JPH01185552A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent generation of unequal transfer at the time of using a dye fixing element and photosensitive element after preservation for a long period of time under low humidity by using a paper base formed of base paper having specific internal bonding strength for one base. CONSTITUTION:The dye fixing element and/or photosensitive element is formed by using the paper base as its base and this paper base is formed of the base paper having 0.5-20kg.cm, more preferably 1.0-1.5kg.cm internal bonding strength. The internal bonding strength refers to the energy required for peeling the paper along the surface thereof. The internal bonding strength of the base paper to be used for the base is thereby eventually lowered, by which the rate of expansion and contraction is relieved. The good image which is free from the generation of the unequal transfer, etc., is thus obtd. even if the dye fixing element or photosensitive element preserved for a long period time under low humidity is used.

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 color image forming method using thermal development.

Prior art and its problems Heat-developable photosensitive elements are well known in this technical field, and the heat-developable photosensitive elements and their processes can be found, for example, in ``Fundamentals of Photographic Engineering'' Non-Silver Salt Photography Edition (published by Corona Publishing, 1982), Vol.
It is described on pages 42 to 255.

Many methods have also been proposed for obtaining color images by heat development.

For example, U.S. Patent Nos. 3,531.286 and 3,7
61,270, Belgian Patent No. 4,021゜240, Belgian Patent No. 802,519, Research Disclosure (hereinafter referred to as RD), September 1975, pages 31-32, etc. A method of forming a color image by combining the two has been proposed.

However, since the heat-developable photosensitive elements that produce the above color images are non-fixing type, silver halide remains even after the image is formed, and the white background gradually becomes colored if exposed to strong light or stored for a long time. This poses a serious problem.
Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high fog and low image density.

In order to improve these drawbacks, a diffusive dye is formed or released in an image form by heating, and this diffusible dye is
A method of transferring to a dye fixing element (image receiving element) having a mordant using a solvent such as water has been proposed (U.S. Pat. No. 137, No. 4.559.290;
JP-A-59-165054, etc.).

In such image forming methods, a dye fixing element and/or a photosensitive element with a paper support is used to reduce the cost of the product, to make it easier to process, and to make it easier to cut and paste. It is commonly used.

However, if such a dye-fixing element and/or photosensitive element is stored for a long period of time under low humidity and then thermal development transfer is performed by bringing the photosensitive element and dye-fixing element into close contact, the original dye image of the dye-fixing element is lost. In some cases, irregular circular portions having an extremely low dye concentration and having a diameter of about 10 μm to about 1 mm are scattered in the desired region.

In particular, JP-A Nos. 59-218443 and 61-2380
No. 56, European Patent Rate No. 210.66OA2, etc., in the method in which a dye fixing element and a photosensitive element are overlapped and heated in the presence of water, a base and/or a base precursor, the above-mentioned density unevenness can be avoided. The occurrence is noticeable. The reason for this is not clear, but when such heating is performed, the surface of the dye-fixing element and the light-sensitive element are in direct contact with each other in some areas and in others not in direct contact due to the unevenness of the support. Dye transfer proceeds smoothly in some areas, but in areas where they are not in contact, transfer is difficult to occur unless the areas are forcibly brought into close contact with each other using a pressure roller, etc. In addition, when a base or base precursor is added to the dye fixing element, it is difficult to transfer the dye. This is thought to be because when the base is in direct contact with the photosensitive element, more base moves to the photosensitive element, and development proceeds there more than in other areas, resulting in uneven development.

This density unevenness occurs significantly when the dye-fixing element and/or the photosensitive element is stored for a long period of time under low humidity. This is thought to be because the shrinkage of the fibers constituting the paper support causes unevenness on the support. In order to solve such problems, it is necessary to consider various materials for the paper support.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide an image forming method that provides a good image without uneven transfer even when using a dye-fixing element or a photosensitive element that has been stored for a long period of time under low humidity. It is in.

III Disclosure of the invention Such objects are achieved by the invention described below.

That is, the present invention provides at least a photosensitive silver halide on a support, a binder, and when the photosensitive silver halide is reduced to silver under high temperature conditions, a diffusible dye is produced in response to or inversely to this reaction. Alternatively, a light-sensitive element having a dye-providing compound to be released is heated in the presence of water and a base and/or a base precursor after or simultaneously with imagewise exposure, and the diffusible dye produced or released is transferred onto a support. In an image forming method of transferring to a dye fixing element having a dye fixing layer, at least one of the two supports has an internal bonding strength of 0.5 to 2.0 g-c.
This image forming method is characterized in that the paper support is formed from II+ base paper.

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

The dye-fixing element and/or photosensitive element in the present invention uses a paper support as a support, and this paper support has an internal bond strength of 0.5 to 2.0 g'cm, preferably 1.0 g'cm.
~1. It is formed from 5Kg-cm paper.

Here, Internal Bond
is the energy required to peel paper along its surface and is defined by TAPPI RC-308. The measurement method is TAPPI LlsefulMe
thod 403.

