JPS63101847A - Image forming method - Google Patents

Abstract

PURPOSE:To increase density of image, and to reduce the generation of fog by bringing in contact a photosensitive material contg. a specific nondiffusive- dye providing compd. and a metal compd. slightly soluble in water with a prescribed complex forming compd., thereby increasing pH of the photosensitive material. CONSTITUTION:The color photosensitive material comprises a photosensitive silver halide, a binder, the dye providing compd. hydroxide). The component (A) is exemplified by the compd. capable of forming or releasing the nondiffusive dye which does not contain a group capable of dissociating proton having <=6PKa. The image is formed by image-wisely exposing the photosensitive material, followed by bringing in contact it with a complex forming compd. (such as guanidine picolate) which is capable of releasing a base by effecting the complex forming reaction with a metal ion constituting said metal compd. slightly soluble in water, in the presence of water or a hydrophilic heat-meltable agent (such as urea). Said complex salt forming compd. is formed a supply sheet on a substrate, followed by supplying said compd. from said sheet, or said compd. can be supplied by dissolving it in water.

Description

BACKGROUND OF THE INVENTION 1. 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. 5B-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 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.

(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 fog, 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 silver halide color photosensitive material having at least a photosensitive silver halide, a binder, a dye-providing compound, and a hardly mixed metal compound on a support in the presence of water or a hydrophilic heat solvent. In an image forming method comprising a step of raising the pH by contacting a metal ion constituting the hardly soluble metal compound with a complex-forming compound that releases a base through a complex-forming reaction, the dye-donating compound has a pKa of 6 or less. This image forming method is characterized by using a non-diffusible dye-providing compound that can form or release a diffusible dye that does not have a proton-dissociating group.

■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 poorly soluble metal compound and a compound (hereinafter referred to as a complex) capable of undergoing a complex formation reaction with the metal ions constituting the poorly soluble metal compound using water or a hydrophilic hot solvent as a medium are added to the image forming reaction system. (referred to as a forming compound), and these two are combined in the presence of water or a hydrophilic hot solvent.
The reaction between the two compounds increases the pH of the reaction system.

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
Carbonates, phosphates, silicates, whose solubility in water (number of grams of substance dissolved in 100 g of water) is 0.5 or less,
Included are double salts of these compounds such as borates, aluminates, hydroxides, oxides, and basic salts.

and 2 Tm xn Those represented by are preferred.

Here, T is a transition metal, such as Zn, Ni, A2, Cu,
Co%Fe%Mn etc. or alkaline earth metals such as C
a, Ba, Mg, 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, etc. , silicate ion, borate ion, aluminate ion, hydroxy 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, calcium magnesium carbonate (CaMg(COs) 2), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, hydroxide Magnesium, 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(O
)I)2-820), basic magnesium carbonate (3JC
O, ・Mg(OH)2 ・31(,0), basic nickel carbonate (Ni[:03・2 N1(0H)2), basic bismuth carbonate (Blz(Ll:03)02 ・N20)
, basic cobalt carbonate (2GOCO3.:Nl:o (
0) 1) 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 10 in logarithm with the metal ion constituting the hardly soluble metal compound.
This produces a complex salt that exhibits the above values.

These complex-forming compounds are described, for example, by N.E. Martill and R.M. Smith.
ell, R.M., Sm1th), “Critical
Stability Constance ((:riticalSt
ability to instants), Volumes 1 to 5”
, Plenun 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 amidine. and quaternary ammonium salts.

Preferred specific examples include picolinic acid, 2゜6-pyridinedicarboxylic acid, 2.5-pyridinedicarboxylic acid, 4-pyridinedicarboxylic acid,
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, 1IQ2CC1120CH2CH2QC1lzCQJ.

110□CGlI□0CII2C02H.

Examples include alkali metal salts such as CH3H2O5P-CH-PO3H2, guanidine salts, amidine salts, and quaternary ammonium salts.

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 o and M are bonded to the ring is particularly preferably α-position relative 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.

