JPS62220953A - Image forming process - Google Patents

Abstract

PURPOSE:To obtain a picture image having high density, high preservability, and low fog but contg. no unevenness, in a process for forming a picture image contg. a scarcely water-soluble metal compd. and a complexing agent capable of causing a complex-forming reaction between the metal ion constituting the scarcely water-soluble basic metal compd. in aq. medium and elevating pH, by incorporating further a high molecular corporating further a high molecular complexing agent into the system. CONSTITUTION:A scarcely water-soluble basic metal compd, a complexing agent (movable complexing agent) capable of causing a complex forming reaction between the metal ion constituting said scarcely water-soluble basic metal compd in aq. medium to elevate pH by the reaction, and further a high molecular complexing agent is incorporated in a picture image forming reaction system, thus the pH of the reaction system is elevated by the reaction among the three compds. in the presence of water. In this case, the movable complexing agent functions catalytically in the reaction between the scarcely water-soluble basic metal compd. and the high molecular complexing agent in the water. By this method, a picture image having high density, low fog, but no unevenness is provided, permitting preparation of picture image having high preservability is obtd. with easy treatment.

Description

Detailed Description of the Invention (1) Background Technical Field of the Invention The present invention relates to an image forming method, and particularly to a method of forming a dye image by heating in an alkaline atmosphere.

Prior art and its problems Photography using silver halide has been the most popular method in the past because it has superior photographic properties such as sensitivity and level 2 adjustment compared to other photographic methods such as electrophotography and diazo photography. Widely used. 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.

By the way, in order to develop a photosensitive material, 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 contained 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.

In order to solve these problems, the present inventors have developed a method for adjusting the pH by a reaction between a basic metal compound that is sparingly soluble in water and a complexing agent.
(Japanese Patent Application No. 60-169585) has proposed a method for increasing the

However, since the complexing agent used in this case is a crystalline salt, if it is incorporated into the image forming reaction system in large quantities, crystals will precipitate, which may deteriorate the surface condition of the photographic material or cause cracks. Problems such as Such problems become especially noticeable during storage.

When such photographic materials are used, image unevenness occurs.

■ Purpose of the Invention The purpose of the present invention is to provide uniform images with high density and low fog. It is an object of the present invention to provide an image forming method that is easy to process, has excellent storage stability, and is easy to process.

■Disclosure of invention One such objective is achieved by the present invention described below.

That is, the present invention provides a complexing agent capable of raising the pH through a complex formation reaction with a basic metal compound that is sparingly soluble in water and gold H ions constituting the basic metal compound that is sparingly soluble in water, using water as a medium. This image forming method is characterized in that the image forming reaction system further includes a polymer complexing agent.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

In the image forming method of the present invention, a basic metal compound (I) that is sparingly soluble in water is added to the image forming reaction system, and a complex is formed with metal ions constituting the basic metal compound that is sparingly soluble in water using water as a medium. A complexing agent (I) that can react and raise the pH
I) (mobile complexing agent) and further polymeric complexing agent (m)
and the reaction between these three compounds in the presence of water raises the pH of the reaction system.

In this case, the mobile complexing agent (II) plays a catalytic role in the reaction between the basic metal compound that is sparingly soluble in water and the polymeric complexing agent.

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.

A particularly preferred image-forming reaction system in the present invention is a system in which heating is performed for development or for diffusion of dyes distributed in an image. In particular, it is an image forming reaction system that is heated in the presence of water to diffuse a diffusible dye that is generated in the form of an image at the same time as development.

In the present invention, the water used as a medium can be supplied by a method of supplying water from the outside, a method of pre-existing a capsule containing water in the image forming reaction system, and a method of destroying the capsule by heating etc. and supplying water. can.

Examples of the basic metal compound (I) that is sparingly soluble in water used in the present invention are compounds whose solubility in water (the number of grams of a substance dissolved in 100 g of water) is 0.5 or less; Those represented by are preferred.

