JPS6334541A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain easily an image having high density in a short period by heating an image forming reaction system comprising a slightly soluble metal compd. and a compd. which effects a complex forming reaction with the metal ion constituting said metal compd. in a medium of a hydrophilic heat-meltable agent in a molten state, thereby raising pH of the reaction system, in presence of the hydrophilic heat-meltable agent. CONSTITUTION:The image forming reaction system comprising the slightly soluble metal compd. and the compd. which effects the complex forming reaction with the metal ion constituting the slightly soluble metal compd. in the medium of hydrophilic heat-meltable agent in the molten state, thereby raising pH of the reaction system, is heated in presence of the hydrophilic heat-meltable agent. The hyrophilic heat-meltable agent means a compd. which is solid state at ordinary temperature, but, is liquid state at >=60 deg.C, and has >=1 the ratio of inorg. property to org. property, and solubility of >=1g compd./100g water at ordinary temperature. The hydrophilic heating solvent is exemplified by urea, phridine, amide, sulfonamide, imide, alcohol, oxime and a various kinds of heterocyclic compds.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an image forming method, and relates to an image forming method in which the pH of an image forming reaction system is raised to 1% under heating.

[Prior art and its problems] In image forming methods such as thermal development image forming methods and diazo photography using silver halide, p of the image forming reaction system is
Increase Ht and perform the present task.

In order to increase the pH of the image forming reaction system, it is common to bring the base itself into the image forming reaction system or to use a base precursor that decomposes upon heating to generate an alkali.

However, bases have problems with stability, such as absorbing and neutralizing CO2 in the air, and also have adverse effects on the human body, such as irritating the skin when handled.

In addition, conventionally known base precursors do not have sufficient stability, and can decompose even when the environmental temperature rises during storage before the start of development.

There is a problem in that it impairs the storage stability of photographic elements incorporating it.

(Objective of the Invention) An object of the present invention is to provide an image forming method that has excellent storage stability, is simple and easy to perform main processing, and is capable of obtaining high-quality images.

C) Structure of the Invention) An object of the present invention is to produce an image containing a poorly soluble metal compound, a metal ion constituting the hardly soluble metal compound, and a compound that causes a complex formation reaction using a molten hydrophilic hot solvent as a medium to increase the pHt. Formation reaction system e--Achieved by an image forming method characterized by heating in the presence of a hydrophilic hot solvent.

In the image forming method of the present invention, the image forming reaction system includes a poorly soluble metal compound and a compound C that can undergo a complex formation reaction with a metal ion constituting the hardly soluble metal compound using a molten hydrophilic hot solvent as a medium; These λ
The reaction between the two compounds raises the pH' of the imaging reaction system.

The image forming reaction system in the present invention means a region where one image forming reaction occurs. Specifically, examples thereof include a layer existing on a support of a light-sensitive material, and, when a photographic element includes a light-sensitive element and a dye-fixing element, layers belonging to both elements. When one or more layers are present, all or one layer may be used.

Examples of poorly soluble metal compounds used in the present invention include
The solubility of a substance in water (i. the number of grams of a substance that dissolves in 100 ml of water) is 0. Carbonates below j.

Phosphates, silicates, aluminates, aluminates.

Included are hydroxide-oxides, and double salts of these compounds, such as basic salts.

and Formula TmXn The one represented by is preferable.

Here, T is a transition metal 1, for example, Zn=Ni, Co.

Fe-Mn etc. or alkali metals such as Ca, Mg
, Ba, etc., and X represents an ion that can serve as a counter ion for M, which will be mentioned later in the explanation of complex-forming compounds in the molten hydrophilic heat solvent, and exhibits alkalinity, such as carbonate ion, phosphorus ion, etc. Represents acid ions, silicate ions, borate ions, aluminate ions, hydroxy ions, and oxygen atoms.

m and n represent integers such that the valences of T and X are balanced, respectively.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate-calcium magnesium carbonate (CaMg(CO3)2), magnesium oxide, zinc oxide, tin oxide, cobalt oxide-zinc hydroxide, aluminum hydroxide, magnesium hydroxide, Calcium hydroxide, antimony hydroxide.

tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate-magnesium borate-calcium silicate, magnesium silicate,
Zinc aluminate, calcium aluminate, basic zinc carbonate (JZnCO3・j Zn (OH12・H20),
Basic magnesium carbonate (7MgCO3・Mg (OH
)2ΦJH20L Basic nickel carbonate (NiCO3@
Ni(OH)2)-basic bismuth carbonate (Bi
Among these compounds, one that is not colored is particularly preferred.

The complex-forming compound used in the present invention forms a complex salt having a stability constant of 1 or more in LogK with the metal ion constituting the 'S-soluble metal compound.

These complex-forming compounds are described by, for example, N. E. Martill and R. M. Smith (A, E.).

Martell, R, M, Sm1th l, @Critical Stability Constance (Cr
1tica l5tability Con5tant
s1. Volumes 1-7”, Plenum Press
Details are given in Pressl.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives - anilinecarboxylic acids - pyridinecarboxylic acids - aminophosphoric acids, carboxylic acids (mono, di, tritetracarboxylic acids and also phosphono, hydroxy, oxo, ester, amide, alkoxy, Examples include compounds having substituents such as mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, amidines, and salts such as μ-class ammonium salts.

Preferred specific examples include monopyriconic acid, 2. Loupyridinedicarboxylic acid-1! -Pyridinedicarboxylic acid, ≠-
dimethylaminopyridine-λ, 6-dicarboxylic acid, quinoline-2-carboxylic acid, λ-pyridylacetic acid-oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid - EDTA, NTA, CyDTA, DTPA, D
PTA-OH-hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid.

