JPH02236542A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To prevent thermal fogging by incorporating a part contg. polyvalent metal ions at a specific ratio or above into a photosensitive silver halide at >=10% weight of the silver halide. CONSTITUTION:The Frenkel balance in silver halide particles collapses and the concn. of interlattice silver ions lower when a large amt. of the polyvalent metal ions are doped. On the other hand, the silver ion vacancy concn. having the equil. relation with the interlattice silver ions increases. The salt of the polyvalent metal ions is required to be made present during the particle formation of the silver halide in order to dope a large amt. of the polyvalent metal ions. The part where the silver ion vacancy governs, namely, the part where the polyvalent metal ions are doped at >=1X10<-4>mol/molAg is required to be >=10% of the weight of the total silver halide even if any structure is assumed. The heat developable photosensitive material which prevents the thermal fogging is obtd. in this way without hindering the development.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a heat-developable photosensitive material, and particularly to a heat-developable photosensitive material that exhibits low fog when thermally developed and is highly sensitive.

(Background Art) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (published by Corona Publishing, 1982), pages 242 to 255. Page, US Pat. No. 4,500,626, etc. In addition, methods of forming a dye box image by a coupling reaction between an oxidized developing agent and a coupler are described in US Pat. No. 3,761,270 and US Pat. No. 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957, etc. Recently, a method has been proposed in which a diffusive dye is released or formed in an image by thermal development and the diffusible dye is transferred to a dye-fixing element. In this method, both negative and positive dye images can be obtained by changing the dye-providing compound #1M4 or the type of silver halide used. For more details, see US Patent Nos. 4,500,626, 4,483,914, and 4,50313
No. 7, No. 4559290, JP-A-58-149046
No., JP-A-60-133449, No. 5 9-2 18
No. 443, No. 61-238056, European Patent Publication 22
No. 0746A2, Technical Report No. 87-6199, European Patent Publication No. 210660A2, etc. Many methods have been proposed for obtaining clear color images by heat development.

For example, US Pat. No. 4,559,290 describes the so-called DRR.
A reducing agent or its precursor is coexisted with an oxidized compound that does not have the ability to emit a color image, and the reducing agent is oxidized according to the amount of exposure of the halogenated group by heat development, and the reducing agent that remains unoxidized is A method has been proposed in which a diffusible dye is released by reduction. Also, European Patent Publication No. 22074
No. 6, Technical Report 87-6199 (Volume 12, No. 22) describes compounds that release diffusible dyes by a similar mechanism.
A heat-developable color photosensitive material using a compound that releases a diffusible dye upon reductive cleavage of an N--X bond (X represents an oxygen atom, nitrogen atom, or sulfur atom) has been described. By the way, thermal development often produces fog (thermal fog) that cannot be predicted from normal wet development (processing in a developer). This thermal fog is a major problem in image formation. Thermal fog leads to an increase in the minimum density in negative-type heat-developable photosensitive materials that produce color images corresponding to latent images, and in positive-type photothermographic materials that produce color images in inverse correspondence to latent images. This results in a decrease in the maximum concentration. In particular, when an emulsion containing large-sized silver halide grains is used to obtain high sensitivity, this thermal fog is likely to occur and is a factor that inhibits the high sensitivity. Conventionally, in order to prevent this thermal fog, it is common to use an organic compound called an antifoggant. However, conventional antifoggants are unsatisfactory because they have a weak effect of suppressing fog, or they inhibit development while suppressing fog, resulting in a decrease in image density.

For these reasons, there is no clear guideline on how to design a photosensitive silver halide emulsion that can be passed through a heat-developable photosensitive material, and various performances (especially thermal fogging) have been determined through trial and error. The reality is that we are pursuing countermeasures and sensitization.

Furthermore, the present inventor previously reported in Japanese Patent Application No. 62-274843 that as a photosensitive silver halide for a heat-developable photosensitive material, IX10-'~! It has been reported that using silver halide containing XIO-S moles of iridium results in high sensitivity and low thermal fog.
There was no knowledge whatsoever regarding the performance when containing more than 10-5 mol of iridium or when containing a large amount of heavy metals other than iridium.

Attempts to use polyvalent metal compounds in silver halide emulsions have been studied for a long time. Research Disclosure Magazine 1
RD-17643 in Volume 76 (December 1978)
There are descriptions of gold, platinum, palladium, iridium, osmium, rhenium, etc. as chemical exacerbants, and also Research Disclosure Vol. 184 <197
RD-18431 (August 1999) states that when copper, thallium, cadmium, rhodium, tungsten, thorium, or iridium is present during precipitation of a halogenated emulsion, sensitization occurs in the case of X-ray photography. There is. In addition, it is preferable that the emulsion used in the photo-developable photosensitive material has high internal sensitivity and low surface sensitivity.
It is stated that it may contain l * or trivalent metals (Fundamentals of Photographic Engineering, edited by the Photographic Society of Japan, Corona Publishing, 1978, Page 545). RD-17643 describes that a direct print emulsion is prepared in the presence of soot, lead, copper, cadmium, bismuth, magnesium, rhodium, and iridium. U.S. Patent No. 3,923.513 describes that an internal latent image type emulsion is prepared by doping with polyvalent metal ions, including doping with divalent metal ions such as lead, antimony, bismuth, arsenic, etc.
Trivalent ions such as gold, iridium, and rhodium, and tetravalent ions such as platinum, osmium, and iridium are said to be useful. As can be seen from these examples, emulsions doped with polyvalent metal ions are used to increase internal sensitivity, and polyvalent metal ions increase internal defects and create electronic trasops. It is considered. Therefore, in ordinary high-sensitivity emulsions in which photosensitive nuclei are intentionally created using sulfur sensitizers or gold sensitizers, doping -a with polyvalent metal ions introduces competitive centers, resulting in quantum sensitivity. It is considered undesirable in terms of For example, Rh, a typical polyvalent metal ion, is used in emulsions whose surfaces are chemically sensitized.
It is well known that when '゜ is doped, Rh''' acts as an electron capture center, resulting in desensitization and high contrast, and this is used in practical applications such as printing sensitive materials that require high contrast. Iridium is a unique example of a typical polyvalent metal ion.In this case, 104 to 10-'
It is known that when grains are formed in the presence of approximately mol/mol Ag, effects such as sensitization and improvement of high illuminance failure can be obtained even in emulsions whose surfaces have been chemically sensitized (Japanese Patent Publication No. 43-4
935, 45-32738, or JP-A-58-221
839, 59-152438). However, in these reports, the amount of iridium added is 10-10-
At the same time, it has been reported that mole/mole Ag is preferable, and that when it exceeds to-', a significant decrease in sensitivity occurs, and no improvement in characteristics is observed, making it impractical. Therefore, there has been almost no study on increasing the sensitivity of emulsions containing a large amount of 10-' moles or more.

Representative examples of divalent metal ions include Cd'' and Pbl''. Examples of the presence of large amounts of these compounds during particle formation are described in the literature, such as Wyrsh's AgCINj
During the preparation of FJ, Cd(NOx
)* was present, but it was reported that the amount of doping was less than 10 −6 mol/mol.

(International Congress o
f Photographic Science, 1
9 7 8) Furthermore, Lloyen reported that although a large amount of Pb(NO3)x was present during the preparation of an AgBr emulsion, only a small amount could be doped.

(Journal or＾pplied Physics
s, Vol. 4, p. 3784, 1976) As can be seen from these examples, it was known to dope silver halide emulsion grains with small amounts of divalent metal ions such as Pb and Cd'''; The technique of doping with a large amount of impurities of 4 mol/mol Ag or more was unknown.Therefore, there was no knowledge of the photographic sensitivity of emulsions doped with a large amount of divalent metals, especially the effect of applying them to heat-developable photosensitive materials. (Problem B to be solved by the invention) An object of the present invention is to provide a heat-developable photosensitive material that prevents thermal fog without inhibiting development, and also has high sensitivity and little thermal fog. The purpose of the present invention is to provide a heat-developable photosensitive material.