Here, T is the transition total bending, such as Zn, Ni, Cu, Co,
Fe, Mn etc. or alkaline earth metals such as Ca, M
G, 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 water, and exhibits alkalinity, such as carbonate ion, phosphate ion, silicate ion, etc. Represents acid 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, magnesium calcium carbonate (CaMg(GO3) 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 (2ZnC03.:1Zn(
011) 2 ・1120), basic magnesium carbonate (3MgCO3・Mg(Oll)z ・311z O
), basic nickel carbonate (Ni(:03 ・2Ni(
011) 2), basic bismuth carbonate (Bi 2
((:03)02 ・1120), basic cobalt carbonate (2GO(:03 ・3Co(Off) 2 )
, aluminum magnesium oxide, Cu(Oll)2
, basic copper carbonate.Among these compounds, uncolored ones are particularly preferred.

The complexing agent (II) used in the present invention is the water-insoluble salt.
, a metal ion forming an ellipsoid of the ζ metal compound (1) and a complex salt having a stability constant of logK of 1 or more.

For these complexing agents (II), e.g.
Marcil, R.M. Smith (8, E, Mar
Lell, It, M, Sm1Lh), “Critical Stability Constance (CriticalS
tabiliLy Con5tanLs), 1st to 5a
”, Plenum f'ress.

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 further substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), hydroxamic acids, alkali metals such as polyphosphoric acids, guanidines, amidines, or quaternary ammonium Examples include salt such as salt.

Preferred specific examples include picolinic acid, 2,6-pyridinedicarboxylic acid, 2,3- and lysinedicarboxylic acid, 2,
5-pyridinedicarboxylic 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, N.T.A.
, CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, +102 CG1120CI+ 201120C112
CrJ2 II.

++02 (:C1120(:112 CO211.

Examples include alkali metal salts such as guanidine salts, amidine salts, and quaternary ammonium salts.

Among these, Banko group m ring 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 (A).

Formula (A) In the above formula (A), R is a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -CO2M, a hydroxycarbonyl group, and an electron Lp group such as an amino group, a substituted amino group, or an alkyl group. It represents my Izuka. 2
The two Rs may be the same or different.

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

The polymeric complexing agent (I[I) used in the present invention preferably has a structure similar to that of the complexing agent (■) described in n1 mentioned above in its structure.

Among these, preferred are those having a structure similar to that represented by the surface formula (A) as a part thereof.

This is because when forming a polymeric metal complex with metal ions constituting the basic metal compound (I) that is sparingly soluble in water, it is necessary to form a complex as stable as possible in order to increase the efficiency of pH increase. be.

The polymer complexing agent (01) preferably has a molecular weight of to, ooo or more from the viewpoint of photographic properties, coating suitability, etc. In addition, when using the polymer complexing agent (Ill) as a solution, the molecular weight should be 1,000,0
00 or less, especially soo, ooo or less.
Delicious.

Specific examples of the polymer complexing agent (III) include salts such as alkali metals, guanidines, amidines or quaternary ammonium salts of polymers having monomer units of (e) (f) (k) (r). can be mentioned.

Note that the above polymer may be a copolymer of one unit of the above monomer and one unit of another monomer.

These polymer compounds are generally known as chelate resins and the like, and the following literature can be referred to regarding their synthesis.

Journal of Chromatography (, J, (:t
+romaaLogr, ) 18 572 (1965)
Zeitschrift Fear Analytissier Himi (1,8 na1.C11c+n,) 192 36
4 Chemical Abstracts ((:bca+, 8bsL
r-) R Industrial Chemistry Magazine 59 196 (1956) Ion Exchange Technology (Ion, Exch
, Tccgnol, ) 257 (1984) Journal of General Chemistry of the USSR (J, Gcn, ClIcll1. USSR)
43 7 1 9 Macromolekurare Himi (Ma
kromol, 1cm, ) 59 106 (1963) Industrial and Engineering Chemistry (Ind, EnH, Nihem,) 44 2 Chemical and Engineering News (Chcm, Eng, News) 32 1
8 9 7 Himish Tehinik (Chcm, Tc
chn, ) 10 Journal of the American Chemical Society (J, 8m, Chcm, Soc,
) 81st grade.