This internal bonding force is set when the internal bonding force is 2.0.
If it exceeds Kg/cm, unevenness will easily occur on the support during the storage process under low humidity conditions, making it difficult to ensure the smoothness of the support during processing, and resulting in uneven transfer. This is because, if it is less than 0 or 5 g'cm, paper breakage etc. will occur during the paper manufacturing process and manufacturing suitability will deteriorate.

Such internal bonding force is caused by the first raw material used, the second
It can be set by selecting the paper making method that is applicable to the paper.

Raw materials to be used include ■bulbs, ■fillers, ■softening agents, ■paper strength agents, ■surface sizing agents, etc., and by selecting the distribution of these, the desired internal bonding strength can be obtained. .

Paper-making methods include (1) beating machine type and degree of beating, (2) wet pressing conditions, and (2) drying conditions, and by selecting these conditions, desired internal bonding strength can be obtained.

The paper forming the paper support in the present invention has an RP value of 0.5.
~10-1 preferably 2-7 IJM.

Here, the Rp value is a physical quantity proportional to the average depth of depressions on the surface of paper pressed against a reference plane, and is an evaluation measure of printing smoothness. The measurement principle utilizes the wavelength dependence of the optical contact rate. It is evaluated that the smaller the RP value, the better the printing smoothness.

When the Rp value exceeds 104, uneven transfer occurs due to deterioration of smoothness.

This RP value shows a correlation with internal bonding strength, and generally, as the internal bonding strength increases, the R3 value tends to increase.

The paper support used in the present invention is made mainly from wood bulbs, but it is also possible to partially mix synthetic fibers or synthetic bulbs.

As the wood bulb, both softwood bulbs and hardwood bulbs can be used.

In the present invention, it is preferable that hardwood bulbs, which are short fibers and easily exhibit smoothness, account for 50% or more.

It is better for the freeness of the valve to be close to unbeaten from the point of view of internal bonding strength, but from the point of view of suitability for paper making, a freeness of 250 to 500 cc is recommended.
(C, S, F,) is desirable.

There is also a correlation between the freeness and the RP value, and the higher the freeness (ie, the lower the freeness value), the higher the Rp value generally tends to be.

In the present invention, it is preferable to use a chemical valve that contains few impurities and is unlikely to adversely affect the photosensitive characteristics. Generally, kraft valves (sulfate valves) and sulfite valves are used.

Furthermore, it is preferable to use a bleached bulb that has been bleached to increase the whiteness of the bulb.

As the softener, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine is preferred. Epoxidized fatty acid amides are also effective.

This is more effective in reducing internal bonding strength.

The softening agent may be added in an amount of about 0.1 to 20 wt% to the bulb.

Examples of paper strength enhancers include melamine resin, urea resin, polyethyleneimine, glyoxal, etc., which improve wet strength, and polyacrylamide, starch, cationic starch, natural rubber, etc., which improve dry strength. Examples include cellulose flexiconductors and seaweed extracts.

Among these, cationic starch is also effective in regulating surface size.

A paper strength enhancer that improves wet strength should be 0.1 to 1. Approximately 0.2 to 0.2% to pulp to improve dry strength.
2. It may be about Owt%.

Sizing agents include rosin, paraffin wax, higher fatty acid salts such as sodium stearate, alkenyl succinates, fatty acid anhydrides, alkyl ketene dimers, and the like.

The sizing agent may be added in an amount of about 0.5 to 3.0 wt% to the pulp.

In addition, fillers such as clay, talc, calcium carbonate, urea-formalin resin fine powder, and fixing agents such as sulfuric acid bandate and polyamide polyamine epichlorohydrin may be added as necessary.

Fillers improve the flexibility, surface smoothness, printability, opacity, etc. of paper.

Further, the fixing agent fixes the sizing agent to the fiber surface.

The filler is about 1 to 15 wt% based on the bulb, and the fixing agent is about 0.5 to 3. It is sufficient to add about Owt%.

The base paper used for the paper support can be made using the paper described above using a fourdrinier paper machine or a cylinder paper machine. The basis paper weight is 20-200 g/m2
It is preferable that it is, and it is especially preferable that it is 30-100 g/m2. The thickness of mixed paper is 25-250μm
It is preferable that it is, and it is especially preferable that it is 40-150 micrometers.

Further, the base paper is preferably subjected to a calender treatment such as an on-machine calender in a paper machine or a super calender after paper making for the purpose of improving smoothness.

From the above calender treatment, the density of the base paper is JIS-P-
According to the provisions of 8118, it is preferably 0.7 to 1.2 g/m2, and particularly preferably 0.85 to 1.10 g/m2.

In the present invention, the base paper described above can be used as it is as a paper support, but it is more preferable to use a base paper with a hydrophobic polymer coating layer on one or both sides as the support. . The coating layer of the hydrophobic polymer may be provided on one side or both sides of the base paper as a structure in which multiple layers are stacked one on top of the other.

