JPS62244042A - Image forming method - Google Patents

Abstract

PURPOSE:To provide an image high in density and low in fog, to enhance storage stability, and to facilitate processing by reacting a compound capable of forming a complex using water as a medium with a hardly soluble metal compound and the ions of the metal constituting this metal compound in the presence of water, and raising pH in the image forming reaction system containing a specified nondiffusive oxidizable dye donor (coupler). CONSTITUTION:In the image forming reaction system containing the nondiffusive oxidizable dye donor (coupler) represented by the formula shown on the right, A being the residue of a diffusive dye or its precursor, the compound capable of forming a complex using water as a medium with the hardly soluble metal compound and the ions of the metal constituting this metal compound in the presence of water are reacted, and pH is raised, thus permitting the obtained image to be high in density, low in fog, superior in storage stability, and easy in processability.

Description

[Detailed description of the invention]! TECHNICAL FIELD OF THE INVENTION The present invention relates to an image forming method, and more particularly to a method for forming a dye image in an alkaline atmosphere.

Prior art and its problems Photography using silver halide has traditionally been the most popular method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. Widely used.

In this photographic method, a light-sensitive element having a silver halide emulsion layer and an image-receiving element having an image-receiving layer are laminated, and an alkali processing composition is spread in a layer within this laminate. There is a color diffusion transfer method that involves immersion in a processing solution.

In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. has been done.

A new color image forming method using heat development was published in Japanese Patent Application Laid-Open No. 57-179.
No. 840, No. 57-186774, No. 57-1984
No. 58, No. 57-207250, No. 58-58543
No. 58-79247, No. 58-116537,
No. 58-149046, No. 59-48764, No. 5
No. 9-65839, No. 59-71046, No. 59-8
No. 7450, No. 59-88730, etc.

When photosensitive silver halide and/or organic silver salts are reduced to silver by heat development, a mobile dye is generated or released in response to or inversely to this reaction, and the mobile dye is converted into a dye. This is a method of transferring to a fixed element.

In order to develop photosensitive materials, it is generally desirable to increase the pH of the reaction system. However, when a photosensitive material contains a strongly alkaline material, problems tend to occur in terms of storage stability. Further, when it is included in an image-receiving material, problems such as accelerated hydrolysis of gelatin arise.
Furthermore, when a substance that changes the pH is added to the water supplied from outside during transfer or development, there are many inconveniences in terms of storage and handling.

(2) Purpose of the Invention An object of the present invention is to provide an image forming method that provides images with high density and low capri, has excellent storage stability, and is easy to process.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the present invention provides a poorly soluble metal compound, a compound that can undergo a complex formation reaction with a metal ion constituting the hardly soluble metal compound using water as a medium, and a non-diffusible oxidizable compound represented by the following general formula (I). In an image forming reaction system containing a dye-providing compound, in the presence of water, a reaction between the above-mentioned sparingly soluble metal compound and a metal ion constituting this sparingly soluble compound and a compound that can undergo a complex-forming reaction using water as a medium. , is an image forming method characterized by increasing pH.

General formula (I) (In the above general formula (I), A represents a residue of a diffusible dye or its surface precursor. X represents a divalent bonding group, and m represents 0 or l.

Yl and Y2 may be the same or different,
Represents a group or a precursor thereof that can be oxidized to form a P-quinoid system by being located at the p-position with respect to each other. However, Y2 is not a secondary amino group. R1 represents a substituted or unsubstituted hydrocarbon group, and R2 represents hydrogen or a substituted or unsubstituted hydrocarbon group. In addition to the same definition as R2, R3 is a group that connects with R4 to complete a fused heterocycle or carbocycle, a hydroxyl group, a halogen atom, a substituted or unsubstituted amino group, an acylamino group, an alkylthio group, an alkoxy group, or an aryloxy group. , or represents a sulfo group. R4 is a hydrocarbon group, or R3
Represents a group that is linked to complete a fused heterocycle or carbocycle. R5 represents a substituted or unsubstituted hydrocarbon group. At least one of R1, R3, R4, and R5 contains a diffusion resistance imparting group. ) ■Specific structure of the invention The specific structure of the present invention will be explained in detail below.