Polyacrylic acid.

HO2CCH20CH2CH20CH2CO2H.

HO2CCH20CH2CO2H.

Examples include alkali metal salts such as CH3H2O5P-CH-PO3H2, salts of guanidines, salts of amidines, and μ-class ammonium salts.

Particularly preferred are salts of organic bases such as guanidines.

Among these, aromatic heterocyclic compounds having at least one -CO2M group and one nitrogen atom in the ring are preferred. The ring may be a monocyclic ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -CO2
Where is M bonded to the ring?

Particularly preferred is the α position relative to the N atom.

M is any one of an alkali metal, guanidine, amidine and ≠-grade ammonium ion.

In this case as well, M is particularly preferably guanidine-amidine or μ-class ammonium ion.

More preferable compounds include those represented by the following formula.

In the above formula, -R is a hydrogen atom or an aryl group.

halogen atom, alkoxy group, -co2M-hydroxycarbonyl group, and amino group-substituted amino group.

Represents any electron-donating group such as an alkyl group. The two Rs may be the same or different.

Zl and Z2 are respectively the same as defined in R,
Further, Zl and Z2 may be combined to form a ring condensed to the pyridine ring.

Next, the most preferred combinations of a dissolvable metal compound and a complex-forming compound will be listed, where Mo represents an alkali metal ion, substituted or unsubstituted guanidinium ion, amidinium ion or μ-class ammonium ion. ) Calcium carbonate - Basic zinc carbonate - Basic magnesium carbonate - Zinc oxide - Basic zinc carbonate - Basic magnesium carbonate - Calcium carbonate - Zinc oxide - Calcium carbonate - ΦMeO2C - CO2θMΦ Calcium carbonate - Carbonate IJ r:y Mu's MeO2C-CO2■Me
Calcium carbonate - Me salt of tripolyphosphate Calcium carbonate - M salt of citric acid Calcium carbonate - M salt of polyacrylic acid Calcium carbonate - Magnesium oxide - Zinc hydroxide - H3C\, cH3 Tin hydroxide - H3C\, cH3 Hydroxide Magnesium - Me salt of hexametaphosphoric acid Zinc hydroxide - JMe salt of ethylenediaminetetraacetic acid Zinc hydroxide -
/, 3M0 salt of 2-cyclohexanediaminetetraacetic acid Aluminum hydroxide-calcium carbonate-Basic magnesium carbonate-~002C-Co□. ? Calcium carbonate - Basic zinc carbonate - These combinations can be used alone or in combination. TE can be used in combination with a known base or base precursor.

Here, the mechanism for increasing the pH of the reaction system in the present invention will be explained using a combination of guanidine picolinate and zinc hydroxide as an example.

The reaction between the two is shown, for example, by the following formula.

Here, GHΦ represents a guanidium ion, and G represents guanidine.

When the hydrophilic thermal solvent melts and functions as a medium, monopicolinate ions undergo a complex formation reaction 1 with zinc ions, and as a result of the reaction represented by the above formula progressing, it exhibits high alkalinity.

The progress of this reaction is due to the stability of the complex formed, but it is important to note that the progress of this reaction is due to the stability of the complex formed, but the difference is that picolinate ion (Le) and zinc ion 1M0)
The stability numbers of the complexes represented by MLlMLz and MLs produced by the reaction are very large as shown below, and explain the progress of this reaction well.

LogK! , Jo ta, tko lλ,
Octopus hydrophilic thermal solvent is a compound that is in a solid state at room temperature but turns into a liquid state at high temperatures (above 400C), has a C(inorganic/organic) value greater than 7, and has a solubility in water/009 at room temperature. means a compound with 72 or more.

For details on the above (inorganic/organic) values, see
"Area of Chemistry" l/Volume 7/? There is a description on page (ivy j7). The (inorganic/organic) value of the hydrophilic heat solvent is preferably 1.5 or more, particularly preferably 2 or more, and needs to be larger than the (inorganic/organic) value of the dye-providing substance.

Further, the molecular weight of the hydrophilic heat solvent is preferably 200 or less, particularly preferably 100 or less. The melting point of hydrophilic thermal solvent is 4Lo
0C,2to'C-preferably da00C-λoo0
C1 is more preferably ≠o'C to 1so0c.

The hydrophilic heat solvent is used by being added to the photosensitive element and/or the dye fixing element. There is no particular restriction on the amount used, but it is within the j-700 weight range of the total coating amount of the photosensitive element and dye fixing element (excluding the amount of hydrophilic heat solvent), preferably 20
It is used in a coating amount of ~200% by weight, more preferably 30~200% by weight.

The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it may also be dissolved in alcohols such as methanol, ethanol, etc. and dispersed in the binder.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and various heterocycles.

Specific examples of these can be found in Tokukaisho! It is written in ter itr ≠ 32 months, etc.

Examples of hydrophilic heat solvents that can be preferably used in the present invention are shown below.

(3) O (≠) 0 H2NCNHC2H5+ CH3NHCNHCH
3(j)0 HOCH2NHCNH2 (t)0 HOCH2NHCNHCH20H (7)O HOC2H4NHCNHC2H40)((t)0 H2NCNHC2H40H H2NCN(C2H40H12 (to) (//)(/2
) O H2N-C-N(CH3)2 H Nl2 C3μ) (3s) CH38
02NH2, HOCH2So2NH2(Jj)
(371H2N S 02 N
H2, 3HcNH8O2NH2(Jri(75F3 (4tol (4At>H (Hiroshi 7) HOCH2(CHOHI3CH20H1(μr)
(≠9)CH3C(CH
20H)3+ C2HsC(CH20H)3(t
o) (ri)02NC
(CH20H)3- Sorbit (j≠) HOCH2-CH=CH-CH20H (jr) D/1)CH3CH
=NOH,HON=CHCH=NOH(z7)
(sr)CH3C=NOHHOCH2
CH=NOHcH3c=.