(Means for Solving the Problems) An object of the present invention is to provide a heat-developable photosensitive material comprising at least a photosensitive silver halide and a binder on a support, in which the photosensitive silver halide contains polyvalent metal ions. This has been achieved by a heat-developable light-sensitive material characterized in that it contains 10-4 mol or more of silver halide in an amount of 1.times.10@-4 mole or more per mole of halide iml. The question of the mechanism by which the effects of the present invention are produced will have to wait for detailed investigation in the future, but the Frenkel equilibrium within the silver halide grains shifts when a large amount of polyvalent metal ions are doped. It is predicted that this will happen. In ordinary photosensitive silver halide grains, the concentration of mobile silver ions called interstitial silver ions is high and exceeds the number of silver ion vacancies, which are holes for silver ions. Mobile silver ion
the Photographic Process
4th ed. T. [l. Jai+esed. ，
According to Maca+Illan 1977), silver halide is considered essential for photosensitivity. When a silver halide crystal is doped with polyvalent metal ions, the interstitial silver ion concentration decreases, while the silver ion vacancy concentration, which is in equilibrium with the interstitial silver ions, increases.
Are known. When a large crystal is doped with an impurity of about lO-1 mol per mol of silver halide, the number of silver ion vacancies exceeds the number of interstitial silver ions, and the ionic conductivity in the crystal becomes dominated by daughter ion vacancies. It is well known (for example, F.C., Brown, The
Physics of Solids, W. A, Bej
asinsha 1967}. However, it is known that in silver halide crystals used as photographic light-sensitive materials, a large amount of interstitial silver ions are present due to surface effects. According to the literature (S. Takada, Photogr.
aphic Science and Englnee
ring, page 18S500, 1974) It has been reported that silver bromide emulsion grains have an interstitial silver ion concentration about two orders of magnitude higher. There are almost no known examples of silver halide microcrystals dominated by silver ion vacancies. Only a few cases have been reported in which AgCl is doped with about 10-' mole of Cd2°. (Hoyen
．． Ehrlich, Briggs, The Inter
nationa) East-West Symposia
um on the factors influen
cingPhotographic Sensitiv
ity, 1984, S. Takada's above-mentioned literature} Silver bromide or iodobromide used in high-strength emulsions has a high concentration of interstitial silver ions, so it is necessary to dope a large amount of polyvalent metal ions to make the silver ions dominate the vacancies. it is conceivable that.

Ionic conductivity measurement is a method for determining the interstitial silver ion concentration and silver ion vacancy concentration in silver halide emulsion grains. In the case of emulsion grains, dielectric loss methods have been developed for this purpose.

(The Theory of the Photo
4th ed. ,T
．． }l. James ed. , Macmillan
1977, page 118 This method measures the frequency characteristics of impedance in a system in which silver halide grains are decomposed in an insulating medium such as gelatin, and is widely used in the industry. In order to provide information on the ionic conductivity inside the particle, it is widely used as an antifoggant on the surface of the particle to cancel the surface effect1.
It is preferable to carry out the measurement after sufficiently adsorbing an adsorbent such as -phenyl-5-mercabutotetrazole.

In order to dope a large amount of polyvalent metal ions according to the present invention, it is necessary to have a polyvalent metal ion salt present during the formation of silver halide grains. As a polyvalent metal, MgSCaSSr. ．． B
a, Aj! ,Sc,Y,La,Crs Mn1FaXC
o, Ni, Cu, Zn, Ga, RuSRh, Pd, Os
,I r,P t,CtL Hgs TISInx S
n. ．． Pbs Bi etc. can be used. These polyvalent metals can be added in the form of salts that can be dissolved during particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, and hydroxides. For example, CdBrg, C
dC1*, Cd(NOs)z, Pb(NOx)*,
P b (C H xc O O)iK 3 [F 43
(CN)hl, (NH4)#[Fe(CN)4]
, K3 [ rclh, ( N E { 4 ) s R
Examples include h C e &. These polyvalent metal compounds may be used alone or in combination of two or three or more. When two or more types are used in combination, the total number of moles of polyvalent metal ions becomes halogenated!
The effects of the present invention can be obtained by containing 10-4 or more per mole. Doping with polyvalent metal ions may have other effects in addition to increasing the silver ion vacancy concentration. Rh
Deep electron traps such as those that compete with latent image formation are undesirable from the viewpoint of high sensitivity. When doping polyvalent metal ions with such properties, it is necessary to devise ways to sufficiently compete with the electron traps caused by the metal ions of the photosensitive nucleus. It is also necessary to select development conditions for polyvalent metal ions that inhibit the development process.

Among polyvalent metal ions, white metal ions (Ru, Rh...
Pd, Os, lr, Pt) have the ability to provide electron traps better than other metal ions, so polyvalent metal ions other than platinum metal ions are preferable. Among the polyvalent metal ions, divalent metal ions are preferred. Among the divalent metal ions, Pb is more preferable.
t", Fe!+, and Cd@*. Particularly preferred is pb".

The polyvalent metal compound is preferably added after being dissolved in water or an appropriate solvent such as methanol or acetone. Hydrogen halide aqueous solution (e.g. HCI, HB
r) or alkali halides (e.g. KCI, N
A method of adding aCl, KBr, NaB, etc.) can be used. Also, acids or alkalis may be added if necessary. The polyvalent metal compound can be added to the reaction vessel before particle formation or during particle formation. Also, water-soluble 1B salts (e.g. A g N O 3) or aqueous alkali halides (e.g. NaCl, KBr, K
It is also possible to add it to l) and continuously add it during the formation of halogenated root particles. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. Furthermore, it is also preferable to combine various addition methods. During particle formation! If the polyvalent metal compound is present in an amount of 10-4 moles or more per mole of Il, the particles will not be doped. In fact, there are examples in the literature where particles were formed in the presence of 10 mol% or more of a polyvalent metal compound (D. Wyrsh, I.
international Congress ofP
Photographic Science+ 1 9
7 8 Dove Cd'' in A g C l emulsion, I
I. A. Iloyen, Journal of App
LiedPhysics. 4 7 S3 7 8 4
Page 1976, AgBr emulsion doped with “Pb”)
It has been reported that in both cases, almost no doping can be formed within the particles. It was extremely difficult to form particles doped with such a large amount of polyvalent metal ions. Therefore, there is almost no knowledge regarding the photographic properties of emulsions containing such grains, and according to the theory of photographic sensitization commonly considered in the industry, the concentration of interstitial silver ions, which is essential for sensitization, is extremely low. It was predicted that the particles would be disadvantageous for photosensitivity. It is completely unexpected and surprising that, as in the present invention, a chemically sensitized emulsion doped with a large amount of polyvalent metal ions has high sensitivity and favorable photographic properties with little thermal fog. .

In order to dope a large amount of polyvalent metal ions, it is necessary not only to have the polyvalent metal compound present during grain formation, but also to devise the grain formation conditions. For this purpose, it is necessary to find preferable particle formation conditions for each polyvalent metal ion through trial and error.

Grain formation temperature, type and concentration of protective colloid in the reaction vessel, pH during reaction, pAg during reaction, method and rate of addition of water-soluble silver salt and alkali halide, selection of appropriate silver halide solvent, and Careful selection of the concentration, amount of polyvalent metal ions, and their ligand species is required. For example, in order to dope a large amount of Pb14, Fe1, Cd'', etc., the reaction temperature is set to a relatively low temperature (for example, 30 to 50
℃》, use a silver halide solvent (for example, ammonia) at 5 cc/l or more, and increase the amount of the aqueous solution of water-soluble silver salt and alkali halide to the limit of the critical growth rate of the halogenated roots to cause the reaction. is preferable. As a method of increasing the amount added, US Patent No. 36507
The method of increasing the addition rate as described in No. 57 and the method of increasing the addition concentration as described in No. 4242445 and No. 4301241 can be preferably used. As for the doping amount of the polyvalent metal, it is preferable that a portion of I X 1 G-' moles or more is present in an amount of 10% by weight or more, particularly 30% by weight or more of the total silver halide grains. In order to quantitatively analyze polyvalent cation impurities doped in silver halide grains, atomic absorption spectrometry and inductively coupled frequency plasma (i)
nductively coupled plasma+
ICP) emission spectroscopic analysis, etc. can be used. For example, lr, etc., which have a high atomization temperature, IC
For analysis of Pb, Cd, Fe, etc. using P emission spectrometry, atomic absorption spectrometry can be used. Samples used for analysis are usually prepared as follows.
In order to separate the emulsion into gelatin and halogenated grains,
Add water and centrifuge. At this time, for example, if polyvalent cation impurities in the form of poorly water-soluble salts are expected to exist outside the particles, it is necessary to remove them by simultaneously adding a solvent capable of dissolving them, such as an acid. In this way, only the silver halide grains can be extracted from the emulsion and dissolved in an ammonium thiosulfate solution to provide an analytical sample. An emulsion with no impurities added can be used as a standard sample, prepared in the same way, and a known amount of impurity added at the end to be used as a standard sample for creating a calibration curve. It is believed that by doping with polyvalent metal ions, a part dominated by silver ion vacancies can be created and the effects of the present invention can be brought out. fs ion vacancy domination means that the conductivity σV''V ・e・μ1 due to silver ion vacancies exceeds the conductivity σl ``ni ・e・μ1 due to interstitial silver ions. Here, n . is the concentration of interstitial silver ions,
μ is the mobility of interstitial silver ions, nv is the concentration of silver ion vacancies, μ is the mobility of root ion vacancies, and e is the elementary charge. Whether conduction within silver halide grains is dominated by interstitial silver ions or by silver ion vacancies can be determined by measuring ion conduction using the dielectric dissipation method described above. It can be predicted that the amount of doping necessary for silver ion vacancy domination will vary depending on factors such as the halogen composition, size, and crystal habit of the emulsion grains, or the properties of the polyvalent metal ions to be doped. However, it has been confirmed that the doping amount of polyvalent metal ions of the present invention of I x 10-' mol/mol Ag or more is sufficient to make silver ion vacancies dominant in a large number of emulsions. More preferably 2
X 10-' mol/mol Ag or more, particularly preferably << is 3X10-' mol/mol A
It must be doped by more than g. When a large amount of polyvalent metal ions are doped and the silver ion vacancies are dominated, there is a recombination prevention effect as proposed by Mallnowski, a reduction in internal latent image formation by lowering the interstitial silver ion concentration inside the particles, and a reduction in the formation of internal latent images in the particles. Possible effects include the effect of charge dispersion by controlling the space charge potential existing inside. The type of inefficiency that occurs varies depending on the method of making emulsion grains, their composition, shape, and grain internal structure, and it is thought that each emulsion has its own inefficiency.