In the image forming method of the present invention, a poorly soluble metal compound and a compound that can undergo a complex formation reaction with water as a medium (hereinafter referred to as a complex forming compound) with metal ions constituting the poorly soluble metal compound are added to the image forming reaction system. The reaction between these two compounds in the presence of water lowers the pH of the reaction system.
to rise.

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

In the present invention, the water used as a medium can be obtained by supplying water from outside, by immersing the element in water or an aqueous solution, or by placing a capsule containing water in the image forming reaction system in advance and destroying the capsule by heating, etc. Water can be supplied using methods such as water supply.

Examples of poorly soluble metal compounds used in the present invention include water solubility (number of grams of substance dissolved in 100 g of water);
Included are carbonates, phosphates, silicates, borates, aluminates, hydroxides, oxides, and double salts of these compounds, such as basic salts, with 0.5 or less.

and 2 TII xn The one represented by is preferable.

Here, T is a transition metal such as Zn, Ni, Co, Fe,
represents Mn, etc., and X can serve as a counter ion for M, which will appear in the explanation of complex-forming compounds described later in water,
It also represents something that is alkaline, such as carbonate ion, phosphate ion, silicate ion, borate ion, aluminate ion, hydroxyl ion, and oxygen atom. 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, magnesium calcium carbonate ((:aMg(C:03) 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 (2ZnCO3・3Zn
(Oll) 2 ・H20), basic magnesium carbonate (3Mg to Os ・Mg(OH)2 ・:IH20)
, basic nickel carbonate (NiCO3.2Ni(OH)
2), basic bismuth carbonate (Bi 2 (GO3)
02 ・R20), basic cobalt carbonate (2GoCO
3-311: o(OH) 2 ), magnesium aluminum oxide Among these compounds, uncolored compounds are particularly preferred.

The complex-forming compound used in the present invention has a stability constant of 1 in IlogK with respect to the metal ion constituting the hardly soluble metal compound.
A complex salt having a value of 0 or more is produced.

These complex-forming compounds are described, for example, by N.E. Martill and R.M. Smith.
ell, R, M, 5siLh) co-author, “Critical
Stability Constant (Critical Sta.
"Bility Con5tants), Volumes 1-5",
Plenus Press.

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acids and compounds with substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, and amidines. Alternatively, salts such as quaternary ammonium salts may be mentioned.

Preferred specific examples include picolinic acid, 2゜6-pyridinedicarboxylic acid, 2.5- and lysinedicarboxylic acid, 4-
Dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA, NTA, CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, 1102 CC1120(:H2(:lI20C112
C02H.

1102CCH21cH2CO2II.

Examples include alkali metal salts such as guanidine salts, amidine salts, quaternary anthonium salts, and the like.

Among these, aromatic heterocyclic compounds having at least one -CO2M and one nitrogen atom in the ring are preferred. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position where O2M is bonded to the ring is particularly preferably α-position with respect to the N atom. M is any one of an alkali metal, guanidine, amidine and quaternary ammonium ion.

More preferable compounds include those represented by the following formula.

Formula In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -co2M, a hydroxycarbonyl group, and an electron-donating group such as an amino group, a substituted amino group, and an alkyl group. Two R's may be the same or different.

zl and 22 each have the same definition as in R, and Zt and 22 may be combined to form a ring fused to the pyridine ring.

Next, the most preferred examples of combinations of poorly soluble metal compounds and complex-forming compounds are listed (here, M (B represents an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion, or a quaternary ammonium ion). ).

Basic magnesium carbonate - Basic zinc carbonate - Basic magnesium carbonate - Calcium carbonate - Zinc oxide - Lucium carbonateee ee Barium carbonate - MO2C-C02M ■ Calcium carbonate - M of tripolyphosphoric acid Calcium carbonate - M of citric acid Salt ■ Calcium carbonate - M of polyacrylic acid Calcium chloride - Magnesium oxide - Zinc hydroxide - H2C (:I13 Tin hydroxide - 83CC113 Calcium salt carbonate - Basic magnesium carbonate - ee ee MO2C・C02M Calcium carbonate - Basic carbonate Lead - A combination of these can be used alone or in combination of two or more. It can also be used in combination with a known base or base precursor.