Hereinafter, a basic metal compound (I) that is sparingly soluble in water, a mobile complexing agent (■), and a polymer complexing agent (
Specific examples of preferred combinations of II[) are shown below.

IF2 (!0) (it) These combinations 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 in the present invention will be explained using the combination (1) as an example.

The reaction is shown by the following formulas (a) and (b).

l \,・---・,/X [1000 And to summarize, the following formula (C) is obtained,
When water comes to exist as a medium, the above-mentioned complex formation reaction progresses, and as a whole, KOH is produced by the complex formation reaction between zinc hydroxide and potassium polyvinyl picolinate, mediated by potassium picolinate. Become.

In the present invention, it is preferable that the water-insoluble basic metal compound (I) and the complexing agents (II) and (m) be contained in at least one layer on separate supports.

For example, it is preferable that the basic metal compound that is sparingly soluble in water is contained in the light-sensitive material, and the complexing agent (■) and ([r) are contained in the image-receiving material. Moreover, the complexing agent (II), (III) is
It may also be supplied dissolved in the water involved. Basic metal compounds that are sparingly soluble in water are described in JP-A-59-174830.
It is desirable to contain it in the form of a fine particle dispersion prepared by the method described in Japanese Patent No. 53-102733, and the average particle size thereof is preferably 50 μm or less, particularly 5 μm or less.

In the present invention, when the water-insoluble basic metal compound (I) or the complexing agent (n), (m) is contained in the layer on the support, the addition amount [complexing agent (II), (III) ) is the total amount] depends on the compound species, the particle size of the basic metal compound that is sparingly soluble in water, the complex formation reaction rate, etc.
It is appropriate to use it in an amount of 50% by weight or less in terms of fl amount, and more preferably a range of 0.01% by weight to 40% by weight and 61% by weight. In addition, when the complexing agent (n) is dissolved in water to make a leap year and supplied, 0.005 moI
A concentration of 1/It to 5moJ2/42 is preferred;
Especially 0.05moffi/Il to 2IIIor! ,
A concentration of /2 is preferred.

The ratio of complexing agent (II) and polymer complexing agent (III) is
The molar ratio of structural units having complex-forming ability is preferably between 2=1 and 1:50, more preferably 1:2 and 1:1.
A value between 0 is good.

Furthermore, in the present invention, the content of the complexing agents (n) and (III) in the reaction system is 17,100 times to 100 times, particularly 1,000 times, in terms of molar ratio, to the content of the basic metal compound (I) that is sparingly soluble in water. /10 times to 20 times is preferable.

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, 35L1-3 of Japanese Patent Application No. 59-228551
p. 6, U.S. Pat. No. 4,500°626, column 50, Research Disclosure, June 1978, p. 9-
Any of the silver halide emulsions described on page 10 (RD17029) can be used.

Silver halide emulsions may be used as they are after ripening, but they are usually used after being chemically sensitized. For emulsions for school-type light-sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used individually or in combination. These chemical sensitizations can also be performed in the presence of nitrogen-containing heterocyclic compounds (
JP 58-126526, JP 58-215644).

The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

The coating amount of the photosensitive silver halide used in the present invention ranges from 1 mg to tog/g of silver.

In the present invention, a metal salt can also be used as an oxidizing agent together with photosensitive silver halide. In this case, the photosensitive silver halide and the metal salt must be in contact with each other or at a close distance.

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

Examples of the beating compound that can be used to form the above-mentioned beating silver salt oxidizing agent include Japanese Patent Application No. 59-228551, page 37.
There are compounds described on page 39, columns 52 to 53111 of US Pat. No. 4,500,626. Also, the special request was made in 1983.
Silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in No. 221535, are also useful.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. It is appropriate that the total coating star of photosensitive silver halide and press silver salt is 50 mH to 10 g/♂.

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, pp. 12-13 (RD17029
), and heat-decolorizable sensitizing dyes described in JP-A-60-111239, Japanese Patent Application No. 60-172967, and the like.

