for 5 hours. After the reaction is completed, the reaction solution is heated to 250 ml.
Pour into 0ml of water, filter out the precipitate, and recycle this solid content.
and 250 ml of dioxane.
It was poured into water and the precipitate was filtered out. Dry the solid desired polymer
-P-10 of 7171 was obtained. Polymerization Example 3 Copolymer of monomer M-15 and methyl acrylate
-Synthesis of dye-donating substance (P-12). 30,! 7n7) Exemplary unit (M-15) and methyl
Acrylate 20. f2 (dissolved in 10 ml of dioxane)
Heat to 78°C while introducing nitrogen gas, 4.4
'-Azobis-4-/anovaleric acid 500m9 was added,
Heated at 78°C for an hour. After the reaction is completed, the reaction solution 'il'
Pour into 2000 ml of water, filter and separate.
This solid content was again dissolved in 200 ml of dioxane, and 2
The mixture was poured into 000ml of water and the precipitate was filtered out. dry solids
17'7 of the desired polymer P-12 was obtained. Polymerization Example 4 Copolymerization poly of monomer M-6 and n-butyl acrylate
Synthesis of mer dye-donating substance (1)-19). Exemplary monomer (M-6) of 30 & and I+-butyl acetate
Relate 20f1 to 125 me dimethylformamide
Dissolve in hydrogen and heat to 85°C while introducing nitrogen gas.
, 2.27-azobisinbutyronitrile 500m9Y
c and heated at 85°C for 5 hours. After the reaction is complete, the reaction solution
Pour into 1250 ml of water, filter out the precipitate, and
Dissolve the solid again in 125ml dimethylformamide
The mixture was poured into 1250 m water and the precipitate was filtered out. The solid was dried to give 47 F of the target polymer P-19.
'i- got it. Polymerization Example 5 Copolymerization of monomer M-9 and lobethyl acrylate
Synthesis of remer dye-donor (I'-21). Exemplary monomer of 25I (M-9) and n-butyl acrylate
25.9 (c-in 125 ml of dimethylformamide)
Dissolve and heat to 80°C while introducing nitrogen gas,
．． 2'-Azobisisobutyronitrile 500rnlj'
e and heated at 80°C for 5 hours. After the reaction is complete, the reaction
Solution '5: Pour into 125Qme water and filter out the precipitate.
This solid content was poured into 125 ml of dimethylformamide again.
Pour into 1250 ml of water and filter out the precipitate.
did. The solid was dried to obtain 48.9% of the target polymer P-21. Polymerization Example 6 Copolymerization poly of monomer M-4 and n-butyl acrylate
Synthesis of mer dye donor (P-17). Exemplary monomer (M-4) of 25.9 and n-butyl acrylate
259 e 250 ml dimethylformamide
and heated to 80°C while introducing nitrogen gas for 2 hours.
．． 2'-7 Zobisisoputiloni!・Lil 50 (lILi
' and heated at 80°C for 5 hours. After the reaction is complete, the reaction
liquid? Pour into 2500 ml of water, filter out the precipitate,
This solid content was again dissolved in 250 ml of dimethylformamide.
The mixture was dissolved, poured into 2500 ml of water, and the precipitate was filtered out. The solid was dried and the desired polymer P-17, 4G 9'. r
:Obtained. Polymerization Example 7 Copolymerization of monomer M-n and methyl methacrylate
Synthesis of remer dye donor (P-22). Exemplary monomer (M − n ) of 30, 9 and methylmer
Tacrylate 20,9 e 125 ml N,N-
Dissolved in dimethylacetamide, while introducing nitrogen gas.
Heat to 78°C and add 500% dimethyl azobisisobutyrate.
m1;”!r was added and heated at 78°C for 5 hours.
After completion, pour the reaction solution into 1250 ml of water to remove the precipitate.
Filtered, and the solid content was again mixed with 125 ml of N, N'
- dissolved in dimethylacetamide and 125Q ml of water
The precipitate was completely filtered out. Dry the solid desired polymer
-18 of 1'-22, 9'! I got f. Polymerization Example 8 Copolymerization of monomer M-13 and n-butyl acrylate
Synthesis of polymeric dye-donor (P-23')
. Exemplary monomer (M-13) of 20, 9 and lobe
Thyl acrylate 30Ef: L70ml dimethylform
Dissolved in Muamide and heated to 72°C while introducing nitrogen gas.
Heat and add 500 r of 4,4'-azobis-4-cyanovaleric acid.
n9 was added and heated at 72°C for 8 hours. After the reaction is complete,
Pour reaction solution K into 1700 ml of water and filter out the precipitate.
, this solid content was added again to 170 ml of dimethylformamide.
Pour into 1700 me water and filter out the precipitate.
Ta. The solid was dried to obtain the target polymer P-B 48,9. Polymerization Example 9 Monomer M −,! Copolymerization of and methyl acrylate
Synthesis of remer dye-donor (f'-25). Exemplary monomer of 25I (M-4) and methyl acrylic
rate 25, 9t 125 ml dimethylform
Dissolved in amide and heated to 65°C without nitrogen gas.
Heat, 4.47-azobis-l-cyanovaleric acid 500
m9 was added and heated at 65°C for 10 hours. After the reaction
, Pour the reaction solution into 1250 m6 of water and filter the precipitate.
, this solid content was added again to 125 m6 of dimethylformamide.
Pour into 1250 m water and filter out the precipitate.
Ta. The solid was dried to obtain 4n of the target polymer P-25. Polymerization Example IO Copolymerization of monomer M-10 and n-butyl acrylate
Synthesis of remer dye donor (P-2G). Exemplary single unit (M-10) of 30& and n-butylene
Luacryle-1-20&'e 125 ml di
Dissolve in methylformamide and introduce nitrogen gas while
Heating to 60℃, 2,2'-azobisinbutyronitrile
and heated at 60'C for 10 hours. After the reaction is complete, pour the reaction solution into 125Qml of water and precipitate.
Filter the filtrate and collect this solid content again at 125m7! dimethyl of
Dissolve in formamide and pour into 1250 ml of water.
The precipitate was filtered and the solid was dried to obtain the desired polymer P-26.
46g was obtained. The dye-providing substance of the present invention can be used alone for one color tone.
or two or more may be used. The total amount of use is for the dye-donating substance of l fiIi period.