In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -002M, 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 are each the same as defined in R,
Further, Zl and 22 may be combined to form a ring condensed to the pyridine ring.

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

Basic magnesium carbonate aluminum hydroxide Basic zinc carbonate Basic magnesium carbonate Zinc hydroxide 3M salt of ethylenediaminetetraacetic acid Zinc hydroxide 1,2-cyclohexanediamine Calcium carbonate Zinc oxide Calcium carbonate ■e　　　e■ Charcoal M Ha’) Ram-M 02 C-CO2M■ Calcium carbonate-M salt of citric acid Calcium carbonate Magnesium oxide Zinc hydroxide 83CCH.

~ Tin hydroxide - 83C (:H3 Calcium salt carbonate - Basic magnesium carbonate - Calcium carbonate - Basic zinc carbonate - These combinations can be used alone or in combination of two or more. Also, known Can be used in combination with a base or base precursor.

Here, the mechanism for increasing the pH of the reaction system in the present invention will be explained using a combination of 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 (or a hydrophilic thermal solvent) is present as a medium, picolinate ions cause 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 M L formed from picolinate ion (Lθ) and zinc ion (M■)
The stability numbers of the complexes represented by , M L 2 , and M L 3 are very large as shown below, and explain the progress of this reaction well.

ML ML, ML.

ILogK 5.30 9.62 12.92 In the present invention, the poorly soluble metal compound and the complex-forming compound are preferably 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. Alternatively, the complex-forming compound may be dispersed in a binder and applied onto a support to create a complex-forming compound supply sheet, and the complex-forming compound may be supplied from that sheet, or it may be supplied by dissolving it in the water involved. May be supplied.

Slightly soluble metal compounds are described in JP-A-59-174830 and JP-A-59-174830.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 3-102733, etc., and the average particle size thereof is preferably 50 μm or less, particularly 5 μm or less.

The poorly soluble metal compound in the present invention may be added to any layer such as an emulsion layer, an intermediate layer, a protective layer, an antihalation layer, or a white pigment layer. Moreover, it may be contained in one layer or in two or more layers.

In the present invention, when a poorly soluble metal compound or a complex-forming compound is contained in a layer on a support, the amount added depends on the type of compound,
Although it depends on the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc., it is appropriate to use the coating film in an amount of 50% by weight or less, more preferably 0.01fi.
A range of % by weight to 40% by weight is useful. When the complex-forming compound is dissolved in water and used, the amount is preferably 1/10 or more of the number of moles of the poorly soluble metal compound to be reacted. Generally 0.01-5ffioIL/I
It is best to set it to about L.

Water used as a medium in the present invention can be supplied externally, by immersing the element in water or an aqueous solution, or by pre-existing capsules containing water in the image forming reaction system and destroying the capsules by heating etc. It can be supplied by the method of supplying.

The water used in the present invention is not limited to so-called "pure water", but includes water in the widely customary sense.
It may be an aqueous solution containing a base and/or a base precursor described below, or a mixed solvent with a low boiling point solvent such as methanol, DMF, acetone, or diisobutyl ketone. Furthermore, an aqueous solution containing an image forming accelerator and a hydrophilic heat solvent described in Japanese Patent Application No. 59-268926 may also be used. Further, the inclusion of a surfactant is advantageous in uniformly supplying water to the photosensitive material, dye fixing material, or complex-forming compound supply sheet.

The amount of water in the present invention is at least 0.1 times the weight of the total coating film of the light-sensitive material and the dye fixing material (or the complex-forming compound supply sheet), preferably 0.1 times the weight of the total coating film of the light-sensitive material and the dye fixing material (or the complex-forming compound supplying sheet).
The weight of water is within the range of 1 to the maximum swelling volume of the entire coated film, and more preferably 0 of the weight of the entire coated film.
．． The amount ranges from 1 to the amount obtained by subtracting the weight of the entire coating from the weight of water corresponding to the maximum swelling volume of the entire coating.