These sensitizing dyes may be used individually or in combinations thereof, 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 light7.
Substances exhibiting supersensitization may be included in the emulsion (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.721, U.S. Pat. No. 613,
3,615°641, 3,617,295, and 3,635,721).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
No. 756, or after the nucleation surface of silver halide grains according to No. 4,225,666.

The amount added is generally 104 to 1 per mole of silver halide.
It is about 0-t mole.

In the present invention, silver can be used as the image forming material. It also contains a compound that generates or releases a mobile dye in response to or inversely to this reaction when photosensitive silver halide is reduced to silver under high temperature conditions, that is, a dye-donating substance. You can also.

Next, the dye-donating substance will be explained.

Examples of dye-donating substances that can be used in the present invention include couplers that react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Specific examples of developers and couplers can be found in "The Theory of the Photographic Process" by James, 4th edition (T. Il., Jamcs.
“ The Theory of the
Photo-graphic Process”)
pages 291-334, and pages 354-361, JP-A-58-123533, JP-A-5B-149046, JP-A-58-149047, JP-A-59-111148, JP-A No. 5
No. 9-124339, No. 59-174835, No. 59-231539, No. 59-2
No. 31540, No. 60-2950, No. 60-2951
No. 60-14242, No. 60-23474, No. 60-66249, etc.

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds are given in Research Disclosure Magazine 1978 (
F May issue, pages 54-58 (RD-16966), etc.

Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances. Specific examples of azo dyes and bleaching methods are disclosed in U.S. Pat. No. 4,235,957.
No., Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433).

Also, U.S. Patent No. 3,985,565, U.S. Patent No. 4.02
Leuco dyes described in No. 2,617 and the like can also be cited as examples of dye-donating substances.

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 (Lr).

(Dye-X)n-Y (Ll)Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, X represents a simple bond or a connecting group, and Y represents a latent image Correspondingly or inversely to the photosensitive silver salt having (Dye- X) represents a group that has the property of causing a difference in diffusivity between n-Y, where n is 1
or 2, and when n is 2, the two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (L), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Pat. , No. 819, No. 3,597゜200, No. 3,544,545, No. 3,482,972
It is stated in the number etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in JP-A-51-63゜618, etc., and a substance that releases a diffusible dye through an intramolecular rewinding reaction of the isoxacilone ring is disclosed in JP-A-51-63゜618. 49-
No. 111,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

Another method is to make the dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its surface precursor, and after development, reduce it with the reducing agent that remains unoxidized to make it diffusible. A method for releasing pigment has also been devised,
Specific examples of dye-donating substances used therein include JP-A-53-110,827 and JP-A-54-130.92.
No. 7, No. 56-164, 342, No. 53-35533
listed in the number.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. .330,524, Special Publication 1977-39
No. 165, US Pat. No. 3,443,940, etc.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised.

A typical example is, for example, U.S. Patent No. 3928.312.
No. 4,053,312, No. 4,055,42
No. 8, No. 4.336.322, JP-A-59-658
No. 39, No. 59-69839, No. 53-3819,
No. 51-104343, Research Disclosure No. 17465, U.S. Patent No. 3,725,062,
3,728゜113, 3,443,939, JP-A-58-116.537, JP-A-57-17984
It is a dye-donating substance described in US Pat. No. 0, US Pat. No. 4,500,626, and the like.

Specific examples of the dye-providing substance used in the present invention include +
Compounds described in columns 22 to 44 of U.S. Pat. No. 4,500,626 mentioned in IF can be mentioned, among which compounds (1) to (:]) described in the said U.S. patent can be mentioned.
, (+0)~(+:11), (16)~(19)
, (28) to (30), (33), (35), (38)
~(40), (42) ~(64) are preferred. Also,
Compounds described on pages 80 to 87 of Japanese Patent Application No. 59-246468 are also useful.

Hydrophobic additives such as the dye-providing compounds described above and the imaging promoters described below are described 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 No. 7. In this case, JP-A-59
No. -83154, No. 59-178451, No. 59-1
No. 78452, No. 59-178453, No. 59-17
No. 8454, No. 59-178455, No. 59-178
A high boiling point battering solvent such as that described in No. 457 can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
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 binder in the form of fine particles in addition to the method described above. Furthermore, when dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used.
) to (38) pages can be used as surfactants.