Among these, ureas (1), (J), (J),
(to), pyridines (/7), (ty), amides (26), (30), (33), sulfonamides (3S, (3t), C3), imides (4Ao)
, (Hiroshi), Jin3)-(Ua) and alcohol (4
I≦), (jl), etc. are particularly preferred.

Furthermore, in the present invention, two or more types of hydrophilic heat solvents can be used in combination.

The imaging method of the present invention can be applied to any imaging method in which the imaging reaction is initiated or accelerated by increasing the pH of the system.

For example, the image forming method of the present invention can be applied to the so-called heat development diazo method. In the thermal development diazo method, in addition to the diazo compound and the coupler, urea or the like is used as an alkali generator, but in the present invention, this urea also functions as a hydrophilic thermal solvent, and the complex-forming compound with the sparingly soluble metal compound of the present invention is used. A combination of can be used.

Further, the image forming method of the present invention can be applied to a thermal development image forming method using silver halide.

The poorly soluble metal compound and the complex-forming compound need to be added at least to the main separate layer in order to prevent them from reacting before the development process. For example, it is preferable that the above-mentioned two additive layers are separate layers, with one or more layers interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable to contain a poorly soluble metal compound in a photosensitive element and a complex-forming compound in a sheet for supplying a complex-forming compound or a dye fixing element having a support separate from the photosensitive element. Hardly soluble metal compounds are covered by Tokukai Sho! 6-/74ArJO issue,
It is desirable to contain it as a fine particle dispersion prepared by the method described in JT3-1027JJ, etc., and the average particle size thereof is preferably 30 microns or less, particularly 3 microns or less.

The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer, or may be added to two or more layers separately.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the releasable metal compound, the rate of complex-forming reaction, etc. It is appropriate to use it in terms of jO weight percent (-cents) or less, and more preferably o, oi weight percent to 4c.

A range of weight percentages is useful. Further, in the present invention, the content of the complex-forming compound in the reaction system is preferably 17 to 100 times, particularly 7710 to 20 times, in molar ratio to the content of the poorly soluble compound.

Below, a heat-developable image forming method using silver halide, which is a particularly preferred application example of the Ryotsu forming method of the present invention, will be explained in particular detail.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, U.S. Patent≠, 200. Buλbu whistle jO column,
Research Disclosure Magazine 1970-10 (RD/70λ), patent application 1976-22116
/ issue, 4O-22j176, same to-λ cotco 17
Any of the silver halide emulsions described in No. 1, etc. can be used.

The silver halide emulsion used in the present invention may be of the surface latent flaw type, in which latent flaws are mainly formed on the grain surfaces, or may be of the internal latent flaw type, in which latent flaws are formed inside the grains. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion which is a combination of an internal latent flaw type emulsion and a nucleating agent can also be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be performed in the presence of a nitrogen-containing heterocyclic compound. Kobu No. JL-Co/744 (No. 4).

The coating amount of the photosensitive silver halide used in the present invention ranges from 1'II9 to 117 m2 in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent are those described in Japanese Patent Application Shojter No. 22IIJ1, pages 37-
Page 3F, U.S. patent μ, zoo, tλ whistle jλ column ~ No. 5
There are compounds listed in column 3, etc.

Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in Japanese Patent Application No. 1987-90019, and silver acetylene described in Japanese Patent Application No. 40-90019. These or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
o, oi to 10 mol, preferably O0O/ to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is calculated in terms of silver! 0 da to 1097 m
2 is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, Japanese Patent Application Publication No. 104110, No. 40
-/≠No. 0333, Research Disclosure Magazine 1
Sensitizing dyes described in y7r ≦ month issue lko-/3 pages (RD/70 kota), etc., JP-A-2008-2003-3, patent application Sho-to-/7-kota no. 67, etc. Examples include thermally decolorizable sensitizing dyes described in .

Although these sensitizing dyes may be used alone, they may also be used in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, 1 is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
Substances exhibiting supersensitization may be included in the emulsion (for example, U.S. Pat. /!, 41
No. 3, same J, 4/! t, 6≠No. 1, same J, t/7.
Kota J, same 3. tJ! , No. 72/).

These sensitizing dyes may be added to the emulsion at or before chemical ripening.
yrt issue, same issue≠, ko 21. It may be carried out before or after nucleation of silver halide grains according to No.ITT.

The amount added is generally equivalent to 1 mole of silver halide.

It has a molar content of 10-8 to 10-2.

In the present invention, silver can be used as the image forming material. 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 substance. can.

Examples of the dye-donating substances used in the present invention include:
Compound C that forms a dye by oxidative coupling reaction
couplers).

The coupler may be a ≠4-equivalent coupler or a co-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. Specific examples of developers and couplers can be found in ``The Theory of the Photographic Process'' by James James, 1st edition.
theory of the Photographic
Process') Kotano ~ page 33μ, and 3j ~
34/page, JP-A No. 11/1983/Ko3j33, SR-Nohiro 20, No. 6, II-/1t904c7, No. 1? −／
///4! ? No., J Turf 2≠3 Tata No., Tata No. 7
7≠No.131, same! ? -23/! JP issue, 69-23
/! No. 170, same≦7−λrijO, same O-2? j1
No. 1aO-/1424-, No. 6O-234474
No. L, 60-4≦2hiro? Details are given in the issue.

Another example of the dye-donating substance 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 CLI).