0-05, S'~100 g (per lnt)
, preferably used from 1.0 to 30.9 (per lr+?)
can be done. Then rF margin again. ．． The silver iodide content of the photosensitive silver halide of the present invention is
The average content in the layer containing photosensitive silver halide.
be. Preferably, in addition to these conditions, photosensitive halogen
Photosensitivity No. 10 of Z/Z contained in the layer containing silver germide
Substantially all of the silver denride grains (J't integral 1 is 9
Particles corresponding to 0 weight % or more) each have an average of 4 mol % to 4
It has a silver iodide content of 0 mol%. In the heat-developable photosensitive material of the present invention, photosensitivity/% lodenization
If the silver iodide content of silver is less than 4 mol%, thermal fogging will be improved.
The positive effect is small, and on the other hand, if it exceeds 40 mol%, the photosensitive fi
l fn8 is decreased, making it unsuitable for practical use. The heat-developable photosensitive material of the present invention is photosensitive/contains silver 10-dendide.
In this case, the photosensitive layer can have two or more layers.
In at least one of the layers containing silver halide
If the above conditions regarding silver iodide content are met i19
However, if the condition is met in all these layers,
It is preferable that The silver iodide content of the photosensitive silver halide in the present invention is
Preferably it is in the range of 4 mol% to 20 mol%. Photosensitive halogenated kite pond storing the iodide system of the present invention
Regarding the halogen component, there is no limit to 1, T, but it is preferable
High silver halide compositions include silver iodobromide and silver chloroiodobromide.
Ru. The photosensitive halogen containing silver iodide used in the present invention is
l', (: Ialkidcs-7? CI+i+aie
et PI+ysique I'l+. tograpl+1que (Paul Momte1 company)
Published, 19f37), G-F-Du[i+r? t N
+oeLoBrapl+ic [E+aulsion
Ceu+1sLry(TI+eFocal Pr
Published by eSs, 19 (16), V, L, ZQlik+nu
ncl a17j Making anJ Co
aLinFI l'l+oLogral+Ieffectc E
mulsion (published by TbeFocal I'ress,
(19134), etc.
can be done. Which of the acid method, neutral method, ammonia method, etc.
may be used, but the ammonia method is particularly suitable. Ma
In addition, there is a method in which a soluble silver salt and a soluble halogen salt are reacted.
There are various methods such as one-sided mixing method, simultaneous mixing method, and combinations thereof.
Either may be used. In addition, silver halide grains are
It is also possible to use a back-mixing method in which it is formed in excess of
. One method of simultaneous mixing is to produce silver halide.
Optionally, the solution p A g in the reaction vessel is
and control the degree of addition of silver and halogen solutions.
Using the Chondrold double jet method
You can also do it. According to this method, crystal shape and particle size
A so-called monodisperse silver halide emulsion with nearly uniformity can be obtained.
It will be done. The photosensitive silver halide used in the present invention has a particle size distribution of
It is preferable that the coefficient of variation is 15% or less, especially 10% or less.
Delicious. In addition, coefficient of variation of particle size distribution (Taro) = ($ plus diameter
Standard deviation of distribution/average particle size) x 100%, and
, the grain size here refers to when the silver halide grains are spherical.
is the direct result, and if the shape is not spherical, its projected image is a circle with the same area.
This is the diameter when converted into an image. Furthermore, preferred photosensitive silver halide used in the present invention
is a core/shell type halogen with a surface latent image type shell.
It consists of silver oxide particles. The photosensitive silver halide grain size used in the present invention is 0
．． A range of 1 μIII to 0.4 μIn is appropriate and preferred.
More preferably, it is in the range of 0.05 μm6 to 0.4 μmn. Silver halide having a shell preferably used in the present invention
Silver halide emulsions with grains are included in monodispersed emulsions.
The halogenated particles are used as a core and the shell is coated on the core.
It can be manufactured by To make the core a monodisperse silver halide grain, add B to p.
Achieve the desired size using the double jet method while keeping it constant.
particles can be obtained. Also highly monodisperse halo
Silver genenide emulsions are described in JP-A No. 54-48521.
It is possible to apply the method described in in that method
In a preferred embodiment, potassium iodobromide-gelatin is used.
The aqueous solution and ammoniacal silver nitrate aqueous solution are mixed into silver halide species.
Addition rate to an aqueous gelatin solution containing particles as a function of time.
It is manufactured by changing and adding it. On this occasion
, time function of addition rate, pH, nΔg, temperature, etc. as appropriate.
By selecting highly monodisperse silver halide emulsions
Obtainable. Using core particles with good monodispersity as described above,
The shell is gradually grown according to the manufacturing method of a dispersible emulsion.
By applying the
Obtaining a silver lodenide emulsion consisting of silver lodenide grains/)
I can do it. The photosensitivity/% silver lodenide used in the present invention is a surface latent image type.
Preferably, the particles are core/shell type particles with a shell.
stomach. and the amount of shell is 0.0 of the particle having the shell.
In the range of 5% to 90% by weight, especially 1% to 80% by weight
It is preferable that the silver iodide content of the core corresponds to
is 4 mol% to 20 mol%, and the silver iodide content of the shell is 6
The silver iodide content in the core is preferably mol% or less.
The content is 2 mol% or more higher than the iodide 1 content of the shell.
It is preferable. Note that the core has a silver halide composition, etc.
Even if you have a core/shell purchase consisting of different layers,
1゜The heat-developable photosensitive material of the present invention has the dye-providing property of the present invention.
Contains photosensitive silver halide along with 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 noette method and double noette method in the field of photographic technology
It can be prepared by any method such as, but in the present invention,
In this case, the conventional silver halide gelatin emulsion preparation method is used.
The preferred result is a light-sensitive silver halide emulsion prepared by vt.
give fruit. 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,
Although fine particles may be used, the preferred particle size is
The diameter of the mound is approximately 0.001μm1 to approximately 1.5μm, and
Preferably about 0.01μIff to about 0.5μm6
. Photosensitive silver halide prepared as above? book cutting
Most of the heat-developable photosensitive layers of the photosensitive material of the invention are layered.