Therefore, in some cases it is preferable to uniformly distribute the polyvalent metal ions throughout the particles, and in other cases it is preferable to distribute them non-uniformly. Possible examples of non-uniform distribution include a core-shell structure, a multilayer structure, and an epitaxial structure. In the case of a core-shell structure, a structure in which the dove concentration in the core part is higher than in the shell part and vice versa can be considered.

In the case of a multilayer structure, a structure in which the inner side of the particle has a higher dove amount, a structure in which the outer side of the particle has a higher dove amount, and a structure in which layers with a higher and lower dove amount are alternately repeated can be considered. In the case of the epitaxial structure, there are two possible structures: a structure in which the host part has a high dove concentration and a structure in which the guest part has a high dove concentration. Which structure is most preferable in the case of non-uniform distribution depends on the following characteristics of the grains: good or normal, halogen composition and structure, crystal habit, surface latent image emulsion or internal latent image emulsion, grain size , cannot be defined in general terms because it depends on the shape of the particles. However, no matter what structure is taken, it is necessary that the part where the daughter ion vacancy dominates, that is, the part where the multivalent metal ion is doped with IXIO-' mol/mol Ag or more, is at least lθ% of the total silver halide weight. It is. The polyvalent metal ion is IXIO-'mol/molA
The part doped with more than g is 3 of the total halogenated weight.
It is preferably 0% or more. The polyvalent metal ion is I
It is further preferred that the portion doped with X 1 0-' mol/mol Ag or more accounts for 50% or more of the total silver halide weight. Grains doped with polyvalent metal ions of 1x10-' mol/mol Ag or more and grains doped with less than that may coexist, but grains doped with polyvalent metal ions of txto-' mol/mol Ag or more are silver halide. lθ by weight
% or more, preferably the silver halide weight is 30% or more, and particularly preferably the silver halide weight is 50% or more. Any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide or silver bromide, silver chlorobromide containing up to 30 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of lθ microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good. The photographic emulsion used in the present invention is based on "Physics and Chemistry of Photography" by Grafkide, published by P. Glafki
Des, Chis+ie et Physique
PhotographiquePaul Mont
el. 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin
+Photographic Emulsion Ch
emiatry (Focal Press1966)
, Zelikman et al. [Production and coating of photographic emulsions], published by Focal Press (V.L., Zelikmanet al.
Making and coating photo
graphicEmulsion,FocaI Pre
It can be prepared using the method described in J.S.S., I964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

A method in which particles are formed with an excess of silver ions (so-called back-mixing method) can also be used. PAg in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
The so-called controlled
The double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pH during grain formation. For more information, see Photographic Science and Engineering.
Science and Engineering) No. 6
Vol. 159-165 (1962) Journal of Photographic Science
fPhotographic Science), 1
2, pp. 242-251 (1964), U.S. Patent No. 3.6'55, '394 and British Patent No. 1.4.
No. 13.748.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cleve's Theory and Practice of Photography J.
hyTheoryandPractlce (193
0) ), 131 pages; Gatoff, Photographic
Science and Engineering (Gutoff)
, Photographic Science and
Engineering), No. 14e:, 248-25.
7 pages (1970); U.S. Patent Nos. 4,434,226, 4,414.310, 4,433,048,
4,439,520 and British Patent No. 2,112,
It can be easily prepared by the method described in No. 157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505,068, U.S. Patent No. 4,44
4.877 and Japanese Patent Application No. 58-248469.

In addition, silver halides having different compositions may be joined by evitaxial joining, and for example, silver halides such as Rodan silver,
It may be bonded with compounds other than silver halide, such as lead oxide. Also, a mixture of particles of various crystal forms may be used. Silver halide solvents are useful to accelerate ripening. For example, it is known that excessive amounts of halogen ions are present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used and these ripening agents can be incorporated in their entirety into the decomposition medium in the reactor prior to addition of the silver and halide salts; Alternatively, two or more halide salts, silver salts, or peptizers may be added and introduced into the reactor. As a further variant, the ripening agent can also be introduced independently at the halide salt and salt addition stages. As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. Special Publication No. 5B-1410, Molsar et al., Journal of Photographic Science, Vol. 25, Eng. 977, 19
As described on page 27, silver halide emulsions can be sensitized by internal reduction of grains during the precipitation formation process.
In the present invention, it is extremely important to perform chemical sensitization such as sulfur sensitization and gold sensitization. As shown in Example 4, the photographic properties of grains doped with polyvalent metal ions of IXIO-' mol/mol Ag or more are not distinctive in the unripe state, but become noticeable when chemically sensitized. It is showing effects. The location where chemical sensitization is applied varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion. There are cases where chemical sensitizing nuclei are embedded inside the particles, cases where they are embedded shallowly from the particle surface, and cases where chemical sensitizing nuclei are created on the surface. Although the effects of the present invention are also effective, it is particularly preferable to create chemically sensitized nuclei near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical sensitization is described in "The Photographic Inc. Process, 4th Edition," by T. Ill. Jase, published by Macmillan, 1977, <T. H. Jasxes. T
heTheory of the Photography
htc Process+ 4th ed, Mac
millan, l 9 1 7) 6 7 7 6
Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, Vol. 34, June 1975, 13452, U.S. Pat. , No. 642.361, No. 3,297,446, No. 3,772.031, No. 3,857,711,
3,901,714, 4,266,018, and 3,904,415, and British Patent No. 1.3.
pAg5-10, pAg5-10 as described in No. 15.755
It can be carried out using sulfur, selenium, chilli, gold, platinum, palladium, iridium or a combination of these sensitizers at H5-8 and a temperature of 30-80°C.

Chemical sensitization is optimally carried out in the presence of a gold compound and a 1,000 ocyanate compound, and with sulfur as described in U.S. Pat. It is carried out in the presence of a sulfur-containing compound or a sulfur-containing compound such as a hybo-containing compound, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. Chemical sensitization aids used include azaindene,
Compounds known to suppress fog and increase sensitivity during the chemical multiplication process are used, such as azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat.
No. 4, No. 3.554,757, JP-A-58-1265
No. 26 and the aforementioned Duffin, "Photographic Emulsion Chemistry", 138
~143 is truly described. In addition to or in place of chemical sensitization, reduction sensitization can be performed, for example with hydrogen, as described in U.S. Pat. U.S. Patent No. 2,
No. 518,698, No. 2,743,182 and No. 2
, using reducing agents such as stannous chloride, thiourea dioxide, and polyamines as described in No. 743.183.
or low pAg (e.g. less than 5) and/or high pAg
Reduction sensitization can be achieved by treatment with H (for example, greater than 8). Color sensitization can also be improved by chemical sensitization methods described in US Pat. No. 3,917;485 and US Pat. No. 3,966,476.

Furthermore, the chemical enhancement method described in JP-A-61-93447 is particularly effective when combined with the emulsion of the present invention. The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure [Laml 7643 (December 1978) and Laml 1teml 8716 (November 1979), and the relevant sections are summarized in the table below. l Chemical sensitization 2 Sensitivity increasing agent Page 23 648 Immediate right column Same as above The photosensitive silver halide used in the present invention is preferably coated in a range of 1 to 1 Og/rrr in terms of silver. 4 Whitening agent Page 24 Dye Image stabilizer Hardener Binder Plasticizer, lubricant Page 25 Page 26 Page 26 Page 27 Page 651 Page left column Same as above page 650 Right column The silver halide used in the present invention includes methine dyes and others. It may be spectrally sensitized by The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex nolocyanine dyes, holobolar cyanine dyes,
Hemicyanine dyes, styryl dyes and hemioxo/-
color dyes are included.

Specifically, U.S. Pat.
No. 5, RD17029 (1978), pages 12-13. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as disclosed in U.S. Patent No. 3). , 6 1 5,641, Tainansho f33
-23145 etc.》. These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
3.756 and 4,225.666 before or after nucleation of silver halide grains. The amount added is generally about 10-1 to 10-2 mol per mol of silver halide. The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide and a binder on a support, and further contains an organometallic salt oxidizing agent, a dye-donating compound (
(As described below, it may also serve as a reducing agent).

These components are often added to the same layer, but if they are in a state where they can react, they can be added separately to separate layers. For example, if a colored dye-donating compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from the dye fixing material described below. In order to obtain a wide range of colors in the chromaticity diagram by combining the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each having sensitivity to different spectral regions are combined.