The state of the film when it swells is unstable, and depending on the conditions, it may cause local bleeding.To avoid this, the maximum total coating film of the light-sensitive material and dye-fixing material (or complex-forming compound supply sheet) must be It is preferable that the amount of water be less than the total amount of water corresponding to the volume at the time of swelling. Specifically, the total area of the photosensitive material and dye fixing material (or complex forming compound supply sheet) is 1
1g to 50g, especially 2g to 35g per square meter,
Furthermore, the range of 3g to 25g is preferable.

A hydrophilic thermal solvent is a compound that is in a solid state at room temperature but turns into a liquid state at high temperatures (60°C or higher), has an (inorganic/organic) value greater than 1, and has a
It means a compound with a solubility of 1 g or more per 0 g.

For details on the above (inorganic/organic) values, see
It is described in Volume 11, page 719 (19-57) of "Region of Chemistry". The (inorganic/organic) value of the hydrophilic heat solvent is preferably 1.5 or more, particularly preferably 2 or more.

Further, the molecular weight of the hydrophilic heat solvent is preferably 200 or less, particularly preferably 100 or less. The melting point of hydrophilic thermal solvent is 40
C1 to 250"C1, preferably 40C to 200C, more preferably 40'e to 150C.

The hydrophilic heat solvent is used by being added to the photosensitive element and/or the dye fixing element. There is no particular restriction on the amount used, but it is 5 to 500% by weight of the total coating amount of the photosensitive element and dye fixing element (excluding the amount of hydrophilic heat solvent), preferably 2
It is used in a coating amount of 0 to 200% by weight, more preferably 30 to 150% by weight.

The wood-philic two agents are usually dissolved in water and dispersed in the binder, but may also be dissolved in alcohols such as methanol, ethanol, etc. and dispersed in the binder.

Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and various heterocycles. Specific examples of these are described in JP-A-59-168439 and the like.

In the present invention, a non-diffusible dye-donating compound that forms or releases a diffusible dye (Dye) that does not have a proton dissociative group with a pka of 6 or less is used.

The dye used in the present invention is disclosed in U.S. Patent No. 4.478.9.
No. 27, No. 4.507.380, JP-A-59-48
No. 765, No. 59-57237, etc.

The dye used in the present invention moves through the binder by thermal diffusion or sublimation diffusion and dyes the dye fixing material, so it has a low molecular weight and is essentially nonionic (non-dissolving material). However, it is desirable that the molecule contains an appropriate amount of polar group. Specifically, molecule-1150
-600, more preferably 200-500.
Further, those having a pKa of 6 or less and having no proton dissociative groups (particularly carboxyl groups and sulfo groups) are used.

Preferred dyes are illustrated below.

Yellow P + Magenta u un Yashishi Inai Cyan 82 to 3 U N! "13 In the above formula, R1-R6 are a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group,
Cyano group, hydroxyl group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen, sulfamoyl group, N -Substituted sulfamoyl group, carbamoyl group, Nu
Represents a substituent selected from a substituted carbamoyl group, an acyloxyalkyl group, an amino group, a substituted amino group, an alkylthio group, and an arylthio group.

Specific examples of Dye are listed below.

Y-2 2H5 -IM-9 しN Nfi(, LJsit13 Examples of non-diffusible dye-donating compounds that form or release such dyes include the following.

The dye-donating compound may be any compound that participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. , depending on their reaction form, a negative dye-donor that acts on a positive function (i.e., forms a negative dye image when negative-working silver halide is used) and a negative dye-donor that acts on a negative function. It can be classified as a positive-working dye-donor (that is, it forms a positive dye image when negative-working silver halide is used).

Examples of dye-releasing compounds include compounds represented by the following general formula (Ll).

(Dye-X)ny (LI)Dye is pK
a Represents a dye or dye precursor that does not have 6 or less proton dissociative groups.

X represents a simple bond or a linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image (Dye
-X) Create a difference in the diffusivity of the compound represented by H-Y, or release Dye and create a difference in diffusivity between the released Dye and (Dye-X)n -Y. and n represents 1 or 2, and when n is 2, two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.
No. 3,362.819, No. 3,597,20
No. 0, No. 3,544,545, No. 3.482,9
It is described in No. 72, etc.