It can be preferably applied. In the present invention, 1) PA-1 of other photosensitive silver halide
As a manufacturing method, a photosensitive silver salt forming component is combined with an organic silver salt described below.
coexist to form photosensitive silver halide in a part of organic silver salt
You can also do it. Photosensitive silver used in this preparation method
Salt-forming components include Kuroiso/% lodenide, such as M
A halide represented by X n (where M is an H atom)
child, N H, group or metal atom, X is CQ, B
r or ■, +1 means that M is ■(atom, N n ,
When M is a group, it is 1, and when M is a metal atom, it shows its valence. Money
Genus atoms include lithium, sodium, potassium,
rubidium, cesium, tears, gold, beryllium, magnesi
um, calcyrano 1, strontium n, barium, zinc
, cadmium, mercury, aluminum, indium, orchid
Tan, ruthenium, thallium, dermanitum, ffi,
I+>, antimony, bismuth, chromium, molybdenum,
Tungsten, manganese, rhenium, iron, cobalt, di
rhodium, paranoum, osmilla n, iridium
Examples include aluminum, platinum, and cerium. ), halogen-containing gold
rfG complex (e.g., 2f'tCIJG+21't
Dr6n1Δu CQ4. (Nll4)2 1rCQ
al(Nll<)z fr CQc. (Nn.) 2Ru CQs, (old I4), Ru C
L, (old l,), RI+ Cn,. (Ml!<)3Rb [lrs etc.), Oniramuno 1 Ride
, (e.g., tetramethylammonium bromide,
Limethylphenylammonium bromide, cetylethyl
dimethylammonium bromide, 3-methylthiazo
Lium bromide, trimethylbenzylammonium
Quaternary ammonium halide such as diromide, tetra
Ethyl 7 male 7 ↑ Quaternary 7 male like nium bromide
7-onium(no)lide,bennoethylmethylsulfony
Umpromite, 1-ethylthiazolium bromide
Tertiary sulfonium halai 1! etc.), no.10den conversion
Hydrocarbons (e.g., iodoform, bromoform,
RN, 2-7'romo-2-methylpropane, etc.), N-
Halogen compounds (N-chlorosuccinimide, N-propylene
Mofusuccinimide, N-bromo heptatalimide, N-butyric acid imide
lomoacetamide, N-iodosuccinimide, N-butylene
lomo7taladinone, N-chloro7talazione, N-bro
Moacetanilide, N,N-dibromobenzenesulfone
Ami+! , N--10mo N-methylbenzenesulfone
Amido, 1,3-)bromo-4,4-nomethylhygund
), other halogen-containing compounds @ (e.g. trichloride),
Phenylmethyl, triphenylmethyl bromide, 2-bromo
butyric acid, 2-bromoethanol, etc.).
Wear. Photosensitive silver halide and photosensitive silver salt forming components
can be used in combination in various ways, and the amounts used are:
0.0 per mole of dye-donating substance monomer 4n position
The amount is preferably from 02 mol to 10 mol, more preferably
The amount is 0.2 mol to 2.0 mol. The heat-developable photosensitive material of the present invention comprises a dye-providing polymer of the present invention.
It is sufficient as long as it has at least one layer containing -, but
Each layer is sensitive to blue light, green light, and red light, i.e. heat
Blue photosensitive layer for development, green photosensitive layer for heat development, red photosensitive layer for heat development
It is also possible to have a multilayer structure. In addition, the same color photosensitive layer
by dividing it into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer).
It is also possible to provide one. 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 /% silver lodenide emulsion.
It can be obtained by adding Typical spectral sensitizing dyes used in the present invention include, for example:
For example, cyanine, merocyanine, complex, (3 nuclear
or tetranuclear) cyanine, holopolar cyanine, stylite
Examples include hemicyanin, oxonol, etc. Shea
Among the pigments of garlic, thiazoline, oxazoline, biro
Phosphorus, birinone, oxazole, thiazole, selenazo
Those with basic nuclei such as alcohol and imidazole are more
preferable. Such nuclei include alkyl groups, alkylene groups,
Hydroxyalkyl group, sulfoalkyl group, carboxy
Alkyl, ami/alkyl or fused carbocyclic
g, has an enamine group that can form a bare cyclic ring.
You may do so. Also, it can be a large/first-person form or an asymmetrical form.
, and methine and polymethine chains have furkyl groups and phenyl groups.
group, enamine group, or a heterocyclic substituent. The merocyanine pigment is added to the basic nucleus pond, for example, by thiophylamine.
guntoin nucleus, logenin nucleus, oxacillinone nucleus, bar
Biruric acid nucleus, thiazolinthion nucleus, malo/nitrile nucleus
, may have an acidic nucleus such as a pyrazolone nucleus. this
These acidic nuclei further contain furkyl groups, alkylene groups, and phenyl groups.
group, carboxyfurkyl 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, asfulvic acid derivatives,
salts, such as sulfonic acid, e.g. U.S. Pat. No. 2,93
3,390, the specifications of the same No. 2.937.089, etc.
Supersensitizing additives that do not absorb visible light as described
Can be used together. C) The amount of dye added is silver halide or halogenated
lXl0-'mol-1 mole per mole of silver-forming component.
. More preferably 1×10 to 4 mol to 1×10−′ mol
It is. In the heat-developable photosensitive material of the present invention, sensitivity may be adjusted as required.
Various growth silver salts are used to increase the
I can be there. The material used with the heat-developable photosensitive material of the present invention is a silver salt.
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. 53-3 (No. 3224 and No. 53-3)
37 (for each publication of No. 310, US Patent No. 3゜330
．． No. 1333, same f:rS3,794,496, same 1
No. 4,105,451, No. 4,123,274, No. 4,123,274, No.
No. 4,168.980, etc., as stated in each specification.
Silver salts of aliphatic carboxylic acids such as silver laurate
, silver tate, silver palmitate, silver stearate,
Silver arachidonic acid, behen [1, α-(1-phenyltetate)
Silver aromatic carboxylates, such as silver acetate (razolthio), e.g.