(Dye −X ) n −Y (L I ]D
ye represents a dye group, a temporarily shortened dye group, or a dye precursor group; to create a difference in the diffusivity of the compound represented by (Dye - represents a group having properties that cause a difference in n
represents / or ko, and when n is ko, two Dye-X
may be the same or different.

As a specific example of the dye-donating substance represented by the general formula [L], for example, a nine-dye developer is produced by linking a hydroquinone developer and a dye component, and US Pat.
No. J, 312. t/ri issue, same number J, jri 7. −
No. 00, No. j, jμμ, Jpi No. 3, No. J, 1At2
．． 72, etc. Furthermore, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in US Patent No. 3.
A substance that releases a diffusible dye by an intramolecular rewinding reaction of an inoxacilone ring is described in JP-A No. 9-///, No. 4-r, etc.

Another example is to make the dye-releasing compound into an oxidized form that does not have the ability to release the dye, and make it coexist with the reducing agent and its precursor, and after development, the reducing agent that remains unoxidized reduces and diffuses. A method for releasing a sex pigment has also been devised, and a specific example of a dye-donating substance used therein is disclosed in Japanese Patent Application Laid-open No. 73
-/10, 7.27 issue, same! Piichi/30. ri 27, same jbu-/lμ, 3 hiro 2, same! J-31. It is described in the jJJ issue. Japanese Patent Application Shobu O-2μμm No. 73 describes a dye-donating substance that releases a diffusible dye using a similar mechanism.
Compounds are described in which the N-0 bond is cleaved by the residual reducing agent, releasing a diffusible dye.

In addition, as described in JP-A No. 333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a coupler that has a diffusible dye as a leaving group and that releases a diffusible dye by reaction with an oxidized form of a reducing agent (I DDR coupler) However, British Patent No. 1,330.3
2μ No., Special Publication Sho≠r-39, /47, British Patent No. J,
It is described in U-Hiro 3.2, No. 0, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, contamination of the painting by the oxidative decomposition products of the reducing agent becomes a serious problem. Dye-releasing compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. A typical example is U.S. Patent No. 3. 21,3/λ issue, same μ, 0!
J, JlJ issue, same number, 011. ≠ No. 2, No. μ, 3
3t, 3koko, Tokukai Showa 3rd tJrJ, same! Tar No. 49132, same! J-31/ri issue, same! /-1041
, 34Aj issue, Research Disclosure Magazine/74
No. 4jj, U.S. Patent No. 3,7coj.

No. 062, No. 3, 72! , No. 113, No. 3゜Sanda 3
．． No. 3, JP-A No. 31-//l, No. 737, same! 7-
It is a dye-donating substance described in US Pat. Specific examples of this type of dye-donating substance include the aforementioned U.S. Pat.
, 626, column 22 to column 4c, among which are compounds (1) to (3), (101 to C13), and C/6 described in the above-mentioned US patent.
)~(/ri), (211~(30), (JJ)~(3
z), (311 to (4!01, C octopus) to (1 cap) are preferred. Compounds described on page 1O-r7 of Japanese Patent Application No. 1972≠tutr are also useful.

In addition, as a dye-donating substance other than those mentioned above, a dye silver compound combining an organic silver salt and a dye C Research Disclosure Magazine / 777! Azo Dye C Used in Heat Developed Silver Dye Bleaching Method, U.S. Patent No. μ, Co 31. 57, Research Disclosure Magazine, 1976 issue, pages 30-3λ, etc.), leuco dyes (U.S. Patent Nos. J, 91!, jGj, ≠, 02, 4/7, etc.) etc. can also be used.

Hydrophobic additives, such as the dye-providing compounds described above and image formation promoters described below, are described in U.S. Patent No. λ.

They can be incorporated into the layers of the photosensitive element by known methods such as those described in JJJ, No. 027. In this case,
Tokukai Shoj? -rJ/Jμ issue, same! ? -171441/issue, same! ? -77ru! No. 2, same! Day/714413
No., same j? -/7rjfi! IA, same! / 71
111! No. 19-/7ruJ7, etc., if necessary, with a boiling point of 10'C-1.
It can be used in combination with a low boiling point organic solvent of 60'C.

The amount of high boiling point organic solvent is 10? Below, preferably! is below.

Also, Tokuko Sho J/-J rzs, Tokuko Sho J/-1991
The dispersion method using polymers described in No. 1J can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids. For example, Tokukai Akira! Turf! The books listed in No. 7bu No. 36, pages 137) to (Jr) can be used as surfactants.

In the present invention, it is desirable to contain a reducing substance in the photosensitive element. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. Also included are reducing agent precursors that do not themselves have reducing properties, but exhibit oxidizing properties through nucleophilic tests or the action of heat during the current process.

Examples of reducing agents used in the present invention include U.S. Pat.
zoo, the first hiro of the A-koro issue? ~to column, same s, 44rJ,
Columns 30-31 of No. 744, JP-A-1976-/Reference 0JJ
No. J, pages (/7) to (/r), JP-A-60-/214
c31, 40-/211736, 0-/21
Reducing agents described in No. 4IJ, No. 60-/2rμ37, etc. can be used. Maku, Tokukai Shojbu-/Jr, m issue, same 1
7-4cO, J4cs, U.S. Patent No. 44,330,6
Reducing agent precursors described in No. 17 and the like can also be used.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,032,262.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
, 0/5-20 mol, particularly preferably 00 lNIO mol.