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

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

That is, when water is present as a medium, picolinate ions undergo a complex formation reaction with zinc ions, and the reaction represented by the above formula proceeds, resulting in high alkalinity.

The progress of this reaction is due to the stability of the complex formed, but the progress of this reaction is due to the stability of the complex formed, and
The stability numbers of the complexes represented by ML, ML2, and ML3 produced from the above are very large as shown below.
The progress of this reaction is well explained.

ML ML2 ML3 jEog 5.30 9.62 12.92 In the present invention, it is desirable that the poorly soluble metal compound and the complex-forming compound be contained in at least one layer on separate supports. .

For example, it is preferable that the poorly soluble metal compound be contained in the light-sensitive material and the complex-forming compound be contained in the image-receiving material. The complex-forming compound may also be supplied dissolved in the water involved. Slightly soluble metal compounds are described in JP-A-59-174830 and JP-A No. 53-! It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 02733, etc., and the average particle size thereof is preferably c30μ or less, particularly preferably 5μ or less.

In the present invention, when a sparingly soluble metal compound or a complex-forming compound is contained in the layer on the support, it depends on the amount added, the compounding process, the particle size of the sparingly soluble metal compound, the complex-forming reaction, the reaction rate, etc. However, each coating film is converted into ffi amount of 50
It is appropriate to use it in an amount of 0.01% to 40% by weight, more preferably 0.01% to 40% by weight.
When the complex-forming compound is dissolved in water and supplied, the amount is 0.005 mol/It to 5 m
A concentration of o l / It is preferred, especially 0.05 m
Concentrations of offi/42 to 2 moIL/IL are preferred. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is 17 molar ratio to the content of the poorly soluble metal compound.
100 times to 100 times, particularly 1/10 times to 20 times is preferable.

In the image forming reaction system of the present invention, the following general formula <1)
It contains a non-diffusible oxidizable dye-providing compound represented by:

General Formula (I) In the above general formula (I), A represents a residue of a diffusible dye or its precursor. X represents a divalent bonding group,
m represents O or l.

Yl and Y2 may be the same or different,
Represents a group or a precursor thereof that can be oxidized to form a p-quinoid system by being located at the 2-position of each other. However, Y2 is not a secondary amino group. R1 represents a substituted or unsubstituted hydrocarbon group, and R2 represents hydrogen or a substituted or unsubstituted hydrocarbon group. In addition to the same definition as R2, R3 is a group that connects with R4 to complete a fused heterocycle or carbocycle, a hydroxyl group, a halogen atom, a substituted or unsubstituted amino group, an acylamino group, an alkylthio group, an alkoxy group, or an aryloxy group. , or represents a sulfo group. R4 is a hydrocarbon group, or R3
Represents a group that is linked to complete a fused heterocycle or carbocycle. R5 represents a substituted or unsubstituted hydrocarbon group. At least one of R1, R3, R4, and R5 contains a diffusion resistance imparting group.

In principle, suitable dye residues may be those having sufficient diffusivity to diffuse through the layers in the light-sensitive material into the image-receiving layer, and preferably have one or more water-solubilizing groups. .

Particularly preferred water-soluble groups include carboxyl groups, sulfo groups, sulfonamido groups, aliphatic or aromatic groups, and droxyl groups. However, if a sulfinic acid group remains in the dye after hydrolysis, the dye itself has sufficient diffusibility, so the water-solubilizing group may not be present. In the present invention, the dyes are particularly azo dyes, azomethine dyes,
Examples include anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, and metal complex dyes.

In the present invention, residues of the dye precursor are oxidized to
It is the residue of a compound that is converted into a dye during photographic processing by standard or additional processing steps, by coupling or by exposure of an auxochrome within the chromophore system, for example by hydrolysis.