Silver benzoate, silver phthalate, etc., Special Publication No. 44-2658
No. 2, No. 45-12700, No. 45-18416,
45-22185, JP-A No. 52-31728, same
52-[No. 7321, JP-A No. 58-n8 (No. i38, same)
As described in each publication such as No. 58-n8639
Silver salts of imino groups, such as silver benzotriazole, 5-methane
Tylbenzotriazole salt, 5-acetamidobenzot
Riazole silver, 5-nitrobenzotriazole silver, 5-
Talolopenzotriazole silver, 5-methoxybenzotriazole
Azole silver, 4-sulfobenzotriazole silver, 4-hydrogen
1r Roxybenzotriazole silver, 5-ami/benzot
Riazole silver, 5-methylsulfobenzotriazole silver
, 5-carboxybenzotriazole silver, imiguzole
Silver, penzimiguzole silver, 6-nidropenzimiguzole
silver, pyrazole silver, urazole silver, 1.2.4-t
Riazole silver, IH-tetrazole silver, 3-ami/-5
-pennorthio-1゜2.4-) lyazole silver, sacca
Silver phosphorus, silver 7 talaimide, silver 7 talimide, etc.
2-mercaptobenzoxazole silver, mercaptooxazole
Thadiazole silver, 2-furcaptobenzoti7zole silver,
2-mercabutobenzimiguzole silver, 3-furcapto
-4-phenyl-1,2,4-) lyazole silver, 4-hyaluronic acid
Droxy-6-methyl-1,3,3a,7-chitrazai
silver and 5-methyl-7-hydroxy-1,2,
Examples include 3,4, (3-pentazaindene silver, etc.) Among the above organic salts, the effect of the present invention is particularly effective when using highly hydrophilic salts.
This is most noticeable when using a simple method. Particularly preferred (as the silver salt, benzotriazole
m-salts of derivatives with high hydrophilicity, such as base
Benzotriazole silver, 5-7cetamidobenzotriazole
silver, sulfobenzotriazole silver, 4-sulfoben
Zotriazole silver, 5-methylsulfobenzotriazole
Examples include silver. The above organic m-salt may be used alone or with 2f! ! Combined use of 1 or more
You can also use it <, Ill use the separated thing in any appropriate way.
It may be used by dispersing it in a binder, or
Prepare the silver salt in a suitable binder and release it without isolation.
It may be used as is. The amount of the organic silver salt used is per mole of photosensitive silver halonanide.
It is preferably 0.01 to 500 mol, more preferably
Preferably, it is 0.1 mol to 100 mol. The reducing agent used in the heat-developable photosensitive material of the present invention is
The method commonly used in the field of color photosensitive materials is used.
For example, U.S. Pat. No. 3,531°286
, No. 13, 7 [No. 31,270, No. 3, 764,
328 specifications, and R D No. 12146,
Same No. 15108, Same No. 15127Sj and Japanese Unexamined Patent Publication No. 56-27132, etc.
ll-phenylenediamine series and 1)-amino
Phenolic developing agent, 7-mole, 7-o-7-mide, 7-er/-
and sulfonamide 7-emer type developing agents, as well as
Examples include Drazon type color developing agents. Matoko, US special
Permit No. 3,342.599, No. 3.719,492
, JP-A-53135G28, JP-A No. 54-79035, etc.
The color developing herbal drug precursors listed in @ are also advantageous.
Can be used. As a particularly preferable reducing agent,
The following general formula [8] written in No. 33 Akira $n1
1] is mentioned. ItJItll In the formula, R' and R2 are hydrogen atoms, or r! 1 substituent
Number of carbon atoms that may be present is 1 to 30 (preferably 1 to 4)
represents a furkyl group, and R' and R2 are ring-closed to form a heterocyclic ring.
may be formed. R3, R', R5 and R6 are hydrogen
Atom, halogen atom, hydroxy group, amine 7 group, alco
xy group, acylamido group, sulfonamide group, alkyl
Sulfonamide group or r! Carbon which may have one substituent
represents an alkyl group of n to 30 (preferably 1 to 4) atoms;
Then, R) and R'S3, I/R' and R2 are respectively closed rings.
may be used to form a heterocycle. M is an alkali metal atom,
ammonium group, nitrogen-containing growth base group or quaternary nitrogen atom
Represents a compound containing. The nitrogen-containing growing base in the above general formula [81] is a non-sulfuric acid
A growing compound containing a basic nitrogen atom that can form a salt with
Amine compounds are the most important IT bases.
can be mentioned. And as a chain amine compound, the first
amines, secondary amines, tertiary amines, etc.
A typical heterocyclic base for amine compounds with
Examples include the young names birinone, quinoline, piperinone, and
Examples include midazole and the like. Other hydroquine luamine
Compounds such as , hydranone, and amidine also form chain amines.
It is useful. In addition, the salts of nitrogen-containing growth bases are as follows:
Inorganic acid salts of organic bases such as hydrochlorides, sulfates,
nitrates, etc.) are preferably used. On the other hand, as a compound containing quaternary nitrogen in the above general formula
For example, a salt of a substituted compound having a tetravalent covalent bond or water
Examples include oxides. Next, preferable reducing agents represented by the above general formula [81]
A specific example is shown below. (R-1) (R-2) (R-3) (R-4) (R-5) (R-8) (R-7) (R-8) (R-12) (R-13> (R-14) (R-15) (R-16) (R-17) (R-ts) (R-19) (R-20) (R-21) ([(-22) (R-23 ) The reducing agent represented by the above general formula [81] can be prepared by a known method.
, e.g. LIoul) en Weyl+Metl+o
den derOrgn++isc! +en Cl+
emie, BanJX I/2.645-70
It is synthesized according to the method described on page 3. Reducing agents such as those described below can also be used.
. For example, 7er/-ols (e.g. p7zyl 7er/-
II-methoxyphenol, 2,6-noterL-b
Chill-n-cresol, N-methyl-1]-7mino7e
), sulfonamidophenol M [e.g. 4-
Benzenesulfonamidophenol, 2benzenesulfonamide
amide 7-er/-ol, 216-nochlor a-4~benzene
Sulfonamide 7ヱ/-l, 2,6-dipromo 4-(
p) luenesulfonamide) 7 ether, etc.], or poly
Hydroxybenzenes (e.g. hydroquinone s L
erL-butylhydroquinone, 2,6-dimethylhydroquinone
Dooquinone, chlorohydroquinone, carboxyhydride
Roki/N, catechol, 3-carboxylic acid, tefur, etc.)
, naphthol M (e.g. α-su7tol, β-su7tol)
4-ami7su7thol, 4-methoxynaphthol, etc.