Examples include a combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can have various arrangement orders known for conventional color photosensitive materials. Further, each of these photosensitive layers may be divided into two or more layers as necessary. The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer. In the present invention, an organic metal salt is used together with photosensitive silver octalodenide as an oxidizing agent. Among such organic metal salts, Ariiso silver salt is particularly preferably used. Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include those described in U.S. Pat. SOO. [No. 326 No. 5
There are penzotrizoles, fatty acids, and other compounds described in 2 to 53a. Tokukai D again? { 6 0 − 1
Also useful are silver salts of carboxylic acids having a 7-rukynyl group, such as silver 7-enylbutybutiolate described in No. 1 3 2 3 5, and silver acetylene described in JP-A-61-249044. There are 8! 2 liters of silver salt! One or more may be used together. The above Ariiso silver salts have a content of 1 mole of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50B to 10g/+ in terms of silver.
o2 is appropriate.

Various anti-capri agents or photographic stabilizers can be used in the present invention. An example is RD17 (
343 (1978) pages 24 to 25, nitrogen-containing carboxylic acids Ojopurin WIM described in JP-A-59-168442, or merkabut compounds described in JP-A-59-111636, and Metal salts thereof include acenalene compounds described in JP-A No. 62-87951. Hydrophilic binders are preferably used in the constituent layers of photosensitive materials and dye-fixing materials. Examples include those described on pages (26) to (28) of JP-A-62-253159. In terms of the A-form, transparent or translucent water-visible pingu is preferable, and natural compounds such as protein or cellulose derivatives such as zeftin and gelatin derivatives, polysaccharides such as starch, 7rabi7 gum, dextran, pullulan, etc. Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylic heptad polymer, and other synthetic polymer compounds. In addition, Tainansho 62-24
Super water absorbent polymer described in No. 5260 etc., tnahchi-C
OOM*taha-SO. A homopolymer of vinyl monomers having M (M is a hydrogen atom or an alkali metal) or a copolymer of these vinyl monomers with each other or with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd.) !!Sumikadel L-5
8) is also used. Two or more of these binders can also be used in combination.

When using a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. In addition, if a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to other materials after dedication. is 1 theory 2 per 2
0. The following is preferable, particularly 10 g or less, more preferably 7 g or less.

The constituent layers (including the bank layer) of the sensitive material or dye-fixing material contain various materials for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It is possible to contain a voluminous latte/decoction. Specifically, JP-A-62-245258 and JP-A-62-1
Any of the polymer latexes described in No. 36648, No. 82-1 10066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40'C or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and a polymer latex with a high glass transition point can be used in the back layer. As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. It also includes dye-donating compounds with reducing properties, which will be described later (in this case, it is also possible to use other reducing agents together). Reducing agent precursors that exhibit reducing properties through the action of reagents or heat can also be used. Examples of reducing agents used in the present invention include U.S. Pat.
, 50θl626 No. 49-5081, #4.4
8 3.9 1 No. 4 No. 30-31m, PI4, 3
3 0.6 1 7, same No. 4,590.152,
JP-A No. 60-140335, pages (I7) to (18), No. 57-40245, No. 56-138736, No. 59-178458, No. 59-53831, No. 59
-182449, 59-182450, 60-
No. 119555, No. 60-128436 to No. 60-
Up to No. 128439, No. 60198540, No. 60-
No. 181742, No. 61-259253, No. 62-2
No. 44044, No. 62-131253 to No. 62-1
There are reducing agents and reducing agent precursors described in European Patent No. 220.746A2, pages 78 to 96, and the like. Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869. If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Precursors can be used in combination. The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its promoter is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 17-enyl-3-virazolidones or amino-7 enols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Examples include sulfonamide F7-ols, sulfonamide donatols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below. It will be done. In the present invention, the amount of the reducing agent added is 0.001 to 20 mol, particularly preferably 0.01 to 20 mol, per 1 mol of silver.
It is 10 moles. In the present invention, silver can be used as the image forming substance. It may also contain a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. It ends with. Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a single chain of polymer. A specific example of a color developer and 1 coupler is James:X:'! ! [
The Theory of the 7 Otographic Bu a 7th] Part 4
Edition (T.H, James 'TI+e Tbeory
or tl+e PI+otograpl+ic P
rocess'') 291-3341, and 354-3
61 pages, JP-A-58-123533, JP-A No. 58-14
No. 9046, No. 58-149047, No. 59-1 1
1 1 48, 59-124399, 59-
No. 174835, No. 59-231539, No. 5, 9-
No. 231540, No. 60-2950, No. 60-295
No. 1, No. 60-14242, No. 60-23474,
It is described in detail in No. 60-66249, etc. Another example of a dye-donating compound is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula [LI].

(Dye Y) n-Z (LllDye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a connecting group, and Zli is a photosensitive material that has a latent image in image form. Correspondingly or inversely to the silver salt, a difference is created in the diffusivity of the compound represented by (Dye-Y)n-Z, or Dye is released, and the released Dye and (Dye-Y)n - Represents a group that has the property of causing a difference in diffusivity between it and Z, n represents 1 or 2, and when n is 2, the two Dye-Ys may be the same or different. ．General formula [L
! Specific examples of the dye-providing compound represented by ] include the following compounds Φ to ■. In addition, ■ to ■ below correspond inversely to the development of silver halide to form a diffusible dye image (Bonn dye image), and ■ and ■ correspond to the development of silver halide to form a diffusible dye image. It forms a dye image (ne dye image).

■U.S. Patent No. 3.1 3 4.7 6 4, PpJ
3. No. 362,819, brother No. 3,597,200,
Same No. 3,5 4 4,5 4 5, Same No. 3,482.
A dye developer in which a hydroquine-based developer and a dye component are linked, as described in No. 972 and the like. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■As described in U.S. Patent tiS4.5 0 3, 1 3 7, etc., non-diffusible compounds are also used that release diffusible dyes in an alkaline environment but lose that ability when they react with silver halide. can. Examples include compounds that release diffusible dyes through intramolecular nucleophilic exchange reactions described in U.S. Patent No. 3.98 0,479, etc.; Examples include compounds that release diffusible dyes through an intramolecular rewinding reaction of the inoxazolone ring described in No. 4. ■US Patent #IJ4,55 9,2 90, European Patent No. 220.746A2, US Patent No. 4.7 8 3.
As described in No. 396, Technical Report 87-6199, etc., non-diffusible compounds that release diffusible dyes by reacting with the reducing agent remaining unoxidized during development can also be used. For example, U.S. Patent No. 4,139,38
9, PIS No. 4,139.379, JP-A-59-185333, JP-A No. 57-84453, etc., the intramolecular 4fr! A compound that releases a diffusible dye through a monoconversion reaction, US Special Ff
No. 4,232.107, JP-A-59-101649, JP-A-61-88257, RD24025 (1984), etc. After being reduced, a diffusible dye is released by an intramolecular electron transfer reaction. Compound, West German Patent No. 3,
No. 008,588A, JP-A-56-142530, U.S. Pat. No. 4.34-3.893, U.S. Pat.
No. 19,884, etc., the single bond releases a diffusible dye after reduction, lj Examples thereof include bipolar compounds that release diffusible dyes, and compounds that release diffusible dyes after receiving electrons S' as described in US Pat. No. 4,609,610 and the like.

Also, more preferably, European Patent No. 220,7
No. 46A2, public technique! 1187-6199, U.S. Patent f
fs4, 783.396, Vf leap number 63-20165
Compounds having an N-X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule as described in No. 3, No. 63-201654, etc., Patent Application No. 10688/1988
SQ. -X (X has the same meaning as above) and an electron-withdrawing group, JP-A-63-271
A compound having a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 344, JP-A-Sho f3
The compound described in No. 3-271341 has a C1X' bond (X' is synonymous with X or represents -S02-) and an electron-withdrawing group in one molecule. Also, wait for the 62nd year.
Compounds described in No. 319989 and No. 62-320771 that release a diffusible dye by cleaving a single bond after reduction due to a π bond conjugated with an electron-accepting group can also be used.

Among these, compounds having an N-X bond and an electron-withdrawing group in one molecule are particularly preferred. A specific example is European Patent No. 22
0.746A2 or U.S. Patent No. 4,78 3,3
9 Compounds (1) to (3), (7) to described in No. 6
(10), (12), (13), (15), (23)~
(26), (31), (32), (35), (36)
, (40), (41), (44), (53)-(59)
, (64), (70), and compounds (11) to (23) of Kounen Giho 87-6199. ■A compound (D
DR Kabler》. In military terms, British Patent No. 1.330.
No. 524, Japanese Patent Publication No. 48-39,165, U.S. Patent No. 3
．． No. 443.940, same No. 4,4 7 4,8 6 7
No. 4, 4, 8, 3.9, 1, 4, etc.