A dye precursor so defined may be a leuco dye, a coupler, or a dye that is converted to another dye during processing.

X is -R-(L) p-(R)q- [where R represents a substituted or unsubstituted alkylene group or arylene group having 1 to 6 carbon atoms, and the two Rs are the same or different; Good too. L is -0-1-CO-1-CONRllll-
1-502NR'-1-0-CO-NR6-, -5-.

-5O- or -5o2- (R6 represents hydrogen or an alkyl group), and P is O or! , 9 represents 0 or l. ] represents.

Specifically, the following can be mentioned.

-CH2-CH2-0-CH2-CH2-5(ΣC2H
, - -CH2-CH2-S O□ -C6HI2-1Yl and Y2 include, for example, -OR'', -NH-R', -
NH-Ra, -N (Ra)2, -NH-3o2-R
' (Here, R7 represents hydrogen or a photographically inert group that is hydrolyzed under alkaline conditions, and R
a is a photographically inert organic group, preferably an alkyl group, particularly preferably a lower alkyl group having 1 to 4 carbon atoms, or an aryl group, which is bonded to the N-atom or the -5O2- group through its C-atom; , particularly preferably a phenyl group or a tolyl group. ). however,
Y2 is not -NCR')2.

A hydroxyl group is preferred as Yl and Y2.
If Yl and/or Y2 represent -NH-8O, -R8, R6 is preferably a photographically inert group, such as an unsubstituted alkyl group or a phenyl group.

R1 is a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, such as a methyl group, ethyl group, n-hexyl group, n-octyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-heptadecyl group ring; substituted or unsubstituted aralkyl group having 7 to 22 carbon atoms, such as benzyl group ring; substituted or unsubstituted aryl group having 6 to 22 carbon atoms, such as phenyl group.

The hydrocarbon group represented by R2 has 1 to 22 carbon atoms.
a substituted or unsubstituted alkyl group, such as a methyl group,
Ethyl group, propyl group, isopropyl group %n-hexyl group, n-octyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-heptadecyl group Ring: Substituted or unsubstituted with 7 to 22 carbon atoms Examples include an aralkyl group such as a benzyl ring; a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, such as a phenyl group.

Examples of the halogen atom represented by R3 include a chlorine atom and a bromine atom ring; and examples of the amino group include an amino group, an alkylamino group, a dialkylamino group, and a cyclic amino group (eg, a piperidino group, a sulfolino group, etc.).

The hydrocarbon group represented by R4 has 1 to 22 carbon atoms.
a substituted or unsubstituted alkyl group, such as a methyl group, ethyl group, or n-hexyl group; a substituted or unsubstituted aralkyl group having 7 to 22 carbon atoms, such as a benzyl group;
Examples include substituted or unsubstituted aryl groups having 6 to 22 carbon atoms, such as phenyl groups.

When R3 and R4 are connected to form a carbocyclic ring, examples of the fused ring include a benzene ring and a 2-bicyclo[2,2,13-heptene ring.

RIS includes substituted or unsubstituted alkyl, aralkyl, or aryl groups, especially n-
Propyl group is preferred.

Diffusion-resistance-imparting groups are groups that enable the compounds of the invention to be incorporated in diffusion-resistant form into the hydrophilic colloids commonly used in photographic materials.

Preferably a linear or branched aliphatic group or a carbocyclic group (
It is an organic group containing an aromatic ring (containing an aromatic ring) or a heterocyclic group, and has 8 to 22 carbon atoms. These groups are attached to the rest of the molecule directly or indirectly, for example through one of the groups described below.

-NHCO-1-N HSO*-1-NR- (R: hydrogen, alkyl group), -0-1-S-1-SO,- These groups are preferably grouped by at least two carbon atoms or a methylene group. From the aromatic ring of general formula (I) (R3,
)j4, when R1+ contains a diffusion resistance imparting group),
or -502-(x).

-A (removable group) is released from the carbon atom (if R1 contains).