In the present invention, a compound that activates development and simultaneously stabilizes the image can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. ≠, 20
0. No. 26! It is written in the /-j column.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, research
Disclosure magazine 17th layer /, February issue Fueko Part 2 ~ 2
! azoles and azaindenes as described in JP-A No. 1 TR4CA, nitrogen-containing carboxylic acids and phosphoric acids as described in JP-A No. 1 TR4CA, mercapto compounds and metal salts thereof as described in JP-A No. Acetylene compounds described in O-Coco 1 No. 25, etc. may be used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. For specific examples of effective toning agents, please ask! Tar261? There are compounds described in No. 92-3, page 3.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use at least three different layers, each of which has a silver halide emulsion layer sensitive to the color range. You can use elements. For example, the blue-sensing layer,
A combination of three layers: a green-sensitive layer, a red-sensitive layer, a green-sensitive layer, a red-sensitive layer,
There are combinations of infrared-sensitive layers, etc. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The photosensitive element used in the present invention may contain various additives known for use in heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye. It can have a release layer, a matte layer, etc. to facilitate peeling off from the fixing element. For each additive, please refer to Research Disclosure Magazine / 7, April 2016 issue, pages ~ /j, and special requests from Shōjō. -Plasticizers, matting agents, sharpness improving dyes, anti-nolation dyes, surfactants, fluorescent whitening agents, etc., as described in No. 209!63, etc.
Additives include anti-slip agents, antioxidants, and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. Each of the protective layer and the intermediate layer may be composed of one or more layers.

Further, the intermediate layer may contain a reducing agent for preventing color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

The photographic element of the present invention is comprised of a light-sensitive element that forms or releases a dye upon heat development and, optionally, a dye-fixing element that fixes the dye.

In particular, in a system that forms an image by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in a typical form, the photosensitive element and dye fixing element are separately coated on two supports. There are two types of coatings: those that are coated on the same support and those that are coated on the same support. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer is explained by Akiyoshi Tokuhara.
Turcoro T Octopus, page 71-3 of the patent specification and the US patent μ
.

The relationship described in column 37 of the Zoo, T-coro issue is applicable to the present application.

The dye fixing element preferably used in the present invention has four layers, including a layer containing a mordant and a binder. As the mordant, any known mordant in the field of tinnitus can be used, and specific examples thereof include those described in Japanese Patent Application No. 143 of Shoj Turquoise. The dye fixing element can 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. One or more of the above layers may include hydrophilic heat solvents, plasticizers, anti-fade agents,
UV absorbers, slip agents, matting agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, superabsorbent polymers, surfactants, fluorescent whitening agents, etc. may be included. Specific examples of these additives are given in Japanese Patent Application Shoj Turquoise 313.
Issue No. 10/Page ~ 1 O1 [K is described.

In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. 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. It has functions such as promoting the movement of dye from the dye to the dye fixed layer, and from a physicochemical function, it interacts with nucleophilic compounds, high boiling point organic solvents (C oil), surfactants, silver or silver ions. It is classified as a chemical compound, etc. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For more information on these, please contact us. It is described on pages 67-7 of Taa 3ri No. 71.

Various development stoppers can be used in the photosensitive element and/or dye-fixing element of the present invention 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;
Electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors, etc., which undergo capping reaction with coexisting bases when heated, are magnetized, for example, by patent application Sho J1-Col.
Butako! No., same JOj No., same! tar try3
≠ No. 9 is the compound described in Tata rJrJ No. 6, etc.)
.

Compounds that release mercapto compounds when heated are also useful, for example, Japanese Patent Application No. 190173/1973, Ibid. Turco TR Tacobu issue, same j5'-λg 1st issue, same too
-2tOJr, tO-22602, 60-2
603rd issue, same to-λμAAj issue, same to-kota 19
There are compounds described in No. λ, No. 176330, and K.

A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the present invention.

Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, gelatin, cellulose derivatives, starch,
These include natural substances such as polysaccharides such as gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers.

Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used. These binders can be used alone or in combination.

In the present invention, the coating amount of the binder is 20 f or less per m2, preferably 10'1 or less, more preferably 7 f or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is less than or equal to solvent/CC to binder/f, preferably O,
Za:, or less, more preferably 0, JCC or less is appropriate.

Constituent layers C (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardening agents are given in Japanese Patent Application No. 1983-2 Try No. Participation to Pages yz, No. 10-λJ10P3, Pages J to J, and Japanese Patent Application Publication No. 1988-10-10P3, Pages J to J. Examples include those described on page 7tJ Bubu (JI), and these can be used alone or in combination.

The support used in the photosensitive element and/or dye-fixing element of the present invention is one that can withstand processing temperatures.

Common supports include glass, paper, polymeric films, metals and their analogs, as well as patent applications! The supports described in Turcoro R926, pages 2j to 6 can be used.

The photosensitive element and/or the dye fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements. As a resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting semiconductivity, and the other uses a thin film of an organic material by dispersing conductive fine particles in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. Shoj Tarriz.

In the present invention, the method of coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, pack layer, dye fixing layer, and other layers is described in US Pat. No. 300,626, No. 33~! The method described in the column can be applied.

Radiation, including visible light, can be used as a light source for image fogging to write an image on the photosensitive element. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (I LED), etc.
1 octopus issue 100 pages and US Patent Hong,! The light source described in column (j) of No. 00626 can be used.

When creating a transferred dye image, the steps of thermal development and dye transfer may be performed independently or simultaneously. Further, it may be continuous in the sense that transfer is performed following development in one step.

For example, (1) After imagewise exposing the photosensitive element and heating it,
There are two methods: (2) a method in which the dye-fixing elements are stacked one on top of the other and the mobile dye is transferred to the dye-fixing element by heating if necessary; and (2) a method in which the light-sensitive element is image-fogged and the dye-fixing elements are stacked and heated.

However, in any case, the alkali generating system based on the slightly soluble metal compound and the complex-forming compound of the present invention is made to function at the time of thermal development.