■It is reducible to silver halide or saturated silver salt,
A compound that releases a diffusible dye upon reduction of its partner (DR
R compound). Since this compound does not require the use of other reducing agents, it is preferable since there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example is U.S. Patent No. 3,92
8.312, 14.0 5 3, 3 1 2, 4.0 5 5.4 2 8, 4.3 3 6
, 3 2 2, JP-A-59-65839, JP-A No. 59
-69839, 53-3819, 51-104
, 343, RD17465, U.S. Patent No. 3,72
No. 5,06 2, No. 3,728.113, m.
3,443,939, JP-A-58-116,537, JP-A-57-179840, U.S. Patent No. 4,500.6
It is described in No. 26, etc. As an example of a prefectural DRR compound, the above-mentioned Kakokumachi Ff No. 4.500.62Q No. 22
Compounds listed in Column to Column 44 can be mentioned,
Among them, compounds (1) to (3) described in the above US patent,
(lO) ~ (13), (16) ~ (19), (28) ~
(30), (33) to (35), (38) to (40),
(42) to (64) are preferred. Also, U.S. Patent No. 4.6
Also useful are the compounds described in No. 39,408, Nos. 37-39m. In addition, as the above-mentioned couplers and dye-donating compounds other than the general formula [L I ], dye silver compounds in which a silver salt and a dye are combined (Research Disc.
May 1978 issue, pp. 54-58], 7zo dye used in heat-developable silver dye bleaching method (U.S. Pat. No. 4.23-5.9)
5 No. 7, Research Disclosure Magazine, 197
6, April issue, pp. 30-32), leuco dyes (U.S. Pat. No. 3.98, 5.5, 65, U.S. Pat. No. 4,022, etc.),
6, 1, 7, etc.) can also be used. Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents are described in U.S. Patent No. 2.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 322.027. In this case,
Taiyo No. 59-83154, No. 59-178451,
No. 59-178452, No. 59-178453, No. 59-178454, No. 59-178455, No. 5
A high boiling point organic solvent such as those described in Japanese Patent No. 9-178457 can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less per 1 bi of the dye-providing compound used. Also, icc or less, and even 0.5c per 1g of binder.
cc or less, especially 0.3cc or less is suitable. Dispersion methods using m compounds described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used. In the case of compounds that are practically insoluble in water, in addition to the above method, they can be dispersed and contained in fine particles in the bangu. Various surfactants can be used to disperse hydrophobic compounds in hydrophilic colloids. For example, JP-A-59
The surfactants listed on pages (37) to (38) of No. 157636 can be used. In the present invention, a compound can be used in the photosensitive material to activate the development and stabilize the image at the same time. Regarding preferably used military compounds, US Patent tt%4,
It is described in columns 51-52 of No. 500, 626. In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. Even if the dye-fixing material is coated separately on a support separate from the light-sensitive material, it can be coated on the same support as the light-sensitive material. 1i
It may also be in a form where it is installed. Regarding the relationship between the light-sensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in US Pat. No. 57491 of US Pat. No. 14,500,626 can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and examples of the A-type mordant are those described in U.S. Pat. ! R (32) ~ (41
) and those described in JP-A-62-244043 and JP-A-62-244036. Also, dye-receiving polymeric compounds such as those described in U.S. Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be used as a plasticizer, a slippery agent, or a releasability improver for the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 62 of JP-A-62-253159.
-245253, etc. Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into nomethylsiloxane. For example,
[Modified silicone oil] issued by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in technical fee P6-18B, especially carboxy-modified silicone (trade name X-22-
37io) etc. are effective. Also, JP-A-62-215953 and JP-A No. 63-46449.
The silicone oil described in this issue is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents may include, for example, antioxidants, ultraviolet absorbers, or certain complexes. Examples of antioxidants include chroman compounds, coumaran compounds, and 7-enol compounds (for example, Hingood 7).
2/-ols), hydroquinone derivatives, hindered amine derivatives, and spiroingone compounds. Compounds described in JP-A-61-159644 are also effective.

As ultraviolet absorbers, penzotriazole compounds (
U.S. Pat. No. 13,533,794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,681, etc.),
Benzo-7 enone compounds (JP-A-46-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, etc. Further, the ultraviolet absorbing polymer described in Tokuya Sho 62-260152 is also effective.

As metal complexes, U.S. Patent No. 4,241.155,
Same fjS4, 245.018 f:ttJ3-36 columns,
No. 4,25 4,195, columns 3-8, JP-A-62-174741, JP-A No. 61-88256 (27)
~ (29) pages, No. 63-199248, Patent application 1982-
There are compounds described in No. 234103 and No. 62-230595.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material externally such as a photosensitive material. ．． The above antioxidants, ultraviolet absorbers,
Metal complexes may be used in combination.
Optical brighteners may be used in photosensitive materials and dye-fixing materials. In particular, it is preferable to incorporate a fluorescent brightener into the dye-fixing material or to supply it from outside the light-sensitive material. An example is K. Veenkataraman (ed.) [The
CI+cmistry of Synthetic D
Examples include compounds described in yesJ, Chapter V8, Chapter 8, JP-A-61-143752, and the like. More specifically, stilbene compounds, coumarin compounds,
Examples include bi7enyl compounds, penzoxazolyl compounds, natalimide compounds, pyrazoline compounds, and carbostyryl compounds. Optical brighteners can be used in combination with anti-fading agents. Examples of dura removal used for constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Hardeners described in No. 1, No. 61-18942, and the like can be mentioned. I) For military purposes, aldehyde hardeners (formaldehyde, etc.), 7-nolinone hardeners, epoxy hardeners, vinyl sulfone hardeners (N.N'-ethylenebis(
(vinylsulfonylacetamido)ethane, etc.), N-methylol-based hardeners (such as tumethylol urea), and polymer hardeners (compounds described in Tainan Sho 62-234157, etc.). Various surfactants can be used in the constituent layers of photosensitive materials and dye-fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Surface active M
Examples of military units are Tainan Sho 62-173463 and Sho 62-18.
It is described in No. 3457, etc. The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
A*7 fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic heptafluoro compounds include Japanese Patent Publication No. 57-9053 No. 8-17m, Japanese Patent Application Publication No. 61-1988
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetra7tethylene resin. can be mentioned. Matting agents can be used in photosensitive materials and dye fixing materials. As a matting agent, silicon dioxide, polyolefin, or polymethacrylate may be used.
In addition to the compounds described on page 29 of No. 6, patent applications No. 62-110064 and No. 62-11 include Penzog 7 Namine resin beads, polycarbonate resin beads, and AS resin beads.
There is a compound described in No. 0065. In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an anti-spill agent, a colloidal mineral, and the like. Specific examples of these additives are
It is described on pages 26 to 32 of No. 88256.

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. ! Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and silver. It is also classified as a compound that interacts with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details on these see U.S. Patent 4,67
8,739 No. 38-404IQ. Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines through intramolecular nucleophilic substitution reactions, a-tusene rearrangements, or Beckman rearrangements. Specific examples thereof are described in US Pat. No. 4,511,493, Japanese Patent Application Laid-Open No. 62-65038, etc. In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, compounds that can undergo rust-forming reactions with sparingly soluble metal compounds and metal ions constituting the sparingly soluble metal compounds described in European Patent Publication No. 210.660 and U.S. Patent No. 4,740.445 ( Combinations of complex-forming compounds (complex-forming compounds) and compounds that generate bases by electrolysis as described in Tokuban No. 61-232451 can also be used as base precursors. The former method is particularly effective.
It is advantageous to add the II-soluble metal compound and the complex-prone compound separately to the light-sensitive material and the dye-fixing material. The light-sensitive material and/or dye-fixing material of the present invention may contain various development stoppers in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, merkabuto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32). As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. Generally, paper and synthetic polymers (films) are mentioned.Specifically, polyethylene tere7talate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimides, celluloses (e.g. triacetylcellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin pulp such as polyethylene, and natural pulp. Mixed paper, Yankee paper, Paraita paper, footed paper (especially cast coat grade), metal, cloth, glass, etc. are used. These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used. The surface of these supports may be coated with hydrophilic paint, alumina sol, semiconductive metal oxide such as tin oxide, carbon plaque, or other antistatic agent. Methods for exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and copying machines. Image fl? How to emit light from a light-emitting diode, various lasers, etc. via electrical signals to expose image information, and display image information on CRT, liquid display, Electa Lumine/Sense display, plasma display, etc.! ! There are methods such as outputting the image to a device and exposing it directly or through an optical system.