Note that a known surface sizing agent may be applied to the surface of the base paper, and a coating layer of a hydrophobic polymer may be provided thereon. Examples of surface sizes include polyvinyl alcohol, starch,
Polyacrylamide, gelatin, casein, styrene
Examples include maleic anhydride copolymers, alkyl ketene dimers, polyurethanes, and epoxidized fatty acid amides.

The hydrophobic polymer used for the coating layer has a glass transition point of 12
Polymers between 0°C and 50°C are preferred. The polymer may be a homopolymer or a copolymer. Further, in the case of a copolymer, even if a portion thereof has hydrophilic repeating units, it is sufficient that the copolymer is hydrophobic as a whole. Examples of the above hydrophobic polymers include vinylidene chloride, styrene-butadiene,
copolymer, methyl methacrylate-butadiene copolymer, styrene-acrylic ester copolymer,
Examples include methyl methacrylate-acrylic ester copolymer and styrene-methacrylate-acrylic ester copolymer.

It is further preferable that the hydrophobic polymer has a crosslinked structure. In order to form a crosslinked structure in a hydrophobic polymer, a known curing agent (crosslinking agent) may be used together with the hydrophobic polymer during production of the paper support. Examples of the curing agent include 1,3-bis(vinylsulfonyl)-2
- Active vinyl compounds such as propatool, methylene bismaleimide; 2,4-dichloro-6-hydroxy-8-
Active halogen compounds such as triazine sodium salt, 2,4-dichloro-6-hydroxy-s-triazine, N,N'-bis(2-chloroethylcarbamyl)piperazine; bis(2,3-epoxypropyl) Examples include epoxy compounds such as methylpropylammonium/P-toluenesulfonate, and methanesulfonic acid ester compounds such as 1,2-di(methanesulfonoxy)ethane.

The hydrophobic polymer coating layer has the following properties: improving the smoothness of the coating layer,
Pigments may be added for the purpose of facilitating layer formation during production. As the pigment, pigments used in known coated papers (coated paper, art paper, baryta paper, etc.) can be used. Examples of pigments include titanium dioxide,
Inorganic pigments such as barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, crystalline silica, synthetic alumina silica; and organic pigments such as polystyrene resin, acrylic resin, urea-formalin resin, etc. can.

A water-resistant agent may be further added to the hydrophobic polymer coating layer. Examples of the water-resistant agent include polyamide polyamine epichlorohydrin resin, polyamide polyurea resin, glyoxal resin, and the like.

Among these, formalin-free polyamide polyamine epichlorohydrin resins and polyamide polyurea resins are particularly preferred.

The coating layer of the hydrophobic polymer as described above is obtained by applying a latex-like coating liquid in which components such as a hydrophobic polymer, a curing agent, a pigment, and a waterproofing agent are dissolved, dispersed, or emulsified onto a base paper. It can be easily installed. As a method for applying the coating liquid onto the base paper, a known cast coating method, dip coating method, air knife method, curtain coating method, roller coating method, doctor coating method, gravure coating method, etc. can be used.

The hydrophobic polymer coating layer has a coating amount of 3 g/m2 or more (
When providing multiple layers, it is preferable to provide the total amount) on the base paper. A more preferable coating amount is 5 to 30 g/
m2.

In addition, for the purpose of improving the smoothness of the paper support, a calender treatment such as a gloss calender or a super calender may be performed during or after coating the above-mentioned coating layer.

In systems that form images by diffusion transfer of dyes, such as the present invention, a dye fixing element is used in conjunction with the photosensitive element.

The base paper in the present invention is used as a support for at least one of the dye fixing element and the photosensitive element. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Pat. No. 4,500,626, No. 57.
The relationships described in Ill are also applicable to the present application.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder, that is, a dye fixing layer. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat.
, No. 626, columns 58-59 and the mordant described in JP-A-61-88256, pages (32)-(41) of JP-A-61-88256;
Examples include those described in No. 2-244043 and No. 62-24403. Also, U.S. Patent No. 4.4
Dye-receiving polymeric compounds such as those described in No. 63.079 may also be used.

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

It is particularly useful to provide a protective layer.

Hydrophilic binders are preferably used for the constituent layers of the photosensitive element and dye fixing element in the present invention. Examples include those described on pages (26) to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, such as natural compounds such as proteinaceous binders such as gelatin, gelatin derivatives, cellulose derivatives, starch, polysaccharides such as acacia, dextran, pullulan, and polyvinyl alcohol. , polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds.

In addition, super absorbent polymers described in JP-A No. 62-245260, i.e., homopolymers of vinyl monomers having -COOM or -3O3M (M is a hydrogen atom or an alkali metal), these vinyl monomers together, or other vinyl Copolymers with monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-58 manufactured by Sumitomo Chemical ■) are also used. Two or more of these binders can also be used in combination.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. Furthermore, when a highly water-absorbing polymer is used in the dye-fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye-fixing element to another object after transfer.