Furthermore, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in US Pat. -111628 etc.

Another example is to make a dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized to produce a diffusible dye. A method of releasing dye has also been devised, and a specific example of the dye-donating substance used therein is disclosed in Japanese Patent Application Laid-Open No. 53
-110827, 54-130927, 56-
It is described in No. 164342 and No. 53-35533. Japanese Patent Application No. 60-244873 describes a compound that releases a diffusible dye when the N-0 bond is cleaved by a remaining reducing agent as a dye-donating substance that releases a diffusible dye by a similar mechanism. There is.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a coupler having a diffusible dye as a leaving group and which releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler 1) is used. ) is British Patent No. 1.330.52
No. 4, Special Publication No. 4B-39,165, British Patent No. 3゜4
43.940, JP-A-57-207250, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent becomes a serious problem. Release compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. Representative examples are U.S. Pat. No. 3,928,312 and U.S. Pat.
No. 53,312, No. 4,055.428, No. 4,
No. 336,322, Japanese Unexamined Patent Publication No. 57-179840, No. 5
No. 9-65839, No. 59-69839, No. 53-3
No. 819, No. 51-104,343, Research Disclosure No. 17465, U.S. Patent No. 3゜725
．． No. 062, No. 3,728,113, No. 3,44
No. 3,939, JP-A-58-116.537, JP-A No. 57
-179840, US Pat. No. 4,500,626, and the like.

Specific examples of this type of dye-donating substance are described in the aforementioned Japanese Patent Application Laid-Open No. 57-207250 (pages 101-101 to (12)) and No. 57-179840, pages (12) to (15). Mention may be made of the compounds described.

As a coupling dye-forming compound, general formula (L■)
Examples include compounds represented by:

Cp −e X +−+Q ) (L
II) In the formula, Cp is an organic group (so-called coupler residue) that can react (coupling reaction) with the oxidized form of the reducing agent to form a diffusible dye, and X represents a divalent bonding group. where Q represents a ballast group.

The coupler residue represented by Cp preferably has a molecular weight of 700 or less for the diffusibility of the dye formed.
More preferably it is 500 or less.

The ballast group is preferably a group having 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group, and more preferably a polymer group.

The coupling dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by the general formula (x).

General formula (x) Cp2+x-)+YtonaZHL) In the formula, Cp2 and x have the same meaning as defined in general formula (LII), Y represents an alkylene group, arylene group or aralkylene group, and 2 is 2 represents a valent organic group,
L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds include JP-A-59-124339, JP-A-59-181345, JP-A-58-109293, JP-A-59-179657, JP-A-59-181604, and JP-A-59-182506. , same 5
It is described in each specification of No. 9-182507.

Specific examples of the dye-providing compound of the present invention are listed below.

(lO) CH+ t13 n These dye-donating substances may be used alone or in combination of two or more. The amount used is not limited and may be determined depending on the hierarchy of the dye-donating substance, whether it is used alone or in combination of two or more, etc., but for example, the amount used is 1 = 0,005g ~ 50g, preferably 0.1g-1
0g can be used.

The dye-providing substance used in the present invention can be incorporated into the photosensitive layer of the heat-developable color photosensitive material using any method. tricresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in alkaline water-soluble Ti (e.g., 10% aqueous sodium hydroxide solution, etc.), followed by strong acid (
For example, it can be used after being neutralized with hydrochloric acid or nitric acid, or after being dispersed with an appropriate polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.

The thermal development and the transfer step for fixing the diffusible dye produced thereby may be performed simultaneously (one step) or separately (two steps). It is not necessarily necessary to apply heat in the developing step, and processing can be performed at room temperature.

A pattern of bars is used in the process of forming an image, and an example thereof is shown below.

l) A method of forming an image in one step by heating a photographic material in which a photosensitive element and a dye-fixing element containing a complex-forming compound are laminated.