As a light source for recording an image on a photosensitive material, as mentioned above, 1 is used.
U.S. Patent No. 4,50 for natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc.
The light source described in No. 0,626, column tI456 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appears when a strong optical electric field such as a laser beam is applied, such as lithium diobate, potassium dihydrogen phosphate ( KDP), lithium iodate, Ba[lzO-, etc., inorganic compounds, urea wing conductors, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), 1961
-53462 and 62-210432 are preferably used. Shape of wavelength conversion element. ! ! As for i, single crystal optical waveguide type, fiber type, etc. are known, and both are useful. In addition, the above-mentioned image information can be obtained by dividing an image signal obtained from a video camera, an electronic still camera, etc., a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into three elements that are often damaged by a scanner. image signal, CG
Image signals created using computers such as %CAD can be used. The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye. In this case, the transparent or opaque heating element described in Japanese Patent Application Laid-Open No. 145544/1983 can be used. Note that these conductive layers also function as a stop layer for band W1#. The heating temperature in the heat development process is approximately 50°C to approximately 250°C.
IjL images are possible, but temperatures of about 80°C to about 180°C are useful. The dye expansion process may be performed simultaneously with heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the eave copying process can be transferred in the range from the temperature in the heat development process to room temperature, but it is particularly preferable to set the heating temperature at 50 °C or higher and about 10 °C lower than the temperature in the heat development process. ．． Dye migration can be caused by heat alone, but a solvent may also be used to promote dye migration. Also, vt leap @59
-218443, No. 61-238056, etc., a small amount of melting! It is also useful to perform development and printing simultaneously or sequentially by heating in the presence of water (especially water). In this method, the heating temperature is preferably 50°C or higher and below the boiling point of the solvent. For example, if the solvent is water, it is preferably 50°C or higher and 100°C or lower. Examples of solvents that can be used to accelerate development and/or transfer the #4 secondary dye to the dye fixing layer include water or basic aqueous solvents containing inorganic alkali metal salts and organic bases.
Examples of these bases include those described in the section on image-forming accelerators. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. In addition, a surfactant, an anti-capri agent, a poorly soluble metal salt, a complex-forming compound, etc. may be included in the solvent. These solvents can be used by applying them to both the dye-fixing material and the light-sensitive material. A small amount (less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the film minus the iit of the entire coated film) may be sufficient. As a method for applying a solvent to the dye layer or the dye fixing layer, there is, for example, the method described in V# Kaisho 61-147244, page 26. Also, solvent! It can also be used in advance by enclosing it in a photosensitive material or a dye fixing material, or both. Also, in order to promote dye transfer, it is solid at room temperature.
It is also possible to incorporate a hydrophilic thermal solvent that dissolves at high temperatures into the light-sensitive material or dye-fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both. *Although the waste to be incorporated may be in the emulsion layer, intermediate layer, or ML dye fixing layer, it is preferably incorporated in the dye fixing layer and/or its adjacent layer.
Examples of hydrophilic heat solvents include ureas, pyrinones, amides, sulfonamides, imides, alnyls, oximes, and other heterocyclic compounds. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material. Heating methods during the development/transfer process include contact with a heated block or plate, hot plate, hot breather, hot roller, halogen lamp heater, infrared and far infrared lamp heater, etc. , passing through a high-temperature atmosphere, etc.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye fixing material and bringing them into close contact are described in vPrJl1 1986-
The method described in No. 147244, page 27 can be applied. Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
No. 59-177547, No. 59-181353, No. 60-18951, Utility Model No. 6 2-2 5 9 4
The devices described in No. 4 etc. are preferably used. Example I An example of doping with Pb"" is shown. l) Emulsion preparation solution Bone gelatin 20g Potassium bromide 0.6g f{go 1 0 0 0cc solution 0 Nitrate #I Silver 10g Ammonium nitrate 0.25K Hz0 40cc solution O Potassium bromide 7gH! 0
50cc solution 0 nitric ftltf1
200gH, 0 75
0cc solution■ Potassium bromide 1708H,
0 Add the solution to a 1100cc reaction vessel and stir at 75℃. Solution ■ and solution 0 at the same time for 40
Add in seconds. After adding 7.5 g of ammonium nitrate and 15 cc of 25% ammonia and aging for 5 minutes, solutions O and [F] were heated at 60°C for 100 minutes until the silver potential reached +70 mV.
It was added at a constant flow rate while controlling it so that

The obtained particles had an average size of 1.2 μm and a coefficient of variation of 1.
It was a 3% cube. This is for comparison and is called Emulsion-1. After adding solutions (1) and (O) in the same manner as for 1 liter of emulsion, 2 g of ammonium nitrate and 15 cc of 25% ammonia were added and ripened for 5 minutes. After adding 1.3 g of pb(NOs)x to solution 0, solutions O and [F] were added at 40°C while controlling the silver potential to be +90 mV. The flow rate was accelerated so that the final flow rate was four times the initial addition flow rate. The obtained particles were cubic with an average size of 1.1 μm and a coefficient of variation of 15%. This is called emulsion-2.
After adding solutions 1 and 0 in the same manner as in Emulsion-1, 4 g of heptammonium nitrate and 9 cc of 25% ammonia were added and ripened for 10 minutes. After adding 0.48 g of pb(NOx) to solution O, solution 0 and O were added at 50°C while controlling the silver potential to be +70 mV. The flow rate was accelerated so that the final iJtl was three times the initial flow rate. The obtained particles were cubic with an average size of 1.2 μm and a coefficient of variation of 12%. This is called Emulsion-3.

After adding solutions 1 and 0 in the same manner as emulsion-1, 2 g of ammonium nitrate and 4 cc of 25% ammonia were added and the mixture was aged for 20 minutes. 0.04g of P b (NOx) in the melt 0
After adding *, the solution O and [F] were heated to 60°C until the silver potential was +
It was added at a constant flow rate while controlling the voltage to be 70 mV. The particles obtained were cubic with an average size of 1.3 μm and a coefficient of variation of 14%. This is called Emulsion-4.

After adding solutions (1) and (0) in the same manner as in Emulsion-1, 2 g of ammonium nitrate and 15 cc of 25% ammonia were added and ripened for 5 minutes. After adding 0.48 pb(NOs)z to solution 0, solution 0 and [F] were heated to a silver potential of -30 mV at 40°C.
It was added while controlling the amount. The flow rate was accelerated so that the final flow rate was four times the initial flow rate. The obtained particles had an average size of 1.3 μm and a coefficient of variation of 1.
It was 2% octahedral. This is called Emulsion-5.

After adding solution ■ and O in the same way as emulsion = 1, ? 2 g of ammonium acid and 1 cc of 25% ammonia were added and aged for 30 minutes. After adding 0.4g of pb(NOs)* to solution 0, the solution 0 and [F] were heated to 75℃ so that the silver potential was +70m.
It was added at a constant flow rate while controlling the amount to be V. The obtained particles were cubic with an average size of 1.1 μm and a coefficient of variation of 14%. This is called Emulsion-6.

2》Measurement of dove The amount of pb doped in emulsions 1 to 6 was analyzed.

After enzymatically decomposing the gelatin, the particles were extracted by centrifugation. Furthermore, H20 was added and centrifugation was repeated twice. Further, the process of adding IN HNO2 and centrifuging was repeated twice, and then thoroughly washed with water. After dissolving the precipitate in ammonium thiosulfate, Pb was determined by atomic absorption spectrometry. A known amount of pb(NOs) was added to emulsion-1.
)* was added to create a calibration curve. The results are shown in Table 1. Table 1 It can be seen that emulsions 2, 3, and 5 are doped with a large amount of PB''.
This is surprising given the knowledge that /IQOOL is not doped. In addition, in the case of emulsion-6, l/10
It can be understood that whether Pb1° is doped or not depends significantly on the conditions of grain formation. Example 2 LHt0 1 0 0 0cc solution■ Silver nitrate 10g8.0
40cc solution 0 Okuka potassium 7gHz0
50cc solution 0 silver nitrate 200
gHt0 800cc solution O Okuka potassium 165g potassium iodide
4.7g Hz0 Add the solution to a 1100cc reaction vessel and stir at 50℃. Add solution ① and solution 0 at the same time for 40 seconds. Add 15cc of 25% ammonia 1
After aging for 5 minutes, solutions 0 and 0 were added simultaneously. Emulsion-
In the case of 7, 0.78g of K. 1rCl. In the case of emulsion-8, 1.2 g of CdBrz was added to the e solution, and in the case of emulsion-9, 0 solution (in this case, potassium bromide 168
g and Hm01100cc), 0.63g of K*
(Fe(CN)J・3HzO is added.Solution 0 and ■
The addition was carried out at 50°C, and the silver potential was controlled to be 80mV. The flow rate was accelerated so that the final flow rate was three times the initial flow rate. The obtained particles were 0.
They were cubic silver iodobromide grains with a diameter of 5 μm. After sample treatment similar to the method described in Example 1, Cd
and Fa were determined by atomic absorption spectrometry using Ir., which has a high atomization temperature. In this case, quantification was performed using inductively coupled radio-frequency plasma emission spectroscopy. The results are shown in Table 2] In all cases of rSCtL Fa, it is shown that a large amount of doping of 10-' mol/mol Ag or more is possible. Example 3 Example 3 shows that the silver halide emulsion of the present invention provides excellent performance in a positive photothermographic material. Emulsion 1.0 (comparative emulsion for blue-sensitive layer)! FJ! ! Let's talk about the law. A well-stirred gelatin solution (800 cc of water)
20 g of gelatin, 3 g of potassium bromide, and H O
(C Hz)*S (C Hz) is (C Hz)g
0.3 g of oH was added and kept at 55°C), and the following ill solution and solution (2) were added simultaneously over 30 minutes. Thereafter, the following solutions (3) and (4) were added simultaneously. The flow rate was accelerated so that the flow rate at Saihiragi was four times the initial flow rate. Furthermore, after starting addition of solution (3), the following dye solution was added over 18 minutes from 5 minutes. After washing with water and desalting, 20g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 8.5, and then sodium thiosulfate and 4-hydroxy6-methyl-1.3.3
a,? - Tetrazaindene and chloroauric acid were added to optimally chemically sensitize. Thus the average particle size, 0.40
600 g of a monodispersed tetradecahedral silver iodobromide emulsion of μ was obtained.

dye solution 0.12g (CHHz)ashs (CHZ). SO3H・NEmu, 0.12g is dissolved in 160cc of methanol.