In the present invention, the amount of binder applied is preferably 20 g or less per ltn', particularly 10 g or less, and more preferably 7 g.
The following is suitable as a hardening agent for use in the constituent layers of the light-sensitive element and the dye-fixing element: U.S. Pat.
No. 9-116655, No. 62-245261, No. 61
Examples include hardeners described in Kasa No. 18942. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, and epoxy hardeners (CH2-C)I-C)12-0-(CH2)
4 -0 -C)+2\ 1 -Cl (-CH2, etc.) \ 1 Vinylsulfone hardener (N,N'-ethylene-bis(vinylsulfonylacetamido)ethane, etc.), N-methylol hardener agents (such as dimethylol urea), or polymeric hardening agents (compounds described in JP-A No. 62-234157, etc.).

In the present invention, a base or a base precursor is used as an image formation accelerator in the photosensitive element and/or the dye fixing element. In addition, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, compounds that interact with silver or silver ions, etc. may be used in combination.For details, see U.S. Pat. 678,739 No. 38-4
It is written in column 0.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. No. 4,511,493, Japanese Patent Application Laid-Open No. 62-65038, etc.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing element in order to improve the storage stability of the photosensitive element.

In addition to the above, combinations of sparingly soluble metal compounds and compounds that undergo a score-forming reaction with the metal ions that constitute the sparingly soluble metal compounds (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

Various development stoppers can be used in the photosensitive element and/or dye fixing element in the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors. For more details, see JP-A No. 62-253159 (
It is described on pages 311-(32).

Constituent layers of the photosensitive element or dye fixing element in the present invention (
(including the back layer) may contain various polymer latexes for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure increase and desensitization. Specifically, any of the polymer latexes described in JP-A-62-245258, JP-A-62-136648, JP-A-62-110066, etc. can be used.
In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. can get.

In the constituent layers of the light-sensitive element and dye-fixing element in the present invention, a high-boiling organic solvent can be used as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive element and the dye-fixing element. Specifically, there are those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. Examples include various modified silicone oils, especially carboxy-modified silicone (trade name: X-22
-3710) etc. are effective. Also, JP-A-62-2
Silicone oils described in No. 15953 and Japanese Patent Application No. 62-23687 are also effective.

Antifading agents may be used in the photosensitive element and dye fixing element in the present invention. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, and other JP-A-54-48535, JP-A No. 62-1366
There are compounds described in No. 41, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Patent No. 4.241゜155,
No. 4,245.018, columns 3 to 36, No. 4,25 of the same
4. No. 195, columns 3 to 8, JP-A-50-87649,
No. 62-174741, No. 61-88256 (2
Pages 7) to (29), Patent Application No. 1983-234103, No. 6
There are compounds described in Japanese Patent Application No. 2-31096, Japanese Patent Application No. 62-230596, etc.

An example of a useful anti-fading agent is JP-A-62-21527215.
No. 272, pp. 137-(137).

The antifading agent for preventing fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance, or may be supplied to the dye fixing element from outside such as a photosensitive element. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent brightener may be used in the photosensitive element and dye fixing element in the present invention. In particular, it is preferable to incorporate the fluorescent whitening agent into the dye-fixing element or to supply it from outside the photosensitive element.

Examples include K. Veenkataraman class The Chemistry of 5ynthet
ic Dyes J Volume V Chapter 8, JP-A-61-143
Examples include compounds described in No. 752 and the like.

More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

The constituent layers of the photosensitive element and dye fixing element in the present invention include:
Various surfactants can be used for purposes such as coating aids, improving releasability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A No. 62-173463.
No. 62-183457, etc.

The constituent layers of the photosensitive element and dye fixing element in the present invention include:
An organic fluoro compound may be included for the purpose of improving slipperiness, preventing static electricity, improving peelability, etc. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 1, Japanese Patent Publication No. 61-20944, 62-1358-2
Examples thereof include fluorine-based surfactants described in No. 6, etc., or hydrophobic fluorine compounds such as oily fluorine-based compounds such as fluorine oil, or solid fluorine compound resins such as tetrafluoroethylene resin.

A matting agent can be used in the photosensitive element and dye fixing element in the present invention. As matting agents, in addition to the compounds described in JP-A-61-88256, page (29) such as silicon dioxide, polyolefin, or polymethacrylate, there are also compounds such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc. 11006
There are compounds described in No. 4 and No. 62-110065.

In addition, the constituent layers of the photosensitive element and the dye fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61
-88256, pages (26) to (32).

As a support for the light-sensitive element and the dye-fixing element in the present invention, at least one of the supports is used as described above, but when using a support other than this for the other one, a support that can withstand the processing temperature is used. It is fine as long as it is something. - In terms of numbers, paper and synthetic polymers (films) can be mentioned.

Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose (for example, triacetyl cellulose), or films containing pigments such as titanium oxide, 2, and polypropylene, etc. Film-based synthetic paper, mixed paper made from synthetic resin bulbs such as polyethylene and natural bulbs, Yankee paper, baryta paper, coachite paper (especially cast-coated paper), metals, fabrics, glass, etc. are used. .

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A No. 62-253159 tea canister 29) ~ (
The supports described on page 31) can be used. A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

The heat-developable photosensitive element of the present invention basically has a photosensitive silver halide and a binder on a support, and further contains an organometallic salt oxidizing agent and a dye-donating compound (as described below) as necessary. may also serve as a reducing agent). These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers.