Furthermore, the diffusion-resistance-imparting groups can also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which can also be present in anionic form. Since diffusivity depends on the molecular size of the entire compound used, in some cases, for example, if the entire molecule used is sufficiently large, it is possible to use a shorter chain group as the diffusion resistance imparting group. It is sufficient to use it.

Examples of non-diffusible oxidizable dye-providing compounds used in the present invention are shown below.

(I) c2H5 ■ H3 Zhan H3 url For the synthesis method of these compounds, please refer to JP-A-55-88
The method described in No. 054 can be applied.

Such a compound is usually contained in a photosensitive layer or a layer adjacent thereto in a photosensitive material.

Hydrophobic additives such as the dye-providing compounds described above and the image-forming accelerators described below are disclosed in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in the above. In this case, JP-A-59-
No. 83154, No. 59-178451, No. 59-17
No. 8452, No. 59-178453, No. 59-178
No. 454, No. 59-178455, No. 59-1784
A high boiling point organic solvent such as that described in No. 57 may 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 high-boiling organic solvent is 1 g of the dye-donating compound used.
10g or less, preferably 5gN.
The dispersion method using a polymer described in No. 3 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. Further, when dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used, and examples of these surfactants include No. 37 of JP-A-59-157636.
) to (38) pages can be used as surfactants.

In the present invention, it is particularly preferred to use silver halide as the photosensitive material.

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, pages 35 to 36 of Japanese Patent Application No. 59-228551.
Page, U.S. Pat. No. 4,500,626, No. 508I,
Research Disclosure Magazine! June 978 issue, page 9! Any of the silver halide emulsions described on page O (RD17029) etc. can be used.

The silver halide emulsion may be used as it is after heating, or it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, 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 carried out in the presence of a nitrogen-containing m-ring compound (
JP 58-126526, JP 58-215644).

The silver halide emulsion used in the present invention may be of the surface latent image type where the latent image is mainly formed on the grain surface, or may be of the internal latent image type where the latent image is formed inside the grain. Direct reversal emulsions combining internal latent image emulsions and imaging agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 rag to 10 g/- 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 include Japanese Patent Application No. 59-22855! No.37 Sada~
There are compounds described on page 39, columns 52 to 53 of U.S. Pat. No. 4,500,626. Also, special application 1986-2
Silver salts of carboxylic acids having alkynyl groups, such as silver phenylpropiolate described in No. 21535, are also useful.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.0 to 1 mole
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10 g/rn'
is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, JP-A-59-180550.

No. 60-140335, Research Disclosure Magazine, June 1978 issue 12~! 3 Sada (RD17029
), and thermochromic sensitizing dyes described in JP-A-60-111239, Japanese Patent Application No. 80-172967, and the like.

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, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
IMI color Ha may also be included in the paint (for example, U.S. Pat. No. 2.933.390, U.S. Pat. No. 3,635).
, No. 721, No. 3.743.510, No. 3.61
5゜613, same No. 3,615,641, same No. 3.6
Nos. 17,295 and 3,635,721).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in U.S. Pat. No. 4,183.
．． It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666.

The amount added is generally on the order of 1 G-8 to 10-R per mole of silver halide.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. 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 develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500,626, columns 49-50, same No. 4,483
, No. 914, columns 30-31, JP-A-60-14033
No. 5, pages (I7) to (I8), JP-A-60-1284
No. 38, No. 60-128436, No. 60-12843
Reducing agents described in No. 9, No. 60-128437, etc. can be used. Also, JP-A-56-138736 and JP-A-57
Reducing agent precursors described in US Pat. No. 4,330,617 and the like can also be used.

Combinations of various developers can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, an image formation accelerator can be used in the light-sensitive 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 mobile 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 groups of substances generally have multiple functions and usually combine some of the above-mentioned promoting effects.

For details of these, see Japanese Patent Application No. 59-213978 6.
It is described on pages 7-71.

In the present invention, various development stoppers can be used 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 Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, patent application No. 58-216928, No. 59-4
No. 8305, No. 59-85834 or No. 59-85
836).