), hydroxybinaphthyls and methylenebisnaphthyls
For example, 1,1''-dihi1!roxy2,2'-
Binaphthyl, 6,6′-dibromo-2,2′-nohydro
xy1.1'-binaphthyl, 6.6-sinitro2.
2'-dihydroxy-1,1'-binaphthyl, 4.4'
-dimethoxy-1,1'-dihydroxy-2,2'-bi
Naphthyl, bis(2-hydroxy-1-7thyl)meth
1, methylene bisphenols [e.g. 1.1-bisphenols]
Su(2-hydroxy-3,5-tmethyl7enyl)-3
,5,5-)methylhexane, 1,1-bis(2-hydroxy
Droxy-3-terL-butyl-5-methylphenyl
) methane, 1,1-bis(2-hydroxy-3,5-no
-tcrL-butylphenyl)methane, 2,6-methylene
bis(2-hydroxy-3-LerL-butyl-5-
Methyl 7enyl)-4-methylphenol, α-7enyl
Le α, α-bis(2-hydroxy-3,5-No Le
rt-butylphenyl)methane, α-phenyl-α, α
-bis(2-hy1rroxy3-terL-butyl-
5-methyl7enyl)methane, 1,1-bis(2-hydro)
Roxy-3,5-dimethyl7enyl)-2-methylpro
Pan, 1.1.5.5-tetrakis(2-hydroxy-
3,5-trimethylphenyl)-2,4-ditylpenkun
, 2,2-bis(4-hydroxy-3,5-dimethylphenate)
phenyl)propane, 2,2-bis(4-hydroxy-3
-methyl-5-terL-butylphenyl)propane,
2.2-bis(4-human axy-3,5-noLert
-butylphenyl) to fropan! Pl, ascorbic t
[I'[,3-pyrazolidones, ascorbic acids, 3
-pyrazolidones, pyrazolones, hydrazones and
Examples include para-7-functional nylennoamines. These reducing agents can be used alone or in combination of 2 fi1 or more.
You can also be there. The amount of reducing agent used depends on the sensitizer used.
Types of silver halides, types of organic acid silver salts, and others
Depends on the type of additive used, but usually the dye donor
The amount is in the range of 0.05 to 10 mol per mol of monomer.
The amount is preferably 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, heptalated 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 vinylpyrrolidoneff
This includes 1 organization. Vinylpyrrolidone polymer is
Polyvinylpyrroli, which is the 4n-polymerized version of nilpyrrolidone
It can also be a copolymer with vinylpyrrolidone.
copolymers with one or more other monomers capable of
Contains copolymers. ). These polymers
- can be used regardless of its synthetic leather. Polybi
Nilpyrrolidone device 1 Capolyvinylpyrrolidone
The preferred polyvinylpyrrolidone has a molecular weight of 1,
000 to 400.000. vinyl pyrrolide
Other monomers that can be copolymerized with acrylic acid,
Such as methacrylic acid and its alkyl esters (meth)
Acrylic esters, vinyl alcohols, vinyl alcohols
Coal type, (meth)acrylic 7 types, vinyl ruby/
- vinyl monomers such as vinyl alkyl ether M, etc.
- etc., but at least 20% of the composition ratio (by weight)
%, hereinafter the same) is preferably polyvinylpyrrolidone.
Delicious. A preferred example of a darkening copolymer has a molecular weight of 5
, 000 to 400.000. Gelatin is either lime-treated or acid-treated. thing
However, ossein gelatin, big skin gelatin,
Hyde gelatin or esterification of these, phenylcal
Modified gelatin that has been bamoylated 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%.
, it is preferred that the polymer of the present invention has a molecular weight of 5 to 9096.
It is 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 vinyl, lolidone, and one or more other polymeric substances
Mixture, gelatin and molecular Ji5,000-400゜0
00 vinylpyrrolidone copolymer and one or more other
Mixtures with polymeric substances are preferred. Other polymers used
Substances include polyvinyl alcohol and polyacrylic.
Amide, polymethacrylamide, polyvinyl butyral
, polyethylene glycol, polyethylene glycol
Proteins such as esters or cellulose derivatives
Natural substances such as polysaccharides such as , starch, gum arabic etc.
can be mentioned. These range from 0 to 85%, preferably from 0 to 7
It may be contained in an amount of 0%. 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 of additional cross-linking reaction due to natural standing)
) is preferred. The amount of binder used is usually 90% for 1+n2 supports.
．． 005B to 100g, preferably 0.0.1F
1 to 408. In addition, the binder is a dye-donating substance.
0.18 to 108 to be used per 1 g of quality monomer unit
The amount is preferably 0.25 to 4 g, 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
Magawara paper, printing paper, baryta paper and Renonoko-1 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 heat development and
/ or any substance that promotes thermal transfer, preferably
is solid, semi-solid, or liquid at room temperature and cannot be heated.
It is a substance that dissolves or acts as a solvent in the binder.
Therefore, preferably urea derivatives (e.g. dimethylurea) are used.
, diethylurea, phenylthure 7, etc.), amide derivatives
, (e.g. acetamide, benzamide, etc.), polyvalent amines
Lecol U (fJII + r, i, s-bentanedio
1,6-bentanediol, 1,2-cyclohexane
diol, pentaerythritol, trimethylol
ethane, etc.) or polyethylene glycols.
Ru. As a detailed example, vfHn 1986-1042
It is written @ in 49. These thermal solvents can be used alone or in two types.
The above may be used in combination. 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. Pat.
No. 40, No. 3,531,285, fjS4,01
No. 2,260, No. 4,060,420, Pt54
, No. 088,496 No. 4,207,392 Specifications
, RD No. 15733, RD No. 15734
No. 15776, JP-A-56-13074
Urea described in No. 5, No. 56-1323i32, etc.
Alkali release agents such as guanidium trichloroacetate
, U.S. Patent No. 12700/1983
-c o -, +s described in No. 3,667.959
Non-aqueous polar solvation with o 2- , + s o- groups
compound, mel described in U.S. Patent No. fjS3,438,776
National Patent No. 3,666.477, Japanese Patent Publication No. 3,666.477
Polyalkylene glycol described in No. 51-19525
There are other types. In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5
No. 020, No. 49-91215, No. 49-10772
No. 7, No. 50-2524, No. 50-67132, No. 50-67132, No. 50-2524, No. 50-67132, No.