For example, when a colored dye-providing compound is present in the lower layer of the silver halide emulsion, it prevents a decrease in sensitivity. Although the reducing agent is preferably incorporated into the photothermographic element, it may also be supplied from the outside, for example by diffusing it from a dye fixing element as described below.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination. For example, blue-sensitive layer, green-sensitive layer,
There are combinations of three layers such as a red-sensitive layer, a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in a variety of arrangements known from conventional color photosensitive elements. Further, each of these photosensitive layers may be divided into two or more layers as necessary. For example, each photosensitive layer is a highly sensitive layer,
There are two layers, a low-sensitivity layer, or three layers, a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer.

The heat-developable photosensitive element can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a backing layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofog. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Silver halide emulsions may be monodisperse or polydisperse;
A mixture of monodispersed emulsions may be used.

The particle size is preferably 0.1-2μ, particularly 0.2-15μ. The crystal habits of silver halide grains are cubic, octahedral, and 1
It may be a tetrahedron, a flat plate with a high aspect ratio, or any other shape.

Specifically, U.S. Patent No. 4,500.626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

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.

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, U.S. Pat.
I 7029 (1978) pages 12-13 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, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat.゜615.641, patent application 1986-22
6294 etc.).

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. 4.225.686. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

In the present invention, an organic metal salt can be used together with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like.・Also, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A No. 60-113235, and JP-A No. 61-249044.
Also useful is acetylene silver, described in No. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
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 in terms of silver.
/go is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD17
643 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and their Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

As the reducing agent used in the present invention, those known in the field of heat-developable photosensitive elements can be used. Further, a dye-donating compound having reducing properties, which will be described later, is also included (in this case, other reducing agents can also be used in combination).
Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

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, No. 30-31 (1, No. 4,330,61)
No. 7, same No. 4゜590.152, JP-A-60-140
No. 335, pages (17) to (18), 57-4024
No. 5, No. 56-138736, No. 59-178458
No. 59-53831, No. 59-182449,
No. 59-182450, No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-198540, No. 60-181742,
There are reducing agents and reducing agent precursors described in European Patent No. 220.746A2, pages 78 to 96, etc. .

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

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent is optionally added to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of precursors can be used.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are 1-phenyl-3-virazolidones or aminephenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive element, and preferably hydroquinones, Examples include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

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, when silver ions are reduced to silver under high temperature conditions, a compound that generates or releases a mobile (diffusible) dye in response to or inversely to this reaction, i.e., a dye. Using a donating compound.

Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through oxidative coupling reactions. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction.
Specific examples of developers and couplers can be found in James, The Theory of the Photographic Process, 4th Edition (T,) I.

James The Theory of the
PhotographicProcess” ) 2
91-334 pages and 354-361 pages, Japanese Patent Application Publication No. 1986-
No. 123533, No. 58-149046, No. 58-1
No. 49047, No. 59-111148, No. 59-12
No. 4399, No. 59-174835, No. 59-231
No. 539, No. 59-231540, No. 60-2950
No. 60-2951, No. 60-14242, No. 6
No. 0-23474, No. 60-66249, Special Publication No. 1973
-24849, Japanese Unexamined Patent Publication No. 53-129036, etc., in detail.

Further, as another example of the dye-providing compound, there can be mentioned a compound having a function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (Ll).

(Dye-Y)1-Z (Ll)Dye represents a dye group, -temporally shortened dye group or dye precursor group, Y represents a mere bond or linking group, and Z represents an imagewise latent dye group. Correspondingly or inversely to the image-bearing photosensitive silver salt, causing a difference in the diffusivity of the compound represented by (D ye −Y ) n−Z or releasing Dye,
Represents a group having a property that causes a difference in diffusivity between released Dye and (Dye-Y)1-Z, n represents 1 or 2, and when n is 2, two Dye
e-Y may be the same or different.

Specific examples of the dye-providing compound represented by the general formula (Ll) include the following compounds (1) to (2).

Note that ■ to ■ below correspond inversely to the development of silver halide to form a diffusible dye image (positive dye image), and ■ and ■ correspond to the development of silver halide to form a diffusible dye image. It forms a dye image (negative dye image).

■U.S. Patent No. 3.134,764, U.S. Patent No. 3.362,
No. 819, No. 3,597,200, No. 3.544
, No. 545, No. 3.482.972, etc., in which a hydroquinone developer and a dye component are linked can be used. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■As described in US Pat. No. 4,503,137, etc., non-diffusible compounds that release diffusible dyes in an alkaline environment but lose this ability when reacted with silver halide can also be used.

Examples include compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions described in U.S. Patent No. 3,980,479, and isoxacilone rings described in U.S. Pat. Examples include compounds that release diffusible dyes through intramolecular rewinding reactions.

■US Patent No. 4.559.290, European Patent No. 220
, No. 746A2, Technical Report No. 87-6199, non-diffusible compounds that react with the reducing agent remaining unoxidized by development to release a diffusible dye can also be used.