The preparation method of Emulsion 11 (emulsion of the present invention for blue-sensitive layer) is described below. 0.7 g of Pb(N
Emulsion 11 was prepared in exactly the same manner as Emulsion 10 except that O3)z was added.

The method for preparing Emulsion 12 (comparative emulsion for green-sensitive layer) will be described. A well-stirred aqueous solution (730 parts water to 2 parts gelatin)
The following solutions (1) and (It) were added at the same time to 0g1 (0.30g of potassium bromide, 6g of sodium chloride, and 0.015g of the following chemical A and kept at 60.0°C). The flow rate was accelerated so that the final flow rate was three times the initial flow rate.

(1) After the addition of the solution, a methanol solution of the following sensitizing dye (I
II) solution was added. In this way, the average particle size is 0
．． A monodisperse cubic emulsion adsorbed with 45μ dye was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting pAg to 7.8, chemical sensitization was performed at 60.0°C. The chemical used at this time was triethylthiourea 1
．． 6■ and 4-hydroxy6-methyl-1.3.3a,7
-Tetrazaindene lOO■ The aging time was 55 minutes. The yield of this emulsion was 635 g.

(Drug A) C]1, CI1. (Sensitizing Dye C) The preparation method of Emulsion 13 (emulsion of the present invention for green-sensitive layer) will be described. 0.7 g of pb (NOs
) Emulsion 13 was prepared in the same manner as Emulsion 12, except that E was added. Emulsion 14 (Comparative Example of Red Sensation) Good《Aqueous gelatin solution with stirring (20g of gelatin in 80ml of water, 1g of potassium chloride and OH (CH.)
Is(CHI)! The following solutions (1), (n) and (In) were added at the same time to 0.5 g of OH and kept at 50°C. The flow rate was accelerated so that the final flow rate was four times the initial flow rate. In this way, a monodisperse silver bromide emulsion having an average grain size of 0.42 μm and adsorbing a dye was prepared.

After washing with water and desalting, add 20 g of lime-treated ossein gelatin and adjust the pH to 6.4.
Keep warm at ℃, add sodium thiosulfate 9■, chlorauric acid 0,0
1% aqueous solution 6-,4-hydroxy-6-methyl-1.3
,' 3a,? -Add 190■ tetrazaindene, 4
Chemical sensitization was performed for 5 minutes. The yield of emulsion was 635g. Dye (a) Pigment Mountain》 The method for preparing Emulsion 15 (emulsion of the present invention for red-sensitive layer) will be described. 0.7 g of PB (NO!
Emulsion 15 was prepared in exactly the same manner as emulsion 14 except that 1) was added.

Emulsion 16 (green-sensitive layer comparison emulsion) A well-stirred aqueous solution (2 gelatin in 730 ml of water)
0 g, potassium bromide 0.30 g, sodium chloride 6 g, and the chemical AO used in Emulsion 12. Add 015g and 5
The following solutions (1) and (■) were added at the same time at equal flow rates over 30 minutes. Then (I[l)
Liquid and (IV) were each added at an accelerated rate so that the final flow rate was 2.5 times the initial flow rate. (■)
After adding the liquid, dye liquid C used in emulsion 12 was added. washing with water,
After desalting, add 22g of lime-treated ossein gelatin to adjust the pH.
After adjusting pAg to 6.2 and pAg to 8.0, triethylthiourea and 4-hydroxy6-methyl-1.3.3a,?
Optimal chemical sensitization at 60° C. using -tetrazaindene. The resulting emulsion was a 0.4μ cubic monodisperse emulsion with a yield of 630g. Next, the preparation method of emulsions 17, 18, and 19 (the emulsions of the present invention) will be described. An emulsion was prepared in the same manner as in Emulsion 16 except that the following chemicals were added to Solution 1. A method for preparing a dispersion of zinc hydroxide will be described.

The average particle size is 0. 12.5g of 2μ zinc hydroxide
1 As a dispersant, carboxymethyl cellulose Ig and 0.1 g of sodium polyacrylate were added to a 4% gelatin aqueous solution 10
In addition to 0 cc, the sample was ground for 30 minutes using glass beads with an average particle size of 0.75 fi. The glass beads were separated to obtain a dispersion of zinc hydroxide. Next, we will discuss the All method for manufacturing activated carbon dispersion. Add 2.5 g of activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical, Demol Nlg manufactured by Kao Soap ■ as a dispersant, and 0.25 g of polyethylene glycol nonyl phenyl ether to a 5% gelatin aqueous solution L O O cc, and average it with a mill. Particle size 0.7
Grind for 120 minutes using 5U glass beads. The glass beads were separated to obtain an activated carbon dispersion with an average particle size of 0.5 μm.

Next, we will discuss how to prepare a dispersion of the electron transfer agent ■. Add 10g of the electron transfer agent below, 0.5g of polyethylene glycol nonyl phenyl ether as a dispersant, and 0.5g of the anionic surfactant below to a 5% aqueous gelatin solution, and mill to obtain an average particle size of 0.75. of glass beads for 60 minutes.

The glass beads were separated and a drink containing the electron transfer agent (■) with an average particle size of 0.3μ was obtained. Electron transfer agent ■ Anionic surfactant CH@COOCH*CH (C1H%) C4H drop NaOs
S CHCOOCHzCH(CzHs)04H*Next, we will discuss how to make a gelatin dispersion of a dye-providing compound. Each of yellow, magenta, and cyan was added to 50 cc of ethyl acetate according to the following recipe, and dissolved by heating at approximately 60°C to form a uniform solution. 1 of this solution and lime-treated gelatin
After stirring and mixing 100 g of 0% aqueous solution, 0.6 g of sodium dodecylbenzenesulfonate, and 50 cc of water, the mixture was dispersed using a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a gelatin dispersion of a dye-providing compound. Dye-donating compound Fil CONHC+ilhs Dye-donating compound (2) rσ CONIC+Js! Dye-donating compound (3) Electron donor ■ High boiling point solvent ■ Using these emulsion dispersion chemicals, photosensitive materials having a multilayer structure as shown in Table 1 were prepared. Electron Transfer Agent Precursor ■ Next, we will explain how to make a gelatin dispersion of electron donor ■ for the intermediate layer. The following electron donor ■23.6g and the above high boiling point solvent ■8
．． 5 g was added to 30 cc of ethyl acetate to make a homogeneous solution.
This solution and 100 g of a 10% aqueous solution of lime-treated gelatin,
After stirring and mixing 0.2581 sodium bisulfite, 0.3 g of sodium dodecylbenzenesulfonate and 3 Qcc of water, the mixture was dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of electron donor (■). Note 1) Surfactant ■ Note 2) Surfactant ■ C H ! C O O C H z C H ( C
* H s ) C a H qN a O s S
- C H C O O C H z C H (
C z H s) C a Hq Note 3》 Water-soluble polymer SOtK Note 4) Antifoggant ■ Note 9》 Hardener [phase] l, 2-bis (vinylsulfonylacetamide) Ethane Note 10) Antifoggant ■ ]I The numbers of the light-sensitive materials used in this example and the emulsions used are as follows.

Note 5) Surfactant ■ Note 6) Surfactant ■ Note 7 >> Electron transfer agent ■ Note 8 >> Electron transfer agent ■ Next, we will discuss how to make the dye fixing material. A dye-fixing material was prepared by coating it on a polyethylene-laminated support (1) according to the composition shown in Table 2 below. Table 2, -11 "I Food Silicone Oil (11 Surfactant (1) Surfactant《2》C FI9S O!N C H!C O O KC3H
．． Surfactant (3) CH Theory I Surfactant (4) C m H s C * Hs Fluorescent brightener {υ 2, 5 bis (5-tert-butylbenzoxazole {2}) Thiophene surfactant ( 5) Water-soluble polymer (1) Sumikagel L5-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant (11 SOsκ High boiling point solvent {1} Hardener (1) Mantle agent (1) )* Silica mantle agent {2) $ Penzoguanamine resin (average particle size 15μ) A tungsten light bulb is used for the color photosensitive material of the multilayer structure, and the colors of B, G, R, and gray whose density changes continuously. 1/10 at 5000 lux through a decomposition filter
Exposure for seconds. While feeding this exposed photosensitive material at a linear speed of 20 am/see, water of 15 d/n was supplied to the emulsion surface using a wire bar, and then the dye-fixing material and the film surface were immediately overlapped so that they were in contact with each other. .

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 80°C. Next, when it was peeled off from the image-receiving material, clear blue, green, red, and gray images corresponding to the B, G, R, and gray color separation filters were uniformly obtained on the image-receiving material.

The results of measuring the emulsion used in the light-sensitive material and the maximum density (Dmax) and minimum density (Diin) of each color of cyan, magenta, and yellow in the gray area are shown.

From the above results, the light-sensitive material containing the emulsion of the present invention has a Dmax of
is high, indicating that the thermal capri of silver halide is low. In addition, the sensitivity of photosensitive materials 101 and 102 is set to Dmin+0.5.
When comparing the relative values using the reciprocal of the exposure amount that gives the density, the following results were obtained (gray exposed area).

was added over a period of 12 minutes, and the solution (■) was added over a period of 8 minutes. From 16 minutes after the addition of liquid 1 was completed, liquid (2) was added over a period of 44 minutes, and from 20 minutes after the addition of liquid (2) was completed, liquid (2) was added over a period of 40 minutes. Also, the PAg from the end of addition of I solution to the start of addition of solution I was 6.7.
Met.