No. 50-07041, No. 50-n4217, No. 52-
No. 33722, No. 52-99813, No. 53-102
No. 0, No. 53-55n5, No. 53-70020, No. 53-55n5, No. 53-70020, No.
No. 53-125014, No. 54-15 (No. 3523, No. 54-15)
No. 54-15+3524, No. 54-156525, No. 54-15+3524, No. 54-156525, No.
No. 54-156526, No. 55-4060, No. 55-
Publications such as No. 4081 and No. 55-32015, as well as
German Patent No. 2,140,406, German Patent No. 2.147.0 (
No. 33, 2,220. +318, U.S. Patent No. 3,0
No. 80,254, No. 3,847,612, fi.
No. 3,782.941, same No. 3゜994, No. 7:72
, PA 4,123.282, PA 4,201,58
7 Tara, which is a compound described in each specification such as No. 2
Nonone, 7-thalimide, pyrazolone, quinazolinone, N
-Hydroxynaphthalimide, benzoxazine, naph
tooxanonedione, 2,3-dihydro-7talanone
on, 2t3-dihydro-1, :(-oxazine-2,
4-dione, oxypyridine, aminopyridine, hydro
xyxylin, ami/quinoline, incarbostyril,
Sulfonamide, 2H-1,3-benzothianone-2,
4-(3H)dione, benzotriazine,/lucapto
Riazole, Nomercaptotetrazabentalene, Heptal
acid, nathalic acid, phthalamic acid, etc., and these 1
a mixture of one or more with an imiguzol compound;
Also, there is a small amount of acids or acid anhydrides such as 7-talic acid and natal acid.
A mixture of at least one and seven talanone compounds, as well as
, 7 Taracin and maleic acid, itafonic acid, quinolinic acid,
Examples include combinations of dentisic acid and the like. Also, JP-A-58-189628, JP-A No. 58-1934
3-7 minnow 5-mercapto described in Publication No. 60
-1゜2.4-) Riazoles, 3-acylamino-5
-mercap)-1,2,4-) lyazoles are also effective.
Ru. Furthermore, as an antifoggant, for example,
7-+n1:) No. 49-90n8, 4
No. 9-10724, No. 49-97013, No. 50-1
No. 01019, No. 49-130720, No. 50-12
No. 3331, No. 51-47419, No. 51-5743
No. 5, No. 51-78227, No. 51-104338
, No. 53-19825, No. 53-20923, No. 5
No. 1-50725, No. 51-3223, No. 51-42
No. 529, No. 51-8n24, No. 54-51821
, Publications such as No. 55-93149, and British Patent No.
L455+271, U.S. Patent 153, 885, 9
No. 68, No. 3,700,457, No. 14,137.
No. 079, No. 4,138°365, West German patent i1)
'$ 2,617.907 etc. as stated in each specification
f52 mercury salt, which is a compound containing
, N-halodenoacetamide, N-halodenosuccinic acid
Mido, perchloric acid and its salts, Kuroiso peroxide, persulfuric acid
salts, etc.), or acids and their salts (e.g., sulfine
acid, lithium laurate, rosin, diterpene acid, thio
sulfonic acids, etc.) or sulfur-containing compounds (e.g.
Lucapato compound-releasing compound, thiouracil, nosulf
ido, simple sulfur, mercapto-1,2,4-triazo
compounds, thiazolinthione, polysulfide compounds, etc.),
Others: oxazoline, 1.2.4-triazole, 7
Examples include compounds such as talimide. Furthermore, as another anti-capri agent, JP-A-59-n1 (33
Thiol (preferably thiophenol) described in No. 6
compounds) are also effective. As an antifoggant, Japanese Patent Application No. 59-56506
Hydroquinone derivatives described in
chillhydroquinone, dodecanylhydroquinone, etc.)
Hydroquinone induction described in Japanese Patent Application No. 59-66380
and benzotriazole derivatives (e.g. 4-sulfoben
Zotriazole, 5-carboxybenzotriazole, etc.
) can be preferably used in combination. Also, as a stabilizer, especially a printout prevention agent after processing.
They may also be used at the same time (for example, JP-A No. 48-45228)
, 5 (No. 1-n9624, No. 50-120328,
Halogenated hydrocarbon water described in Publication No. 53-46020 etc.
elements, basically tetrabromobutane, tribromoeta
nor, 2-bromo-2-tolyl 7cetamide, 2-butyl
lomo 2-tolylsulfonylacetamide, 2-)
+77' lomomethylsulfonylbenzothiazole, 2.
4-bis(tribromomethyl)-6-methyltrianone
etc. Also, JP 40-5393, JP 50-54329
No. 50-77034, sulfur-containing
Post-treatment may be carried out using the compound. Additionally, U.S. Patent No. 3.301. (No. 378, same No. 3
, No. 506,444, trS: No. 1,824,103
, No. 3,844.788, inches listed in each specification town 8
Uronium-based stabilizer precursor, also US special
No. 13,6 Ei9,670, No. 4,012゜260
No. f54,060,420 Mei #I, etc.
Actylvator stabilizer-precursor etc.
May have. Also, sucrose, former 14Fe (SO4)2 ・12! I□
A water release agent such as No. 0 may also 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,
Addition of various agents, hardeners, antistatic agents, plasticizers, and spreading knots.
agents, coating aids, etc. are added. 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. 3.301.078, fjS
No. 3,506,444, No. 3,824,103, No. 3,824,103, No. 3,824,103, No.
No. 3.844.788 Inchiuroni as described in each specification
Um-based stabilizer precursor, and U.S. Patent No. 3
, No. 669,070, ff.54,012゜260,
Act No. 4,060,420 written in Memorandum etc.
May contain beta stabilizer precursor etc.
stomach. In addition, SiM sugar, Nl14Fe(SO4)2 ・12n2
To 0! ? A water release agent may also be used;
Heat development is performed by supplying water as in No. 50-132332.
It's okay to be. In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention further includes
Spectral sensitizing dyes, antihalation dyes, fluorescent
Optical brighteners, hardeners, antistatic agents, plasticizers, various types of spreading knots
Additives, coating aids, etc. can be added. The heat-developable photosensitive material of the present invention basically has (1
) Photosensitive silver halide, (2) 3a base agent, (3) present invention
(4) a dye-donating polymer which is a dye-donating substance;
(5) organic silver salt as necessary.