Examples include U.S. Patent No. 4,139,389, U.S. Pat.
No. 57-84453, etc., a compound that releases a diffusible dye by an intramolecular nucleophilic substitution reaction after being reduced, U.S. Patent No. 4,232.107, JP-A-59
-101649, 461-88257, RD240
25 (1984), etc., a compound that releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3.008.588A, JP-A-1983-1
No. 42530, U.S. Pat. No. 4,343.893, U.S. Pat. No. 4.619,884, etc., compounds whose single bonds are cleaved after reduction to release a diffusible dye; U.S. Pat. No. 4,450; Nitro compounds that release diffusible dyes after accepting electrons, as described in U.S. Pat.
Examples include compounds that release a diffusible dye after accepting electrons, as described in No. 609,610.

Also, more preferably, European Patent No. 220.7
No. 46A2, Public Technical Report 87-6199, Patent Application 1986-3
Compounds having an N-X bond (X represents oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group in one molecule, as described in No. 4953, No. 62-34954, etc., patent application No. 62-106
A compound having SO2-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 885, patent application No. 1988-
106895, a po-x bond (X
has the same meaning as above) and an electron-withdrawing group, c-x' in one molecule described in Japanese Patent Application No. 106887/1983
Examples thereof include compounds having a bond (X' is synonymous with X or represents -302-) and an electron-withdrawing group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the -molecule are particularly preferred. A specific example is European Patent 2
Compounds (1) to (3) described in 20.746A2
, (7) to (1o), (12), (13), (15),
(23) to (26), (31), (32), (35),
(36), (40), (41), (44), (53)~
(59), (64), (70), Technical Report 87-619
9, compounds (11) to (23), and the like.

■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler) can be used. Specifically, British Patent No. 1.330゜524, Japanese Patent Publication No. 48-39165,
U.S. Patent No. 3,443,940, U.S. Patent No. 4,474°8
There are those described in No. 67, No. 4,483,914, etc.

■Reducing to silver halide or organic silver salt,
Compounds that release diffusible dyes upon reduction of their partner (DRR)
compounds) can be used.

Since this compound does not require the use of any other reducing agent, it is preferable since there is no problem of image staining due to oxidative decomposition products of the reducing agent. A typical example is U.S. Patent No. 3,928,312
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,
51-104343, RD17465, U.S. Patent No. 3,725°062, U.S. Patent No. 3,728.113,
No. 3.443,939, JP 58-116537
No. 57-179840, US Patent '$4.500
．． It is described in No. 626, etc.

Specific examples of DRR compounds include the aforementioned U.S. Patent Nos. 4 and 5.
No. 00,626, columns 22 to 44, among which compounds (1) to (3), (10) to (13), and (16) described in the above-mentioned U.S. patent can be mentioned.
) ~ (19), (28) ~ (30), (33) ~ (35
), (38) to (40), and (42) to (64) are preferred. Also, U.S. Patent No. 4.639.408 No. 37-3
Also useful are the compounds listed in column 9.

In addition, as dye-donating compounds other than the couplers and general formula (LI) mentioned above, dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine 1978
May issue, pages 54-58), azo dyes used in heat-developable silver dye bleaching methods (US Pat. No. 4,235.957, etc.),
Research Disclosure magazine, April 1976 issue,
30-32), leuco dye (U.S. Pat. No. 3,985)
, No. 565, No. 4.022,617, etc.) can also be used.

Hydrophobic additives such as the dye-providing compounds and diffusion-resistant reducing agents described above can be incorporated into the layers of the photosensitive element by known methods such as those described in U.S. Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-Open No. 59-83154,
No. 59-178451, No. 59-178452, No. 59-178453, No. 59-178454, No. 5
9-178455, 59-178457, etc., if necessary, at a boiling point of 50°C.
It can be used in combination with a low boiling point organic solvent of ~160°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. Also, lcc or less, and even 0.1cc per 1g of binder.
5 cc or less, particularly 0.3 cc or less is suitable.

Special Publication No. 51-39.853, Japanese Patent Publication No. 51-59943
The dispersion method using polymers described in No.

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

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, JP-A-5
The surfactants listed on pages (37) to (38) of No. 9-157636 can be used.

In the present invention, a compound can be used in the photosensitive element that activates development and simultaneously stabilizes the image. For specific compounds preferably used, see U.S. Patent i4,
No. 500,626, Nos. 51 to 52111.

In the present invention, methods for exposing and recording an image on a photosensitive element include, for example, a method of directly photographing a landscape or person using a camera, a method of exposing through a reversal film or a negative film using a printer or an enlarger, etc.
A method of scanning and exposing an original image through a slit using an exposure device of a copying machine, a method of transmitting image information via an electric signal to a light emitting diode, various lasers, etc., a method of transmitting image information to a CRT, liquid crystal display, etc. There is a method of outputting the image to an image display device such as an electroluminescence display or a plasma display and exposing it directly or through an optical system.