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 (17) to (18), JP-A-1284-1984
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 promoting redox reactions between silver salt oxidizing agents and reducing agents, promoting reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixed layer, and from a physicochemical function, it has a base or base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, a surfactant, It is classified as a compound that interacts with silver or 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.
7-71α, it has been stolen.

In the present invention, various development stoppers can be used in a one-to-one manner to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper mentioned here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or interacts with silver and silver salts to stop development. It is an inhibitory compound. Specific examples include acid precursors that release acids when heated, electrophilic r-compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (e.g. Patent Application No. 58-216928, No. 59-
No. 48305, No. 59-85834 or No. 59-8
5836).

Compounds that release mercapto compounds upon heating are also useful;
-268926.

No. 59-246468, No. 60-26038, No. 6
No. 0-22602, No. 60-26039, [Tsukasa 60-
No. 24665, No. 60-29892, No. 59-176
No. 350 contains the compound a.

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 U.S. Pat. No. 4,500,626, No. 51-52 Jil.

Various anti-fogging methods can be used in the present invention. Antifoggants 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, polyvinylpyrrolidone, Includes synthetic compounds 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 soot stability of photographic materials.

In the present invention, the binder is applied in an amount of 20 g or less per batch, preferably less than tog, more preferably 7 g or less.

The ratio of the binder to the high boiling point solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance is 1 cc or less of solvent per 1 g of binder, preferably 0.
．． 5 cc or less, more preferably 0.3 cc or more F is suitable.

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

Hardening agents 1 (for the body side, those described in Japanese Patent Application No. 59-268926, pages 94 to 95, and Japanese Patent Application Laid-open No. 59-157636 (page 381) are listed, and these can be used alone or in combination. be able to.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. As a general support,
In addition to glass, paper, the polymer Fino-DM, metals and their analogues, those listed as supports on pages 95 to 96 of Japanese Patent Application No. 59-268926 can be used.

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. Although there is no
00,626, No. 5511!1 (lines 41 to 52), filter dyes, absorbent substances, etc. described in the literature can be included.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta and cyan, the light-sensitive element used in the present invention comprises at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer.

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 optionally 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, and an intermediate layer. ,
It can contain an AH layer, a release layer, a matte layer, etc.

Examples of various additives include additives 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 for color mixing prevention IF, a UV absorber, and a white pigment such as TiO2. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing the 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 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. Preferred embodiments include, for example, transparent support/photosensitive layer/white reflective layer/dye fixing layer, transparent support/dye fixing layer/white reflective layer/photosensitive layer, and the like.

Another typical embodiment in which the light-sensitive element and the dye-fixing element are coated on the same support is disclosed in, for example, JP-A-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, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine 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 specification cited therein. 'f can also be applied to the present application.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be peeled off as necessary. ! , a matting agent layer, an anti-curl IF layer, and other auxiliary layers may be provided.

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 in the section of the photosensitive material 0η are used.

The image receiving layer in the present invention includes a dye fixing layer used in heat-developable color photosensitive materials, and can be arbitrarily selected from commonly used mordants, but polymer mordants are particularly preferred. . Here, the polymer mordant refers to a polymer containing a tertiary amino group, a nitrogen-containing EL
These include polymers having a bare ring moiety, and polymers containing these quaternary cation groups.

Specific examples of this can be found in Japanese Patent Application No. 1988-268926, pages 98-100, and U.S. Patent No. 4,500.
, No. 626, columns 57 to 60.

In the present invention, the coating method for the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers is disclosed in U.S. Pat.
The methods described in No. 55-56M11 of No. 0,626 can be applied.