2) A method in which a photosensitive material and a dye-fixing material containing a complex-forming compound are layered and then heated to form an image in one step.

3) A method in which a photographic material in which a photosensitive element and a dye-fixing element containing a complex-forming compound are laminated is heat-developed and then heated again to form an image in two steps.

4) A method in which a photosensitive material is heated, and then a dye-fixing material containing a complex-forming compound is layered and heated to form an image.

5) After supplying water to the photosensitive material, it is overlapped with a complex-forming compound supply sheet, developed at room temperature, and then the complex-forming compound supply sheet is peeled off, and then it is overlapped with a dye-fixing material and heated to transfer the image. Method.

6) Developing a photosensitive material or photosensitive element at room temperature using a processing bath such as a developing bath containing a complex-forming compound, and then transferring it to a dye fixing material or laminated dye fixing element using heat to form an image. how to.

The above method is just an example, and various variations are possible, and the present invention is not limited to the above method.

In the present invention, a conventionally known method can be used as a heating method for development or transfer.

For example, the photosensitive material may be brought into contact with a hot plate such as a hot plate or a drum, or may be transported using a beat roller.

Heating can also be performed using air heated to a high temperature, high frequency heating, or a laser beam. Depending on the photosensitive material, it can also be heated using an infrared heater. Furthermore, it is also possible to apply a method of heating using eddy currents generated by electromagnetic induction.

Alternatively, the photosensitive material may be heated in a bath containing a liquid inert to the photosensitive material, such as a fluorine-based liquid.

Furthermore, the photosensitive material may be heated by providing a heat source separate from the heating means described above. For example, a layer of conductive particles such as carbon black or graphite may be provided in a photosensitive material and/or a dye fixing material, and the Joule heat generated when electricity is applied may be utilized.

Various patterns can be applied to heat-develop the photosensitive material. The most common method is heating at a constant temperature, but depending on the characteristics of the photosensitive material, the heating temperature may be changed during the process. The preferred temperatures for development and transfer are not fixed, but can be selected in the optimum range depending on the form.

In the present invention, the dye fixing element is capable of fixing the mobile dye released by development.

For dye fixation, dye-receptive polymers such as those described in JP-A-57-198458 can be used. Moreover, a polymer mordant can be used if necessary. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

The polymer mordant can function as a dye-fixing element by mixing it with a binder and coating it integrally with the photosensitive element, or by coating it on a support separate from the photosensitive element.

The polymer particularly preferably used in the present invention is composed of a heat-resistant organic polymer substance having a glass transition temperature of 40° C. or higher and 250° C. or lower. In this case, much remains unclear about the mechanism by which the released dye enters the polymer. It is generally believed that at a treatment temperature above the glass transition point, the thermal motion of the polymer chains becomes large, and as a result, the dye can enter the interstitial spaces between the chain molecules. Therefore, by using a layer made of an organic polymer substance with a glass transition temperature of 40° C. or higher and 250° C. or lower as the dye fixing layer, it is possible to form a clear image in which only the dye enters the dye fixing layer.

Examples of organic polymeric substances used in the present invention include the following. To list them, molecules fi2000~
85,000 polystyrene, polystyrene derivatives with substituents having 4 or less carbon atoms, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride , chlorinated polyethylene, polybutylene trichloride, ethylene, polyacrylonitrile, poly N, N-dimethylallylamide, p
-cyanophenyl group, pentachlorophenyl group and 2
．． Polyacrylate with 4-dichlorophenyl group, polyacrylic chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly -2-Cyano-ethyl methacrylate, polyesters such as polyethylene terephthalate, polysulfone, bisphenol A polycarbonate, polycarbonates, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook 2nd Edition G.I. Brandrup, E.H. Immergut (
J., Brandrup, B.

Edited by H, ImmerguL), John l1iley
& 5ons publication glass transition temperature 40
Synthetic polymers with temperatures above 250°C and below 250°C are also useful.