Compounds that release mercapto compounds upon heating are also useful;
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 460-24665, No. 60-29892, and No. 59-176350.

Further, in the present invention, a compound that activates the development and stabilizes the image can be used in the photosensitive material.

Specific compounds preferably used are described in columns 51-52 of US Pat. No. 4,500,626.

Various antifoggants can be used in the present invention. Examples of anti-capri agents include azoles, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, mercapto compounds and their metal salts as described in JP-A-59-111636, and mercapto compounds and their metal salts as described in JP-A-59-111636;
Acetylene compounds described in No. 228267 are used.

In the present invention, the photosensitive material may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-93.

The binders used in the photosensitive material of the present invention may be contained alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent, and include proteins such as gelatin and gelatin derivatives, natural substances such as cellulose derivatives, starch, polysaccharides such as gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric substances include dispersed vinyl compounds, in the form of latexes, which, among other things, increase the quality of photographic materials.

In the present invention, the binder is applied in an amount of 20 g or less per lrn', preferably 10 g or less, more preferably 7 g 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 1 g of binder to 1 g of solvent, preferably 0.
A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The photographic light-sensitive material and dye-fixing material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other binder layers.

Specific examples of hardening agents can be found in Japanese Patent Application No. 59-268926, pages 94-95, and Japanese Patent Application Laid-open No. 59-157636 (
Examples include those described on page 38), and these can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. --Generally used supports include glass, paper, polymer films, metals and their analogues;
Those listed in 9S1jl-96-96 of No. Am can be used as the support.

When the light-sensitive material used in the present invention contains a colored dye-donating substance, it is not so necessary to further contain an irradiation-preventing substance, an anti-halation substance, or various dyes. There is no such thing as Japanese patent application No. 59-268926, pages 97-98, and U.S. Patent No. 4.5.
Filter dyes, absorbent substances, etc. described in the literature exemplified in column 55 (lines 41 to 52) of No. 00.626 can be contained.

Using the three primary colors of yellow, magenta, and cyan, SenWf
A light-sensitive element used in a photosensitive element must have at least three silver halide emulsion layers, each sensitive to a different spectral region.

A typical combination of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions is described in JP-A-59-180550.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

The photosensitive material used in the present invention may contain various additives known as heat-developable photosensitive materials and layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an A
14 layers, a release layer, a matte layer, etc.

Examples of various additives include additives 1 described in Research Disclosure Magazine Vol. 1.170, No. 17029, June 1978, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, matting agents, and interfaces. activator, optical brightener, ultraviolet absorber, slip agent,
There are additives such as antioxidants and anti-fading agents.

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

Further, the intermediate layer may contain a reducing agent, a UV absorber, and a white pigment such as TiO2 to prevent color mixing. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing 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 systems that form images 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. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with the white reflective layer, the relationship described in Japanese Patent Application No. 59-268926, pages 58-59, and U.S. Pat. No. 4,500,626, column 57, can also be applied to the present application.

A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel off the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. As a preferable embodiment, for example, transparent support/li! 5 Optical layer/white reflective layer/dye fixing layer, transparent support/dye fixing layer/white reflective layer/
Examples include an HA optical layer.

Another typical embodiment in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
Canadian Patent No. 674°082, U.S. Patent No. 3,7
30,718, in which part or all of the light-sensitive element is peeled off from the dye-fixing element;
Examples include those having a release layer coated at an appropriate position.

The photosensitive element or 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, Nia II, an inorganic material that exhibits initiative
There are two methods: one that uses a film, and one that uses an organic thin film in which conductive particles are dispersed in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. 151,815/1984.

The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

The layer structure of the dye fixing element and the installation positions of the binder, additives, and mordant addition layers are as described in Japanese Patent Application No. 59-268926, page 62, line 9 to page 63, line 18, and the patent specifications cited therein. What is described is also applicable to this application.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye transfer, a hydrophilic heat solvent, an anti-fade agent to prevent dye fading, a UV absorber, a slip agent, a matte Agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, optical brighteners, etc. may also be included. Specific examples of these additives are given in Japanese Patent Application 1983-
No. 209563, pages 101 to 120.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. Specifically, the binders mentioned above for the photosensitive materials are used.