As a light source for image exposure for recording an image on a heat-developable photosensitive material, radiation including visible light can be used,
For example, the light source described in page 100 of Japanese Patent Application No. 59-268926 or column 56 of U.S. Patent No. 4,500,626 is
■Irogato de 1L The heating temperature in the heat development process can be developed at about 0℃ to about 250℃, but in particular, about 0℃ to about 180℃, and the temperature during the transfer process is Transfer can be performed at a heating temperature ranging from the temperature in the heat development step to room temperature, but a temperature of 50° C. or higher and about 10° C. lower than the temperature in the heat development step is particularly preferable. As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc. can be used.

Also, Japanese Patent Application Publication No. 59-218443, Japanese Patent Application No. 60-79
As detailed in No. 709, etc., a method of heating in the presence of a small amount of a solvent such as water and performing development and transfer simultaneously or successively 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 light-sensitive material, or may be supplied from the outside.

In the method in which the above-mentioned development and transfer are performed simultaneously or continuously, the heating temperature is preferably 50° C. or higher and lower than the boiling point of the solvent. For example, if the solvent is water, 50℃ or more and 100℃
The following are desirable.

Further, a solvent may be used to transfer the mobile dye to the dye fixed layer.

Examples of solvents used to accelerate development and/or transfer mobile dyes to the dye fixed layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may be Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in dye-fixing materials, photosensitive materials, and in methods for applying them to both. The amount used should be less than the weight of the solvent corresponding to the maximum swollen volume of the entire coated film (particularly the weight of the solvent corresponding to the maximum swollen volume of the entire coated film).
It may be as small as the amount calculated by subtracting the weight of the entire tank I511Q from t.

A solvent (for example, 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 transfer. It can also be used by incorporating it into the dye fixing layer or both.

As a method for applying a solvent to the photosensitive layer or dye fixing layer, there is, for example, the method described in Japanese Patent Application No. 59-268926, page 101, line 9 to 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.

A method of applying pressure conditions when overlapping a heat-developable photosensitive material and a dye-fixing material and bringing them into close contact is disclosed in Japanese Patent Application No. 59-2689.
The method described in No. 26, pages 103 to 104 can be applied.

■ Specific effects of the invention According to the present invention, a basic metal compound that is dissolvable in water and a metal ion constituting the basic metal compound that is sparingly soluble in water undergo a complex-forming reaction using water as a medium to lower the pH. In the image forming reaction system that contains a complexing agent that can be used to increase the temperature, it also contains a polymeric complexing agent, which provides high density, low fog, and even images with excellent storage stability and processing properties. This provides an image forming method that is easy to use.

These effects are due to the fact that polymeric complexing agents can form more stable complex salts than low-molecular complexing agents due to the so-called polymer effect, resulting in higher alkali generation efficiency, and ■ Crystal precipitation. This is done to achieve the following advantages: the image-receiving material does not become uneven or cracked, and the film quality is improved.

③ Specific Examples of the Invention Below, specific examples of the present invention will be shown and the effects of the present invention will be explained in more detail.

Example 1 The method for preparing the emulsion for the first layer will now be described.

A well-stirred gelatin aqueous solution (20 g of seratin and 3 ml of sodium chloride in 100 100 O of water)
At the same time, 40 nN of an aqueous solution containing 1-lium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 Iwl of water) were added to Added at equal flow rates over a period of minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene were added to perform chemical sensitization at 60°C. The yield of emulsion was 600 g.

Next, I will talk about how to make the emulsion for the third layer.

A well-stirred gelatin aqueous solution (20 g of gelatin and 3 ml of sodium chloride in 1000 ml of water)
An aqueous solution containing thorium chloride and potassium bromide 600 + d (containing 600 mmol of silver nitrate dissolved in 600 mM water) and an aqueous solution of 600 + d containing thorium chloride and kept at 75 ° C. The dye solution (I) was simultaneously added isothermally over 40 minutes; In this way, a tunic-dispersed cubic silver chlorobromide emulsion (bromine 80 mol %) having a dye adsorbed thereon having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 20B were added to perform chemical sensitization at 60°C. The yield of the emulsion was 600 g.