These polymeric substances may be used alone or in combination, or may be used in combination as a copolymer. These polymers may also serve as a support applied to the photographic element described below, or may form a layer independent of the support. For example, these polymers can be used as a support for the light-sensitive material of the present invention, and this support can also function as a dye-fixing layer, or these polymers can be used as a dye-fixing material independent of the light-sensitive material. Alternatively, the support of the dye fixing material can also serve as the dye fixing layer. Furthermore, the support of the complex-forming compound supply sheet can also function as a dye fixing layer.

Regarding the layer structure of the dye fixing element, the binder, additives, and the installation position of the mordant cross-layer, those described in JP-A-61-147244 and the patent specifications cited therein are applicable to the present 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 JP-A-61-
No. 88256.

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, Japanese Patent Application Laid-Open No. 61-107240, U.S. Patent No. 4
．． No. 500.626, column 50, Research Disclosure Magazine, June 1978 issue, pages 9-10 (RD170
Any of the silver halide emulsions described in 29) etc. 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 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 performed in the presence of nitrogen-containing heterocyclic compounds (
JP-A-58-126526, JP-A No. 5B-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 is in the range of 1 mg to 10 g/rn'' 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 compounds described in JP-A-61-107240 and U.S. Pat. No. 4,500,626, columns 52 to 53. be.

Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-60-113235.

The above-mentioned silver salt per mole of photosensitive silver halide contains
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 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, 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 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,
Substances exhibiting supersensitization may be included in the emulsion (e.g., U.S. Pat. Nos. 2,933,390 and 3,635,72).
No. 1, No. 3,743,510, No. 3,615゜6
No. 13, No. 3,615,641, No. 3.617,
No. 295 and No. 3,635,721).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
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 about 10-8 to 10-1 mol per mol 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 (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 U.S. 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.

When performing normal wet development, a reducing agent may be added to the processing solution.

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.

Details of these are described in JP-A-61-93451.

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 Specifically, 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, No. 60-108837, No. 60-1
No. 92939, No. 60-230133 or No. 60-
230134).

Compounds that convert into mercaptate and release metal compounds when heated are also useful, for example, JP-A-61-67851, JP-A-61-61
-147244, 61-124941, 61-
No. 185743, No. 61-182039, No. 61-1
No. 85744, No. 61-184539, No. 61-18
There are compounds described in No. 8540 and No. 61-53632.

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, columns 51-52.

Various antifoggants 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 JP-A-61-147244.

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 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 increase the dimensional stability of photographic materials, among others.

In the present invention, the binder is applied in an amount of 20 g or less per 1 m'', 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 or less, 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 include those described in JP-A-61-147244 and JP-A-59-157636 (page 381), 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. As a general support,
Glass, paper, polymer films, metals and their analogs can be used, as well as those listed as supports in JP-A-61-147244.

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. No, but Japanese Patent Application Laid-open No. 61-147244 and U.S. Patent No.
Filter dyes, absorbent substances, etc. described in the literature exemplified in column 55 (lines 41 to 52) of the above issue can be contained.

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 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
It can contain an H 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, 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 can be roughly 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 JP-A-61-147244 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. 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 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.

In the present invention, the method of coating the photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers is disclosed in U.S. Pat.
The method described in No. 55-56wA of No. 26 can be used.

As a light source for image exposure to record an image on a photosensitive material, radiation including visible light can be used;
The light source described in column 56 of No. 626 can be used.

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 JP-A-61-1.
The method described in No. 47244 can be applied.

■Specific effects of the invention According to the present invention, in an image forming reaction system containing a non-diffusible dye-providing compound capable of forming or releasing a diffusible dye having a pKa of 6 or less and having no proton-dissociating group, water or a hydrophilic thermal In the presence of a solvent, a reaction between a poorly soluble metal compound and a complex-forming compound that can undergo a complex-forming reaction with the metal ions constituting this poorly soluble metal compound using water or a hydrophilic hot solvent as a medium results in p)l. As a result, it is possible to obtain an image forming method that provides a high-density, low-fog image, has excellent storage stability, and is easy to process.