The image-receiving layer in the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer containing a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Regarding this specific example, please refer to Japanese Patent Application No. 59-268926.
57 of U.S. Pat. No. 4,500,626.
- It is described in column 60.

In the present invention, the coating method for the photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers is based on US NZ4,500.6.
The method described in No. 26, i55-56sIl can be applied.

As a light source for image exposure to record an image on a photosensitive material, radiation including visible light can be used, for example, as described in Japanese Patent Application No. 59-268926, p.
, 500,626, column 56, can be used.

In the treatment according to the present invention, JP-A-59-21844
No. 3, Japanese Patent Application No. 60-79709, etc., a method in which development and transfer are carried out simultaneously or successively by heating in the presence of a small amount of water is also useful. In this method, the image formation accelerator described above may be included in advance in either or both of the dye fixing material and the photosensitive material, or may be supplied from the outside.

The heating temperature is 40°C or higher and lower than the boiling point of the solvent, preferably 5°C.
The temperature is preferably 0°C or higher and 100°C or lower.

Further, a surfactant, an antifoggant, a poorly soluble metal salt and a complex forming compound, etc. may be included in the water.

Water can be used in dye-fixing materials or light-sensitive materials, and in methods for applying them to both.

The amount used may be as small as less than the weight of water corresponding to the maximum swelling volume of the entire coating film (particularly less than m, which is the weight of water corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

Water is applied between the photosensitive layer of the heat-developable photosensitive material and the dye fixing layer of the dye fixing material to promote image formation and/or dye movement. It can also be used built into both.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, page 101, line 9 of Japanese Patent Application No. 59-268926.
There is a method described on page 102, line 4.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated 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.
It may be built into both. Further, the layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto.

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

The heating means in the transfer process is disclosed in Japanese Patent Application No. 59-26892.
There is a means described in No. 6, page 102, line 14 to page 103, line 11. Alternatively, a layer of an electrically conductive material such as graphite, carbon black, or metal may be applied to the dye-fixing material in an overlapping manner, and an electric current may be passed through this electrically conductive layer to heat it directly.

The pressure conditions and method of applying pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application No. 59-2.
The method described on pages 103 to 104 of No. 68928 can be applied.

■Specific effects of the invention According to the invention, in an image forming reaction system containing a non-diffusible oxidizable dye-providing compound represented by the general formula (I), in the presence of water, a sparingly soluble metal compound is The pH is raised by the reaction between the metal ions constituting this poorly soluble metal compound and a compound that can undergo a complex formation reaction using water as a medium, resulting in high density, low fog images and storage stability. An image forming method that is excellent in quality and easy to process can be obtained.

(2) Specific Examples of the Invention In the following, specific examples of the present invention will be shown, and the effects of the present invention will be explained in detail.

Example Preparation of benzotriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and 10 g of gelatin were added to 10 g of water.
Dissolved in 0100O. This solution was kept at 50°C and stirred. Next, a solution prepared by dissolving 8.5 g of silver nitrate in 100 mJ2 of water was added to the above solution over a period of 2 minutes.

Next, a solution of 1.2 g of potassium bromide dissolved in 50 mff1 of water was added over 2 minutes. The prepared emulsion was precipitated by pH adjustment to remove excess salt. Thereafter, the ρ■ of the emulsion was adjusted to 6.0.

Yield was 200g.

Preparation of gelatin dispersion of non-diffusible oxidizable dye-providing compound 5 g of non-diffusible oxidizable dye-providing compound 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, tricresyl phosphate ( TCP
) 10g, cyclohexanone 20I! Add lIL,
The mixture was heated and dissolved at about 60°C. 1 of this solution and gelatin
After stirring and mixing with 100 g of 0% solution, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes.

Next, a method for preparing a photosensitive coating liquid will be described.