For example, in the case of (1), a poorly soluble metal compound is added to the photosensitive element, a complex-forming compound is coated on a separate support together with a binder, and a sheet is prepared, and this sheet is overlapped with the photosensitive element during thermal development. Heat together. At this time, the hydrophilic heat solvent may be added to at least one of the photosensitive element and the sheet.

The heating temperature in the heat development process is about 100c to about 0c
It can be developed at a temperature of about 100C, but a range of about 100C to about 100C is particularly useful. When the transfer process is performed after the heat development process,
The heating temperature in the transfer process can range from the temperature in the heat development process to room temperature, but special VC! It is more preferable that the temperature is O'C or higher and about 1o0C lower than the temperature in the heat development step.

The hydrophilic heat solvent of the present invention also functions to promote the transfer of the dye.

As a heating means in the development and/or transfer process, heat plates, irons, heat rollers, etc. can be used.
r? There is a means described in page 102 of issue 1 to page 103, line //. Alternatively, a layer of conductive material such as graphite, carbon black, metal, etc. may be applied to the photosensitive element and/or the dye fixing element, and an electric current may be passed through the conductive layer to heat it directly. .

As for the pressure conditions and the method of applying pressure when the photosensitive element and the dye fixing element are superimposed and brought into close contact with each other, the method described on pages 103 to 10[mu] of Japanese Patent Application No. Shoj Tarxtr De 2 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, Tokukai Akira! 9-7 eye number 7, same j? -/771μ7, same! 9-/I/J! J No. 6
0-119! The apparatus described in Jitsugan Shobu 0-//17J4c and the like is preferably used.

(f) Specific effects of the invention) According to the invention, an image forming reaction system containing a poorly soluble metal compound and a compound that causes a complex formation reaction with the metal ions constituting the same and a compound that causes a complex formation reaction using a molten hydrophilic heat solvent as a medium to increase pHt is provided. Since image formation is performed by heating in the presence of a hydrophilic hot solvent, it is possible to form an image by heating it in the presence of a hydrophilic hot solvent, so it is possible to form an image without adding a solvent that is liquid at room temperature such as water.
High-density images can be obtained in a short time. Further, an image forming method with excellent storage stability of photosensitive materials and the like can be obtained.

Example/A photosensitive silver bromide-containing benzo) IJ azole silver emulsion was prepared as follows.

A] Benzotriazole 1-2f Isopropyl alcohol CoorII9BE A
fNO3i 7 y H20jOml CHI LiBr λ, /
? Ethanol CoOdμ0°C
Add solution B while stirring solution A.

Solution A becomes white and cloudy, producing a silver salt of benzo (benzo) IJ azole.

When C is added to this solution, silver is supplied from silver benzotriazole, and part of the silver benzotriazole is converted to silver bromide.

The powder crystals thus produced are collected by filtration, added to a polymer solution dissolved in polyvinyl butyral l0ff isopropyl alcohol λood, and dispersed for 30 minutes using a homogenizer.

benzo containing the above-mentioned photosensitive silver bromide) +1 azole silver emulsion iot, 1 dye-donating substance o, pot, H as a reducing agent, λ, but-dichlorol-aminophenol 0. /I? Then, a solution of dimethylsulfamide O,St as a hydrophilic thermal solvent dissolved in ethyl alcohol 1N,N-dimethylformamide was added and stirred.

Next, an aqueous dispersion of zinc hydroxide (content of zinc hydroxide: 7141
209! Processed into polyvinyldutyral liquid (isopropyl alcohol solvent) Joo*l.

Dispersion was performed using a homogenizer for 30 minutes. This zinc hydroxide dispersion J, Of was added to the above photosensitive solution and after stirring, iroμ
1 on a polyethylene terephthalate film with a thickness of
A photosensitive material was prepared by coating to a wet film thickness of 00 μm and drying.

A sheet containing guanidine pyriconate as a complex-forming compound was prepared by pressing as follows. Add urea J to J4 aqueous solution tiNl of polyvinyl alcohol (average molecular weight -〇〇〇)
,! ? , methylurea ginseng, jf.

Ethylene urea λ, Of1 dimethylsulfamitono.

θ1 and guanidine picolinate j, Off were added and stirred to dissolve. This solution was applied to a wet film thickness of 60 μm on a polyethylene terephthalate film with a thickness of @ioo μm and dried to prepare a sheet for supplying a complex-forming compound.

After the photosensitive material is exposed in a self-like manner, it is brought into close contact with the complex-forming compound-containing sheet so that the film surface is aligned, and the pack surface side of the sheet is t-1ro.
It was heated at 0 cvc and brought into contact with a heat block for 9 seconds to uniformly heat it. After the photosensitive material was cooled to room temperature, it was peeled from the sheet and the coated emulsion layer was physically peeled off from the polyethylene terephthalate film using an adhesive tape. A magenta color was obtained on the polyethylene terephthalate film. When measured using a Macbeth transmission densitometer (TD-top), the highest concentration was 1.
．． The lowest concentration of KoO1 was O, Ko3.

Example The method of making the emulsion for the seventh layer will be described.

A well-stirred gelatin solution (water ioo.

- Contains 20 tons of gelatin and 31 tons of sodium chloride 7j
400 ml of an aqueous solution containing sodium chloride and potassium bromide gold (CK kept warm) and a silver nitrate aqueous solution f water a
0.29 mol of silver nitrate dissolved in ootsl) was simultaneously added at an equal flow rate over UO minutes. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion of μm (bromine, tO mol) was prepared.

After washing with water and desalting, sodium thiosulfate J89 and derhydroxy-t-methyl-/, J, Ja, 7-titrazaindene 201Q were added to perform chemical sensitization at 40°C. The yield of emulsion was toot.