However, these are not necessarily simple.
It is not necessary to contain it in one photographic constituent layer, for example, photosensitive
Divide the sexual layer into two pieces and add the above (1), (2), (4), and (5)
) is contained in the photosensitive layer on one side, and this photosensitive layer
on the other side adjacent to the color which is the dye-donating substance of the present invention.
Reacts with each other, such as by containing element-donating polymer (2)
If possible, contain it separately in two or more photographic constituent layers.
You can close it. In addition, the photosensitive layer may be two or more layers, such as a high-sensitivity layer and a bottom-sensitivity layer.
It is also possible to divide the pond on the top, and to make the color sensitivity of the pond different.
It may have one or more photosensitive layers, or an overcoat layer.
, subbing layer, backing layer, intermediate layer, or filter layer.
It may have various photographic constituent layers such as layers. Similar to the heat-developable photosensitive layer of the present invention, a retaining layer, an intermediate layer, and an undercoat.
layer, back layer, and other photographic constituent layers.
Adjust the coating solution and use the dipping method, air knife method, curtain method, etc.
coating method or as described in U.S. Pat. No. 3,881°294.
Create photosensitive materials using various coating methods such as hopper coating method
can do. Further, if necessary, U.S. Pat. No. 2,761.791 and
by the method described in British Patent No. 837,095.
It is also possible to apply 2WI or more at the same time.
Ru. The above-mentioned material used in the photographic constituent layer of the heat-developable photosensitive material of the present invention
1 & min of is applied onto the support and the thickness of the application is determined by
1 to 1,000 μm after drying, more preferably
It is 3 to 20 μIn. After the heat-developable photosensitive material of the present invention is imagewise exposed,
i! + Usually 80°C to 200°C, preferably 102°C to 17°C
Color development is achieved by simply heating for 0 seconds to 120 seconds. In addition, if necessary, develop with a water-impermeable material in close contact with the film.
or a temperature range of 70°C to 180°C before exposure.
Preheating may be performed in an enclosed environment. 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. Usually a normal color
Light sources used for lint, e.g. tungsten lamps,
Mercury lamp, xenon lamp, laser beam, CRT beam, etc.
can be used as a light source. 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, and furthermore, in the photosensitive material of the present invention or
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
First, high temperature for a short time, or low temperature for a long time, continuously.
rising, falling or repeating, and even discontinuous heating
Although it is possible, a simple pattern is preferable. Dew again
A method may also be used in which light and heating are applied repeatedly at the same time. In the present invention, the photographic constituent layers are imagewise exposed and thermally developed.
A receiver (!4
! Use scraps that are commonly used in this field.
For example, paper, cloth, plastic, etc.
Preferably, a mordant or color is applied to the support.
An image-receiving layer containing a compound having elementary-receptive fIR power is provided.
is used. As a particularly preferable image receiving layer, Japanese Patent Application No. 58-97907
Layer made of polyvinyl chloride and vtM described in No. 1983
- Polycarbonate and plasticizer described in No. 128600
There are different 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, and any technique can be used.
can be done. [Example] Examples of the present invention are shown below.
It is not limited to these. In addition, the dye-donating substance port used as a comparative example of the following example
The remers are shown in Table 2 below. Table-2 In Table-2, the abbreviations of comonomers have the same meanings as in Table-1.
Ru. Example 1 <Organic silver salt dispersion> 5-methylbenzotriazole and silver nitrate were dissolved in water-alcohol
5-methylbenzo obtained by reacting in a mixed solvent of
Triazole silver 28.8. and poly(N-vinylpyrroli)
16.0 g and 4-sulbobenzotriazole
Sodium salt 1.33. dispersed in an alumina ball mill.
, pH 5.5 and 200 +aQ. Preparation of silver bromide emulsion for comparison> A silver bromide emulsion for comparison was prepared by the following method.
℃l: t:f i” (, vfn3n 1984-925
Mixing and stirring shown in No. 23 and No. 57-92524
Using a machine, add 20 g of ossein gelatin to 10 g of distilled water.
Add 1 part of potassium bromide to the helium solution containing 0O and ammonia.
．． 500 mQ of an aqueous solution containing 1 mol of B solution and nitric acid
Water-soluble fi500m containing 1 mole of silver and ammonia
Solution C of Q was added at the same time while keeping the pAg constant. The shape and size of the emulsion grains to be prepared are determined by pH, prig and
This was adjusted by controlling the addition rates of liquid B and liquid C. this
A silver bromide emulsion was prepared in this manner. The obtained silver halide grains had an average grain size of 0.3 μm.
The particles were octahedral particles with a coefficient of variation of diameter distribution of 8%. This emulsion was washed with water and desalted. The yield of emulsion is 800 II
IQ (emulsion - 8 toyoko ζ) Made of silver iodobromide emulsion RF4> Four types of emulsions with different silver iodide contents were prepared by the following method.
Prepared. At 50°C, JP-A No. 57-92523, No. 57
-92524 Publication using the mixing agitation method,
Ingelatin 20g 1 distilled water 1000+aQ and ammonium
Potassium iodide and potassium bromide are added to solution A in which Nia is dissolved.
Contains 1500+n (l of B solution and 1 mole of nitrate)
Aqueous solution 500+eQL containing hydrogen and ammonia:
nC solution was added at the same time while keeping the pAg constant. tone
The shape and size of the emulsion particles to be produced are determined by pH, pAg and B solution.
It was adjusted by controlling the addition rate of liquid C and C. like this
and have the same regular octahedral shape and different silver iodide content.
An emulsion was prepared. (variation of grain size distribution of each emulsion)
The number was 9%. ) These emulsions were washed with water and dehydrated.
I salted it. The yield of each emulsion was 800ml. The grain size and silver iodide content of each emulsion thus prepared
The percentage is shown in Table 3 below. Below is a blank table-3 <Dye-donor dispersion liquid> Polymer dye-donor substances P-1, P-8, I'-17, P-
27, 35.5 g each of P-31 and the following hydroquinone
5.00g of each compound was added to 200mQ of ethyl acetate.
Dissolve Alka/-L XC (manufactured by DuPont) in 5% water by weight.