(a) Benzotriazole silver emulsion containing photosensitive silver bromide
10g (b) Dispersion of dye-providing compound 3.5g (C) 5% aqueous solution of the following compound 1.5 + nu C9H+9()0 + CH2CH20)aH (d) Basic zinc carbonate (20% aqueous dispersion) After mixing 3.0 g or more of (a) to (d) and heating and dissolving,
It was coated on a polyethylene terephthalate film to a wet film thickness of 30 μm and dried.

Furthermore, as a protective layer on top of this, 30% of the following composition was added.
The photosensitive material was coated with a wet film thickness of 10 μl and dried.
1 was created.

b) Seratin (I0% aqueous solution) 30g mouth) 1.2-
Bis(vinylsulfonylacetate 17″: 18゛1 go-) “29d★浣'mFsmσc) Water
In the 70IIIt photosensitive material 101, the dye-providing compound is compound (2), (I1), (3), (5
), (I4), and then photosensitive material 10
2.103.104.105.106.

Next, we will discuss how to make the dye fixing material.

Dissolve 10 g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:l) in 175 mj2 of water,
It was uniformly mixed with 100 g of 10% acid-treated gelatin.
Add 25 mj of a 2% aqueous formalin solution to this mixture! was added and uniformly applied to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed.

Furthermore, add 6 g of guanidine picolinate and 18 ml of water.
, 20 g of 10% gelatin, 4.8 mJ of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate
! A mixed and dissolved solution is applied to a wet film thickness of 30 μm, and after drying, it is used as a dye fixing material having a mordant layer.

Each of the photosensitive materials shown above was exposed imagewise for 10 seconds at 2000 lux using a tungsten bulb.

Water at 20 mf/112 was supplied to the emulsion surface of the exposed light-sensitive material using a wire bar, and then the material was superimposed so that the dye-fixing material and the film surface were in contact with each other.

When the dye-fixing material was peeled off from the photosensitive material after heating for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90 to 95°C, a clear image was obtained on the fixing material.

Measure the maximum and minimum density using a Macbeth reflection densitometer (RD-51).
9), the results shown in Table 1 were obtained.

Table 1 106 (I4) 1. 81
0. 23 Furthermore, the above photosensitive material and dye fixing material were each stored at 40°C and 70% relative humidity for 7 days and then processed in the same manner, but both the maximum and minimum densities were almost the same as above.

From the above, the effects of the present invention are clear.

Claims (1)

[Scope of Claims] A poorly soluble metal compound, a compound that can undergo a complex formation reaction with a metal ion constituting the hardly soluble metal compound in water as a medium, and a non-diffusible oxidizable compound represented by the following general formula (I). In an image forming reaction system containing a dye-providing compound, in the presence of water, a reaction between the above-mentioned sparingly soluble metal compound and a metal ion constituting this sparingly soluble compound and a compound that can undergo a complex-forming reaction using water as a medium. , an image forming method characterized by increasing pH. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the above general formula (I), A represents a residue of a diffusible dye or its precursor. X represents a divalent bonding group, and m Represents 0 or 1. Y^1 and Y^2 may be the same or different, and represent a group or its precursor that can be oxidized to form a p-quinoid system by being located at the p-position of each other. However, Y^2 is not a secondary amino group. R^1 represents a substituted or unsubstituted hydrocarbon group, R^2 represents hydrogen or a substituted or unsubstituted hydrocarbon group. R^3 is In addition to those synonymous with R^2, groups that combine with R^4 to complete a fused heterocycle or carbocycle, a hydroxyl group, a halogen atom, a substituted or unsubstituted amino group, an acylamino group, an alkylthio group, an alkoxy group, or Represents an aryloxy group or a sulfo group.R^4 is a hydrocarbon group,
Alternatively, it represents a group that is linked to R^3 to complete a fused heterocycle or carbocycle. R^5 represents a substituted or unsubstituted hydrocarbon group. R^1, R^3, R^4 and R^5
At least one of them contains a diffusion resistance imparting group. )