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

Example 1 A photosensitive material IA was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate support.

Photosensitive materials IB and IC were prepared in exactly the same manner as above except that (10) and (12) were replaced.

A sheet (I) containing guanidine picolinate as a complex-forming compound was prepared as follows. 5% aqueous solution of polyvinyl alcohol (average molecular weight 2000) 68mM
3.5g of urea, 4.5g of methylurea, 2g of ethyleneurea
．． 0 g, dimethylsulfamide 2.0 g, and guanidine picolinate 3.0 g were added and stirred to dissolve. This solution was applied onto a polyethylene terephthalate film having a thickness of 100 IJI to a wet film thickness of 60 mm, and dried to prepare a sheet for supplying a complex-forming compound (1).

After imagewise exposure of the photosensitive material, the film surface is brought into close contact with the complex-forming compound-containing sheet, and the back side of the sheet is heated at 180°C.
The sample was brought into contact with a heat block heated to 100% and heated uniformly for 60 seconds.

After the photosensitive material was cooled to room temperature, it was peeled off from the sheet and the applied emulsion layer was physically peeled off from the polyethylene terephthalate film using an adhesive tape.

A negative image was obtained on polyethylene terephthalate film.

When measured using a Macbell transmission densitometer (TD-504), the results shown in the table below were obtained.

Example 2 Photosensitive materials 2A and 2B were prepared in the same manner as in Example 1 except that the benzotriazole silver emulsion was removed from the photosensitive material of Example 1.
, made 2C. After exposing this light-sensitive material in the same manner as in Example 1, 1 m'' of 9% potassium picolinate aqueous solution was applied.
10mj2. After application and covering with polyethylene terephthalate film, leave at room temperature for 60 minutes.
I kept it in close contact for a second. The polyethylene terephthalate film was peeled off (this film was not colored at all). This photosensitive material was immersed in a 1% acetic acid solution and then dried.

When this developed photosensitive material was layered with polyester cloth (Vylon, manufactured by Toyobo Co., Ltd.) or polyethylene terephthalate film and pressed with an iron at about 160°C for 35 seconds, a negative transfer image was obtained on the cloth or film. Ta.

Further, when the photosensitive materials 2A, 2B, and 2C were subjected to the same operations and treatments as above except that they were immersed in a 9% potassium picolinate aqueous solution for 50 seconds after exposure, the same results as above were obtained.

Procedural amendment (spontaneous) November 18, 1988 Director General of the Patent Office Kunio Ogawa 2. Title of invention Image forming method 3. Relationship with the person making the amendment Case Patent applicant address Minamiashigara City, Kanagawa Prefecture 210 Nakanuma Name (520) Fuji Photo Film Co., Ltd. 4, Agent
101 Telephone 864-4498 Address 3-2-2 Iwamoto-cho, Chiyoda-ku, Tokyo Contents of amendments to column 6 of "Detailed Description of the Invention" of the specification (1) Structural formula (11) on page 57 of the specification ) is corrected as follows.

r (11) H3'' (2) On page 86, line 5, r Dye-providing compound of the present invention (4)'' is corrected to ``Dye-providing compound of the present invention (11)J''.

(3) “Compound (4) of the present invention” on page 87, line 4
" is corrected to "Compound (11)J of the present invention."

(4) Column 2 of the table on page 88 (compound column)' (
4) Correct J to "(11)".

Claims (1)

[Claims] A silver halide color photosensitive material having at least a photosensitive silver halide, a binder, a dye-providing compound, and a sparingly soluble metal compound on a support is prepared by forming the sparingly soluble metal compound in the presence of water or a hydrophilic thermal solvent. In the image forming method, the dye-providing compound does not have a proton-dissociating group with a pKa of 6 or less, and the dye-providing compound does not have a proton-dissociating group with a pKa of 6 or less. 1. An image forming method characterized by using a non-diffusible dye-providing compound capable of forming or releasing a color dye.