Next, I will talk about how to make an emulsion for @3 layers.

Aqueous gelatin solution C water ioo, stirring well.

1 contains gelatin-09 and sodium chloride JTF 7z
An aqueous solution containing sodium chloride and potassium bromide (too-
Dissolve 0.012 moles of silver nitrate in oo-) and the following dye solution (I).

Simultaneously, they were added at equal flow rates over ≠θ minutes. Monodisperse cubic silver chlorobromide emulsion C bromine in which a dye with an average grain size of 0.3 jμ is adsorbed in this way! θmol) was prepared.

After washing with water and desalting, sodium thiosulfate J
Chemical sensitization was performed with gooc by adding O119'i.

The yield of emulsion was toot.

Dye solution + I) Methanol Hiro00yi1st step! This section describes how to make a silver halide emulsion for layers.

A well-stirred gelatin solution (water ioo.

Dissolve gelatin λO1 and ammonia in water θ0C
An aqueous solution containing potassium iodide and potassium bromide (kept warm) / 000- and an aqueous silver nitrate solution f water 100
7 moles of silver nitrate dissolved in 0141 were added at the same time while keeping the pAg constant. In this way, the average particle size is 0. A monodisperse silver iodobromide octahedral emulsion (3 moles of iodine, 4 moles) of jμ was prepared.

After washing with water and desalting, gold and sulfur sensitization was performed by adding chloroauric acid c≠hydrate) and sodium thiosulfate coll9. The yield of the emulsion was i, oKq.

This article describes how to make organic silver salts.

Organic silver salt (11 This article describes how to make benzotriazole silver emulsion.

Gelatin tt and benzotriazole 13.2t water J
OOytlVc was dissolved. This solution was kept at uo"c and stirred. Silver nitrate/7ft water 100yllC
The dissolved liquid was added in t-2 minutes.

The pH of this benzotriazole silver emulsion was adjusted.

Sedimentation was performed to remove excess salt. Then, adjust the pH to A, J
A benzotriazole silver emulsion with a yield of 5 oot was obtained.

Organic silver salt (2) Gelatin 209 and ≠-acetylaminophenylpropiolic acid! , tfO,/l aqueous sodium hydroxide solution 10
0011 and ethanol coOO-.

This solution was kept stirring at UO°CK.

A solution prepared by dissolving silver nitrate 4 in zt water-containing 20011 t was added to this solution over a period of 3 minutes.

The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 913 to obtain a dispersion 1 of organic silver salt (2) with a yield of JOOf.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

The yellow dye-donating substance (A) is I? - Auxiliary developer r
D) as O0λ? , the antifoggant (E) is O, and the surfactant is 0.1f of sodium phosphoric acid --ethyl-hexyl ester sulfonate. ,) 1 ot2 of soisononyl phosphate was weighed out, ethyl acetate JOyd was added thereto, and the mixture was dissolved by heating to about 00C to form a homogeneous solution. After stirring and mixing this solution and 74 solution 709 of lime-treated gelatin, use a homogenizer for 10 minutes at tooorpm.
It was dispersed. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance was prepared by applying the same pressure as described above, except that the magenta dye-providing substance (B) was used and 7 degrees of tricresyl phosphate was used as a high boiling point solvent.

A dispersion of a cyan dye-providing substance was prepared using a cyan dye-providing substance ((j) in the same manner as the yellow dye dispersion.

Dye-donating substance (A) (B) (C) Auxiliary agent (D) Antifoggant (E) A color photosensitive material (coi) having a multilayer structure as shown in Table 7 was prepared using these ingredients.

Furthermore, the second, fourth, and fourth layers of the photosensitive material 20/ are made of metal compounds shown in Table 3 instead of zinc hydroxide, and the arrangement is exactly the same as that of the photosensitive material 0/. 103ft was created.

Tricresyl phosphate N (C2H5) 3 + 4 (iso CgH1@O) 3P=0 plates Size 1 μm +j /, Corbis (hinyl sulfonylacetamide) ethane Solution 7 Size O0-μm Solution 8 Polyethylene terephthalate dye fixation The materials used were those having the configuration shown in the table (D-/).

Dye-fixing material I) -/In place of guanidine picolinate, diguanidine ethylenediaminetetraacetate is used, ≠, /? /m
2 coated material was used as dye fixing material D-2.

B and G, in which a tungsten bulb is used in the above-mentioned multilayered color photosensitive material, and the density changes continuously.

Exposure was performed for 1 second at 2000 lux through an R three-color separation filter.

After the emulsion surface of the exposed light-sensitive material and the film surface of the dye-fixing material are stacked so that they are in contact with each other, the temperature of one film is lμ00.
Using a heat roller whose temperature is adjusted so that C≠θ
After heating for a second, when the dye-fixing material is peeled off from the light-sensitive material, B appears on the fixing material.

Yellow corresponding to G and H three-color separation filters.

A magenta-cyan color was obtained. The maximum density and minimum density of each color were measured using a Macbeth reflection densitometer (RD-J/RI), and the results shown in Table 3 were obtained.

In addition, the photosensitive material was exposed to μo 'C under the condition of 70% relative humidity.
After storing it for a week, I processed it in the same way.

Both the maximum s degree and the minimum concentration were almost the same as the results in Table 3. It was found that the photosensitive material of the present invention had good storage stability.

Example 3 The same emulsion as in Example λ was used.

The dye-donating substance is substituted for (A)-(BL(C)) (F
), (G), and (H) were pressed in the same manner as in Example A to prepare gelatin dispersions of yellow, magenta, and cyan dye-providing substances, respectively.