Next, a method of making a silver halide IL agent for the fifth layer will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin and ammonia dissolved in too much water and kept at 50°C) was mixed with a 10001 M aqueous solution containing potassium iodide and potassium bromide and an aqueous silver nitrate solution (in 1000 ml of water). (1 mole of silver nitrate dissolved in)
were simultaneously added to p while keeping g constant. In this way, a monodispersed silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 211K sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1.0 g.

This article describes how to make organic silver salts.

Hitting machine silver salt (1) This article describes how to make hensitriazole silver emulsion.

28 g of Seratin and 13.2 g of Penzotriazole were dissolved in 3001111 of water. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then the pH was adjusted to 6.30.
A total of 400 g of benzotriazole silver emulsion was obtained.

Organic silver salt (2) 0.1% hydroxylation of 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid!・Rium aqueous solution 1
000- and dissolved in 200ill of ethanol.

This solution was kept at 40°C and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 g of water was added to this solution over 5 minutes.

The pH of this dispersion was adjusted and excess salt was removed by settling. After this, adjust the pH to 6.3 and sorb 300 g of 4
A dispersion of 1° silver salt (2) was obtained.

Next, we will discuss how to make a gelatin dispersion of a dye-donating substance.

5g of yellow dye-donating substance (A), auxiliary developer (
0.2 g of D), 0.2 g of fogging aid + L agent (E), 0.5 g of amber M-2-edylhexyl ester sodium sulfonate as a surfactant, and 10 g of triisononyl phosphate, Ethyl acetate 30 was added and dissolved by heating to about 60°C to form a homogeneous solution.

After stirring and mixing this solution and t 00 g of a lO% solution of lime-treated gelatin, the lO
000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that the magenta dye-providing substance (B) was used and 7.5 g of tricresyl phosphate was used as a high boiling point solvent.

A cyan dye-providing substance dispersion (C) was prepared in the same manner as the yellow dye dispersion.

= − 1 to 5! ]'' Auxiliary developer (D) Antifoggant (E) Color photosensitive materials having a multilayer structure as shown in Table 1 were prepared using these.

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

63 g of gelatin, 130 g of a mordant having the following structure and 80 g of potassium picolinate were dissolved in 1300 ml of water, coated on a paper support laminated with polyethylene to a wet film thickness of 45 mm, and dried.

(vinylsulfonylacetamidoethane) 1.05g
A dye fixing material 101 was prepared by dissolving the dye in 800 ml of water and applying the solution to a wet film thickness of 17 mm and drying. Further, potassium picolinate was changed to 20 g to prepare dye fixing material 102, and potassium picolinate was changed to 20 g and 100 g of the potassium salt of the polymer complexing agent (1) of the present invention was added to prepare dye fixing material 103. .

Using a tungsten light bulb, the multilayered color photosensitive material was exposed to light at 2000 lux for 1 second through a three-color separation filter of B, G, and R whose density was continuously changed.

20IIIl/rn on the emulsion surface of this exposed light-sensitive material.
' water was supplied with a wire bar, and then the dye-fixing material and membrane surface were overlapped so that they were in contact with each other.

The film was heated for 25 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 90°C. Next, when it was peeled off from the dye-fixing material, clear yellow, magenta, and cyan images corresponding to the B, G, and R three-color separation filters were obtained on the dye-fixing material.

Maximum density (Dmax) and minimum density (D win) of each color
The results of the measurements are shown in Table 2.

Table 2 Table 2 shows that sufficient image density can be obtained with the dye fixing material 103 of the present invention.

In addition, when observing the film surface of the dye fixing material, the dye fixing material 10
In Sample No. 1, precipitation occurred on the surface, and image unevenness was observed that was thought to be caused by this, whereas in dye fixing material 103, no precipitation or image unevenness was observed.

The precipitation on the surface of the dye-fixing material 101 became more noticeable after being stored at room temperature for one month, and the image unevenness that was thought to be caused by it further increased. However, in the dye-fixing material 103 of the present invention, such precipitation No phenomenon was observed.

Example 2 A single layer of polymer having the following composition was coated between the first layer of the photosensitive material of Example 1 and the support, and the first to sixth layers of Example 1 were coated thereon.
A photosensitive material was prepared by coating the layers.