Light sources for recording images on the photosensitive element include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., as mentioned above, such as U.S. Pat. No. 4,500,6.
The light source described in No. 26, column 56 can be used.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD can be used.

In the present invention, JP-A-59-218443, JP-A No. 6
As detailed in No. 1-238056, development and transfer are performed simultaneously or sequentially by heating in the presence of a small amount of water. In this method, the heating temperature is 50°C or higher and 100°C.
Desirably below ℃.

An inorganic alkali metal salt or an organic base may be added to the water used to accelerate development and/or transfer the diffusible dye to the dye fixing layer. Further, 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 sparingly soluble metal salt, a complex-forming compound, etc. may be included in the solvent.

Such water can be used in a method of applying it to the dye-fixing element, the light-sensitive element, or both. The amount used may be as small as less than the weight of water corresponding to the maximum swelling volume of the entire coating film (particularly less than the amount obtained by subtracting the weight of the entire coating film from the weight of water corresponding to the maximum swelling volume of the entire coating film).

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, there is a method described in JP-A-61-147244 (page 261).Also, it is also possible to incorporate the solvent into the photosensitive element, the dye fixing element, or both in advance, such as by encapsulating the solvent in microcapsules. .

Heating methods in the development and/or transfer process include contact with a heated block or plate, hot plate, hot breather, heat roller, halogen lamp heater, infrared and far-infrared lamp heater, etc. or passing through a high-temperature atmosphere.

Alternatively, a resistive heating layer may be provided on the photosensitive element or the dye fixing element, and the layer may be heated by supplying electricity to the layer. As the heat generating layer, those described in JP-A-61-145544 and the like can be used.

In the present invention, the method described in JP-A-61-147244 (page 271) can be applied to the pressure conditions and method of applying pressure when the photosensitive element and the dye fixing element are superimposed and brought into close contact with each other.

Any of a variety of thermal development equipment can be used to process the photographic element comprised of the light-sensitive element and dye-fixing element of the present invention. For example, JP-A No. 59-75247, No. 59-177547, No. 59-181353, No. 6
Apparatuses described in No. 0-18951, Utility Model Application Publication No. 62-25944, etc. are preferably used.

■Specific effects of the invention According to the present invention, the expansion and contraction rate is eased by lowering the internal bonding strength of the base paper used as the support, and the dye-fixing element and photosensitive element stored for a long period of time under low humidity can be used. Also, good images without uneven transfer can be obtained.

Such effects are further enhanced by increasing the smoothness of the base paper.

Further, this is particularly noticeable when a thermal development transfer type image forming method is applied.

(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 dye fixing element was prepared as follows.

First, the paper supports shown in Table 1 were used.

In addition, all paper supports in Table 1 have a basis weight of 70 g/l11
2. Thickness is 80 μm.

Additionally, talc and anionic polyacrylamide as shown in Table 1 were added to the paper in this case as additives.
In addition, 1.0 wt% of sodium stearate and 1.5 wt% of aluminum sulfate were each commonly added.

The amounts of these additives added are based on the pulp.

The pulp abbreviations in Table 1 are as follows.

BKP: Bleached hardwood sulfate valve NBKP: Bleached softwood sulfate valve LBSP: Bleached hardwood sulfite pulp NBSP: Bleached softwood sulfite pulp DP; Dissolving pulp The characteristic values in Table 1 are based on the following measurements or definitions. be.

(H) Internal bond strength Prepare at least five 50x50 mm samples from each paper forming the paper support and test them using a ZDT tester (Custom
5 scientific instruments.

(manufactured by Inc.). In this case, double-sided coated pressure-sensitive tape (3M 5c manufactured by 3M Company) was used to seal the sample.
otch Brand No. 410) was used.

fiil Rp A 20×20 mm sample was prepared from each paper forming the paper support and measured using a dynamic printing smoothness measuring device (manufactured by Toyo Seiki Seisakusho ■). In this case, the sample is placed on the prism surface and the step pressure applied is 5 kg/cm.
”.

111) Beating degree Canadian freeness was beaten to 220 to 350 cc.

Using each of these paper supports, each layer was formed on the paper support as shown in Table 2.

Note that the paper support was used by laminating polyethylene of 20 μm on both sides of the paper.

Table 2 *1) Surfactant A, 2) Surfactant B, 3) Mordant compound Nireophos-95 (manufactured by Ajinomoto) Oil droplet preparation and addition method: 5% sodium dodecylbenzenesulfonate to 100g of 10% gelatin aqueous solution Water m? Add 5all at night, further add 9520g of Rheophos, and emulsify and disperse in a homoblender at 10,000r, p, m for 6 minutes.The resulting oil droplet dispersion was used as a coating solution for the dye fixing layer (second layer). added inside.

◆5) Hardener A Medium 6) Slip agent Silicone oil (dimethylpolysiloxane) Oil droplets [Medium 4) These were prepared in the same manner as the oil droplets and added. ] Dye fixing elements 101 to 105 (the present invention) corresponding to the paper support using the dye fixing elements produced in this way,
111 to 113 (comparison).