The gelatin dispersion of the current drug oxidized gasbenger is λ,
! -di(t-pentadecyl)hydroquinone IO? and tricresyl phosphate rt in ethyl acetate, 23m
/, 10h gelatin aqueous solution j3? , water μOmt
Add all of the surfactants and surfactant and use a homogenizer for 10 minutes.
It was prepared by dispersing at 10,000 rpm.

Dye-donating substances (F) (G) (H) A color photosensitive material having a multilayer structure as shown in Table 1 was prepared using these materials. As the dye fixing material, yellow and magenta-cyan color images were obtained by the same procedure as in Example λ using D-/i in Example C. The maximum and minimum densities of each color were as follows.

Ao1 nitricresyl phosphate NICH2H5)3 + 4: (iso CgHlgO)3P-0★5:
Size: 0.2 μm Column 6: /, --BisC vinylsulfonylacetamide) Ethane 7: Polyethylene tere 7 tallate Example ≠ The same emulsion as in Example λ was used.

A method for preparing a gelatin dispersion of a dye-donating substance will be described.

The yellow dye-donating substance (L) is I? , reducing agent (K
)tμ,t? -tricresyl phosphate λ, λ? Heat and dissolve in cyclohexanone/lxl to make a homogeneous solution. 74 solution of lime-treated gelatin At? After adding and stirring and mixing a surfactant, the mixture was dispersed using a homogenizer for 10 minutes at 10oorpm.

Magenta dye-donating substance (M)! ,I? to use,
Further, a dispersion of a magenta or cyan dye-providing substance was prepared in the same manner as above except that the cyan dye-providing substance rN)gtf was used.

The same gelatin dispersion of the existing drug oxidized product scavenger as in Example 3 was used.

Dye-donating substance (L) (M) (N) Table with these! A color photosensitive material with a multilayer structure like this was created.

Jk2) Recreation Silk Phosphate Appetizer 4 Size O
0λμm Appetizer 5 Polyethylene terephthalate Next, we will discuss how to make the dye fixing material.

Urea J, Jt, methyl urea μ, jf, ethylene urea 2. Of, dimethylsulfamide2. Of, guanidine picolinate J, 4t, and an aqueous solution of a mordant having the following structure were mixed, dissolved, and coated onto a polyethylene terephthalate film to a wet film thickness of 0 μm, followed by drying.

A mordant and gelatin JJt, l, Corbis C vinyl sulfonylacetamidoethane) λ.

A solution obtained by dissolving O2 in rOO- water was applied to a wet film thickness of 10 μm and dried to prepare a dye fixing material 1)-J.

The transparent support side of the multilayered color light-sensitive material was exposed to light using a tungsten bulb through a B, G, and H three-color separation filter.

After the emulsion surface of the exposed light-sensitive material and the film surface of the dye-fixing material are overlapped so that they are in contact with each other, the temperature of the film is 74t0°.
Using a heat roller whose temperature is adjusted so that U
Heated for 0 seconds. When viewed from the transparent support side of the dye-fixing material with the dye-fixing materials superimposed, yellow and magenta-cyan color images corresponding to the B, G, and H three-color separation filters were obtained on one fixing material. The maximum and minimum densities of each color were as follows.

Next, the photosensitive material was stored for one week under conditions of uo0c relative humidity of 70%, and then treated in the same manner. Both the maximum and minimum densities were almost the same as above. It was found that the photosensitive material of the present invention had good storage stability.

Example! A coating solution for a heat-sensitive photosensitive layer was prepared as follows, and the weight after drying was t, 197 m on a polyethylene terephthalate support.
2 and dried.

The weight of the next coating solution after drying is 11 on this heat-sensitive photosensitive layer.
Coat it to a total area of 97 m2 and dry it to create a heat-sensitive recording material.

on another polyethylene terephthalate support. .

-μm zinc hydroxide/f/m2. A complete coating containing urea/17m2 and gelatin t7m2 was prepared.

The above heat-sensitive recording material was irradiated with ultraviolet rays for 7 minutes using a diazo exposure device. Thereafter, the zinc hydroxide-containing sheet and the film surface were laminated together and the laminate heated to tzo'c was uniformly exposed for 30 seconds to obtain a blue positive g1 with an optical density of /, /J. In addition, if guanidine picolinate and/or zinc hydroxide of the present invention were excluded, only a concentration of O or U could be obtained.

It has been found that the image forming method of the present invention is also effective in the thermal image forming diazo method.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment (blade side 1, Indication of case: 1937, Japanese Patent Application No. 77-14-2, Title of invention: Painting film forming method 3, Relationship with the person making the amendment: Patent application) Person 4. Date of amendment order: February 30, 1986 Date of dispatch) 5. Target of amendment: Specification 6. Contents of amendment: There is no change in the contents of the detailed statement.

Procedural Amendment 1, Indication of Case, 1985 Patent Application No. 17-41/
No. 2, Title of the invention Image forming method 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment Column 5 of “Detailed explanation of the invention” in the specification, “Invention The description in the section "Detailed explanation of" has been amended as follows.

1) From the bottom of the 1st μ page! row " "of ” and correct it.

2) Correct "rB, G, H three-color separation filter" on lines t to 7 from the bottom of page 77 to "gray filter."

3) From the bottom line of page 77 to page 7r/line, change "yellow, magenta, and cyan color moat corresponding to the three-color separation filter of B, G, and R" to "positive color moat corresponding to the gray filter""Colorimage" and correct it.

that's all

Claims (1)

[Claims] In the presence of a hydrophilic heat solvent, an image forming reaction system containing a poorly soluble metal compound and a compound that causes a complex formation reaction between the metal ions constituting the hardly soluble metal compound and a compound that increases the pH through a complex formation reaction using a molten hydrophilic heat solvent as a medium. An image forming method characterized by downward heating.