Solution 124mQ, 7 z-nylcarbamomolized gelatin
(Rouslow Company, Type 17819 PC) 30.5g
Aqueous gelatin solution containing 72 (mixed with hQ to generate ultra-f wave homo
After dispersing with a genizer and distilling off ethyl acetate, the pH
5.5 and it was 795169. Hydroquinone compound n+1 <Developer> Developer, (R-n) 23.3F1, the following development accelerator 1.
10tr, poly(N-vinylpyrrolidone) 14.6g,
Dissolve 0.50g of the following fluorosurfactant in water and adjust the pH.
5.5 and set it to 250+nQ. Development accelerator surfactant Na0yS C1! -C00CII2(CF2CF2
)mllCn2C00Cn2(CF2CF2)nn(I
I+, ++ = 2 or 3) <Heat-developable photosensitive element> Growing silver dispersion 12.5 mQ, each silver halide emulsion 6.0
0+n, each dye-providing substance dispersion 39.8+J, developer
12.5mQ, and then add a hardener solution (tetra(bicarbonate)
Nilsulfonylmethyl) methane and taurine 1:1 (heavy)
phenylcarbamoylated gelatin 1
Tetra(vinylsulfonylmethyl) dissolved in 96 aqueous solution.
) Contains 3% methane by weight. ) 2,5
(See, Polyethylene Glyfur 300 is used as a thermal solvent.)
After adding 3.80g of (Kanto Kagaku), subtraction was applied.
Photographic polyethylene 7-talate film with a thickness of 180 μm
On the lum, fa fJ is 1.76g/+a2.
Apply the phenylcarbamoyl on top of the sea urchin.
Mixture of gelatin and BoIJ (N-vinylpyrrolidone)
A protective layer consisting of <Image receiving element> Polyvinyl chloride (n=1,10
Apply a tetrahydro 7 run solution of Wako Pure Chemical Industries, Ltd.
Make sure that the polyvinyl chloride is 12 g/+a2.
Ta. Pass the step wedge through the heat-developable photosensitive element.
1600C, M, S, and combined with the image receiving element.
Heat developing machine (developer module 277°3M)
After heat development at 150°C for 1 minute at
If you quickly peel off the element and image-receiving element, the polygons of the image-receiving element will be removed.
Magenta step wedge screws are attached to the vinyl chloride surface.
A moth image was obtained. The reflection density of the obtained negative image was measured using a densitometer (
PAD-65, manufactured by Konishiroku Photo Industry Co., Ltd.)
The maximum concentration and minimum concentration (capri) are shown in Table 4 below. Table-4 As is clear from Table-4, weight average molecular weight 30,00
A heat-developable photosensitive material using a polymeric dye-donating substance of 0 or more is
, silver halide further containing 4 to 20 mol% of silver iodide
Thermal fog can be further reduced by combining with
. Example-2 <Preparation of core/shell type silver iodobromide emulsion> Containing ffi iodide
4 fl with different rate and particle size! Class II core/shell
A double emulsion was prepared by the following method. At 50°C, JP-A-57-92523, JP-A-57-92523;
Using the mixing and stirring method shown in Japanese Patent No. 92524, Osei
gelatin 20B, distilled water 1000J and ammonia
The dissolved Δ solution contains potassium iodide and potassium bromide.
An aqueous solution of 500+nQnn and 1 mol of silver nitrate.
Water solution f (tt500u+Q C solution containing Monia)
were added at the same time while keeping -g constant. to prepare
The shape and size of the particles of A7L agent are 1]1 (and V pAg
, and by controlling the addition rate of liquid 0 and liquid C.
did. In this way, the same shape and particle size of the regular octahedron
and core emulsions with different silver iodide contents were prepared. The coefficient of variation of the particle size distribution of each core emulsion was 8%.
. Next, the 10 silver denide grains of the above core emulsion are used as cores.
This is then coated with a silver halide shell in the same manner as above.
By doing so, the particles have the same regular octahedral shape and particle size.
Then, core/shell emulsions with different silver iodide contents were prepared.
Ta. Each of these emulsions was washed with water and desalted. Yield of each emulsion
was 800+aQ. The grain size of each core/shell emulsion thus prepared was
The silver iodide content and silver iodide content are shown in Table 5 below. Table 5 The silver halide prepared above was mixed with the following sensitizing dye and 4-
Hydroxy-6-methyl-1,3,3a,7-titraza
Sulfur increase by sodium thiosulfate in the presence of indene
A photosensitive silver halide dispersion with the following composition was prepared by sensitization treatment.
Manufactured. Silver halide (converted to ffi) 381gze
Latin 85g/3530+aQ
The sensitizing dye was changed and the polymeric dye-providing substance was changed to P-3, P-12 and
The same procedure as in Example-1 was preferred except that P-28 was used.
The results obtained are shown in Table 6. Margin Table-6 below As is clear from Table-2, silver iodide is in the range of 4 to 20 moles.
If it is, even silver halide with core-shell structure can be used as a thermal coupler
silver halide with a core-shell structure.
is preferable because the capri to the maximum concentration is lower.
I understand. Effect of the invention 1 From the present invention, a photosensitive silver halide, a dye-providing substance,
Reducing agent J: Contains a binder and is diffusible by heat development.
Forms or releases a dye and transfers the dye to an image-receiving layer to create a color.
Obtained by a type of heat-developable photosensitive material that produces an original image
The capri of the dye image is improved.

Claims (1)

[Scope of Claims] In a heat-developable photosensitive material having at least a photosensitive silver halide, a dye-providing substance, a reducing agent, and a binder on a support, the dye-providing substance is represented by the following general formula [1] or [
2) is a polymer having a weight average molecular weight of 30,000 or more and having a repeating unit derived from a monomer represented by the above, and the photosensitive silver halide has a silver iodide content of 4 mol % to 40 mol %. General formula [1] (Q)-(X)-_nCp_1 General formula [2]
] (Q)-Cp_2-(X)-_nDye [In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and Cp_1 and Cp_2 each react with the oxidized form of the reducing agent and diffuse Dye is an organic group that forms or releases a divalent dye, X represents a divalent bonding group, X is bonded to the active site of Cp_1 and Cp_2, n represents 0 or 1, and Dye is a diffusible represents a dye residue. ]