Composition of one layer of polymer: gelatin (coating amount: 1000 mg/rn'), guanidinium salt of the polymer complexing agent (1) of the present invention, (coating amount: 3.2 g/rn'), hardening agent*: +( Used in Example 1; Coating amount: 20 mg/ba) As the dye fixing material, the dye fixing material 102 of Example 1 was used and treated in the same manner as in Example 1 to obtain the results shown in Table 3.

Table 3 It can be seen from Table 3 that sufficient image density can be obtained. Moreover, no image unevenness was observed after processing. Further, even when the light-sensitive material and the dye-fixing material were stored at room temperature for one month and then processed, no image unevenness occurred.

Example 3 Preparation of benzotriazole silver emulsion containing photosensitive silver bromide 6.5 g of benzotriazole and 10 g of gelatin were mixed with 10 g of water.
It was dissolved in 00ml12. This solution was kept at 50°C and stirred. Next, add 8.5 g of silver nitrate to 100 ml 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 mjl of water was added over 2 minutes. The prepared emulsion was precipitated by pH adjustment to remove excess salt. Then the emulsion p
H was adjusted to 6.0. Yield was 200g.

38 Preparation of gelatin dispersion of dye-donating substance 10 g of dye-donating substance with the following structure, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, and tricresyl phosphate (TCP) as surfactants. ) Weigh out 4g of cyclohexanone 2
0 mj2 was added and dissolved by heating to about 60°C to form a homogeneous solution.

After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated to 1100 g for 10 minutes using a homogenizer.
Dispersion was carried out at 00 rpm.

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

(a) Benzotriazole silver emulsion containing photosensitive silver bromide
10g (b) Dispersion of dye-donating substance 3.5g (C) Gelatin (10% aqueous solution) 5g (d) 0.2g of 2.6-dichloro-4-aminophenol mixed with 2ml of methanol1
．． (e) A 10% aqueous solution m1 of a compound with the following structure C9H+900 (CH2CH20)a H ([) Basic zinc carbonate (10% aqueous dispersion; size 0.2μ) 4.0 g or more (a) ~ After mixing ([) and heating and dissolving it,
It was applied to a wet film thickness of 30 μm on a polyethylene terephthalate film having a thickness of 180 μm.

Furthermore, the following composition was applied as a protective layer thereon.

b) Gelatin 10% aqueous solution 30m20) Water
60mj2c) 1,2-bis(vinylsulfonylacetamido)ethane 2% aqueous solution
5mfi Wet II! 30μm wet II! ;! A photosensitive material was prepared by applying a thick coating and drying.

This photosensitive material was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb.

The dye fixing materials are dye fixing materials 101 to 103 of Example 1.
The dye fixing material was prepared by using the following compound in place of potassium picolinate and the polymeric complexing agent (l potassium salt).
1 to 203 were created and used.

Color;
- and potassium lysine dicarboxylate 10g dye fixing material 2
03 2.6-Pyridinedicarboxylic acid potassium 10g
60 g of potassium salt of high content 91 1J (C) was treated in the same manner as in Example 1, and the results shown in Table 4 were 1:I.

Table 4 Dye fixing material No. Dmin Dmax2
01 (comparison) 0.16 1.78202
(Comparison) 0.08 0.42203 (Invention) 0.18 1.82 Table 4 shows that sufficient image density can be obtained with dye fixing material 203 of the invention.

In addition, when observing the film surface of the dye fixing material, the dye fixing material 20
In No. 1, precipitation occurred on the surface and unevenness was observed in the image, but in dye fixing material 203, neither precipitation nor image unevenness was observed.

Furthermore, even after one month of storage at room temperature, no precipitation on the surface or image unevenness was observed in the dye-fixing material 203 of the present invention.

Claims (1)

[Claims] An image forming reaction system containing a basic metal compound that is sparingly soluble in water and a complexing agent capable of raising the pH through a complex formation reaction with metal ions constituting the basic metal compound that is sparingly soluble in water using water as a medium. An image forming method further comprising a polymer complexing agent.