The above results demonstrate that the emulsion of the present invention has high sensitivity.

<<Example 4>> Example 4 shows the effect of the emulsion of the present invention in a negative heat-developable color photosensitive material. A method for preparing 2 liters of emulsion will be described.

Lime-treated bone gelatin (Ca containing 1250
0ppm) solution (20 g of gelatin, 2 g of sodium chloride, and 0.015 g of compound S dissolved in 800 d of water and kept at 50°C) started adding the following solutions I and II at the same time, and a summer solution was obtained. After washing the emulsion with water and desalting it, lime-treated bone gelatin (Ca content 400
Add 0ppm>25g and 10 (ld) water to adjust the pH to 6.0.
The pAg was adjusted to 7.7. Thereafter, triethylthiourea l. IQr and 4-hydroxy 6-methyl-1
．． 3. Optimum chemical sensitization was performed using 60 II lg of 3a,7-tetrazaindene. The yield of emulsion was 650g. The emulsion obtained was cubic monodisperse grains with a grain size of 0.35 μm and a variation coefficient of about 10%.

The method for preparing emulsion 22, which was confirmed to be a multilayer structure type grain when examined using X-ray diffraction, the XPS method, and the EPMA method, will be described below. Lime-treated bone gelatin (ash content 0.4%,
adenine content 0.2 ppm) aqueous solution (50 g of gelatin, 10 g of sodium chloride, and 0 potassium bromide in 800 d of water)
．． A g N O x aqueous solution (A
gNOs 100g dissolved in water to make a total of 600M1) and halide aqueous solution (KBr54.5
g, 12 g of NaC (dissolved in water to make a total of 600 g) were simultaneously added over 30 minutes. Addition completed 1
After 1 minute, add 0.2 g of sensitizing dye (E) and 0.2 g of (F) to 1 part of water.
20- and a dye solution dissolved in methanol 120M4 were added, and after 5 minutes, a 1% aqueous solution of potassium iodide IQm was added. Sensitizing dye (E) [! t Sensitizing dye (F) Bt After washing with water and desalting, lime-treated bone gelatin (adenine content 20
Add 10 g of ppm) and 50 g of water, pH 6.0, pAg 7
．． Adjusted to 6. The emulsion obtained was kept at 60°C and heated using Hypo 2.5
Chemical aging was performed for 0 minutes. The yield of emulsion was 500g. 1 with an average size of 0.32μ and a coefficient of variation of 11%.
It is a tetrahedral single emulsion. The method for preparing emulsion 23 will be described.

A well-stirred gelatin aqueous solution (lime-treated deionized bone gelatin (Ca content 20 ppm) 20 to 800 parts water)
g, sodium chloride 4g and potassium bromide 0. lg and 0.015 g of S were dissolved and kept at 65°C.
Silver nitrate aqueous solution 11) (A g N Ox 50 g
was dissolved in water to give a total of 300 d] and a halogen aqueous solution (22.8 g of KBr and 16 g of NaC were dissolved in water to make a total of 300 d) were added at the same time over 30 minutes.Then, the temperature of the solution was lowered to 35°C. Lower it to Nitsu Mi!
i! Aqueous solution +21 (AgNOs 50 g dissolved in water to give a total of 500-) and halide aqueous solution (31.5 g of KBr, 1.7 g of NaCj dissolved in water to make a total of 300-) were added at the same time to 30 Washed, desalted, lime-treated bone gelatin (guanine content 50%).
Add 25g of ppm) and 100% of water, pH 6.3, pA
Adjusted to g7.9.

The resulting emulsion was kept at 55°C and triethylthiourea 0.8
■, 4-hydroxy-6-methyl-1.3,3a. 7-
Optimal chemical sensitization was performed using 100 μl of tetrazaindene. The yield of emulsion was 650g. This was a cubic monodisperse emulsion with an average size of 0.5 μm and a coefficient of variation of 9%.

Next, a method for preparing emulsion 24 will be described.

Pb (Now)z O. Emulsion 24 was prepared in exactly the same manner as Emulsion 24 except that 7 g was added.
I got it. The method for preparing emulsion 25 will be described. P was added to the A g N O 2 aqueous solution used in the preparation of emulsion 22.
b (NOs) x O. Emulsion 25 was prepared in exactly the same manner as Emulsion 22, except that 6 g was added. The method for preparing emulsion 26 will be described. Emulsion 26 was prepared in exactly the same manner as Emulsion 23, except that 0.3 g and 0.6 g of P b (NOx)* were added to the silver nitrate aqueous solutions (1) and (2) used in the preparation of Emulsion 23, respectively. I got it. Describes how to make organic silver salt (11, (2)). Describes how to make organic silver salt (11, henzotriazole silver emulsion). Add 28 g of lime-treated bone gelatin (seri-strength 250 g) and 13.2 g of penzotriazole to 300 g of water. Dissolved in one.
This solution was kept at 40°C and stirred.

A solution prepared by dissolving 17 g of silver nitrate in 100 m of water was added to this solution over 2 minutes.

The pH of this penzotriazole emulsion was adjusted and allowed to settle to remove excess salt. Then p [1 to 6.30
Accordingly, a yield of 400 g of henzotriazole silver emulsion was obtained.

Organic silver salt (2) 20 g of lime-treated cowhide gelatin and 5.9 g of 4-acetylaminophenylbrobiolic acid were dissolved in 1000ml of 0.1% aqueous sodium hydroxide solution and 200M1 of ethanol.

This solution was kept at 40°C and stirred.

Nitric acid in this solution! A solution prepared by dissolving 4.5 g of 1.1 g in 200 g of water was added over 5 minutes. The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, a dispersion of organic silver salt (2) with a yield of 300 g was obtained with the pH adjusted to 6.3.

Next, we will discuss how to make a gelatin dispersion of a dye-donating substance. Weighed 5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate-2-ethylhexyl ester sulfonate and 10 g of l-liisononyl phosphate as surfactants, and added 30 g of ethyl acetate. was added and dissolved by heating to about 60°C to form a homogeneous solution. This solution and 100 g of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes.

This dispersion is called a yellow dye-providing substance dispersion. A dispersion of a magenta dye-donating substance was prepared in the same manner as described above, except that the magenta dye-donating substance (B) was used. A cyan dye-providing substance (C) was used in the same manner as the yellow dye dispersion.

Dye-donating substance (A) (C) 0H <8) 0H OCIJ33 (n) Using these emulsions, dye-providing substances, organic silver salt (1), and organic silver salt (2), a multilayer structure as shown in Table 3 is created. Composition photosensitive material 2
01 to 202 were produced. The emulsions used are as follows.

OC+Jzs-n Table 3 (continued) Support (polyethylene terephthalate; thickness lOOμ) Table 3 High boiling point solvent 1I (i!10cqH+*o) aP = 0 Surfactant 11 Surfactant゛Mushroom surfactant 0 Zinc hydroxide 1 Size O. 2μ Hardener 1 l Bis(vinylsulfonylacetamide) Ethane Surfactant 04 C+. HztCONHCHgCHxCHzN(CHs)
xcHzcOo Silica 1' Size 3. 5μ Water-soluble polymer 61 Surfactant 0 -{-CHt-CB-}. CHxCOOCHzCH(CiHs)C4HqC O
N H C (C Hs) x C HzS OxN aNa
OsS CHCOOC}IzCH(CgHs)Ca
H* Antifoggant (C) Sensitizing dye i CH3 CJs C Z II S Antifoggant (D) Sensitizing dye 0fI! tI! t Antifoggant (IE) (Cllg) 43Oz Ln)CsH++ NIISOmPh The photosensitive materials 201 and 202 thus obtained were treated with a tungsten light bulb and GS whose concentration was continuously changed.
It was exposed to 2000 Lux for 1/20 seconds through a three-color separation filter of R and IR.

Water of 15 d/n was supplied to the emulsion surface of this exposed light-sensitive material using a wire bar, and then the same dye fixing material used in Example 3 was superimposed so that the film surface was in contact with the emulsion surface of the exposed light-sensitive material.

The film was heated for 25 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90°C.

Next, when peeled off from the dye fixing material, B,
Yellow, magenta, and cyan images were obtained corresponding to the G and R three-color separation filters.

The results obtained are summarized in Table 4. Table 4 This sensitivity is based on the comparative emulsion of each photosensitive layer as 100, and the minimum density (Dmin) + 0. I checked in 3.

From the above results, it is clear that negative-tone photosensitive materials using the emulsion of the present invention have high sensitivity and less fog (thermal fog).

Claims (1)

[Claims] In a heat-developable photosensitive material comprising at least a photosensitive silver halide and a binder on a support, 10^-^4 per mole of silver halide is contained in the silver halide grains.
1. A photothermographic material characterized in that a portion containing polyvalent metal ions of moles or more is present in an amount of 10% by weight or more of silver halide grains.