Such a dye fixing element was heated at a temperature of 50°C and a humidity of 15% RH.
It was stored below for 7 days.

Next, we will explain how to make photosensitive elements -1 and K-2.

Photosensitive element -1 having the structure shown in Table 3 was prepared.

Table 3 Layer number Layer name Additive Addition amount (g/rn”) 6th layer Protective layer Gelatin
0.9 Matte agent Silica 0
．． 116 Water-soluble polymer (1) 0.22
8 Surfactant (1) 0.064 Surfactant (2) 0.036 Hardener
0.018 surfactant (3)
0.06 5th layer green light emulsion (I)
0.4 Photosensitive layer Acetylene compound 0.022 Ikrho dye-donating substance
0.45 High boiling point organic solvent (1) 0.22
5 Reducing agent (1) 0.009 Melt compound (1) 0.009 Water-soluble polymer (2) 0.02 Hardener
0.013 gelatin 0.6
4 Surfactant (5) 0.045Table 3
(Continued 1) Layer number Layer name Additive Addition amount (g/rr?) 4th layer Intermediate layer Gelatin 0.72n(OH) 20.3 Surfactant (1) 0.001 Water-soluble polymer (2) 0 .03 Hardener
0.014 surfactant (4)
0.029 3rd layer red light emulsion (IV)
0.21 Photosensitive layer Organic silver salt (
1) Silver 3i 0.035 organic silver salt (2)
Silver amount 0.035 gelatin
0.44 Magenta dye-donating substance 0.3 High boiling point organic solvent (1) 0.15 Reducing agent (1
) 0.006 melt compound (1) 0.003 water-soluble polymer (2)
0.013 surfactant (5)
0.03 Hardener 0.009
Table 3 (continued 2) Layer number Layer name Additive Additive amount (g/rr?) 2nd layer Intermediate layer Gelatin
0.77Zn(0)1)20.3 Surfactant (4) 0.047 Water-soluble polymer (2) 0.038 Surfactant (1
) 0.046 Hardener
0.016 1st layer red light emulsion (■)
0.26 Photosensitive layer Organic silver salt (1
) Silver amount 0.035 organic silver salt (2)
Silver amount 0.035 Melt compound (2)
4 Xl0-4 sensitizing dye 5
Xl0-S Cyan dye donating substance 0.325 High boiling point organic solvent (1) 0.182 Reducing agent (1
) 8.7
0.032 Water-soluble polymer (2)
o, o1a gelatin 0
・5 Table 3 (continued 3) Layer number Layer name Additive Addition amount (
g/rrl”) 1st layer red light hardener
0.01 support (polyethylene terephthalate: thickness 100μ) back layer
Carbon black 0.44 polyester
0.33 polyvinyl chloride
0.30 High boiling point organic solvent (1) Trinonyl phosphate water-soluble polymer (1) Sumikagel L-5 (11
) Water-soluble polymer manufactured by Sumitomo Chemical (2) Surfactant (1) Aerosol OT surfactant (
2) Silicone oil reducing agent (1) Mercapto compound (1) Mercapto compound (2) We will describe how to make the emulsion for the fifth layer.

Emulsion (1) The following solutions I and II were added to a well-stirred aqueous gelatin solution (20 g of gelatin, 3 g of sodium chloride, and 0.15 g of compound O were dissolved in 800 mj of water and kept at 65°C) for 70 minutes. Added. Simultaneously with the start of addition of Solution II and Solution II, sensitizing dye (A) (I''l2)40s3 (nJl-;
5M++024g (methanol 120cc + water 120g
cc) The dye solution dissolved in the solution was added over a period of 60 minutes.

Ag NO3(g) loo −
Br (g) -56 Nai (g) -7 ■Night and I! Immediately after adding the liquid, add 2 g of KBr to 20 g of water.
It was dissolved in mu, added and left for 10 minutes.

After washing with water and desalting, add 25 g of gelatin, 100 m of water, and 9.
H was adjusted to 6.4, l) Ag to 7.8.

The resulting emulsion was a cubic monodisperse emulsion with a grain size of about 0.5 microns.

This emulsion was kept at 60°C, and 1.3 m of triethylthiourea was added.
g, 4-hydroxy-6-methyl-1,3,3a,7-
Optimal chemical sensitization was achieved by simultaneously adding 100 mg of citrazaindene. Yield was 650g.

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

Emulsion (IV) The following method and solution II were applied to a well-stirred aqueous gelatin solution (20 g of gelatin, 2 g of sodium chloride, and 15 g of compound R dissolved in 800 mj of water and kept at 65°C) for 60 minutes. and added.

■Liquid and ■! At the same time as the addition of the liquid was started, a dye solution in which 0.16 g of sensitizing dye (B) was dissolved in 80 mu of methanol was added over a period of 40 minutes.

8g NO3 (g) 100
-KBr (g) -56 NaCIl (g) -7 After addition of liquids ■ and liquid II, the mixture was allowed to stand for 10 minutes, the temperature was lowered, and the mixture was washed with water and desalted. Then, 25 g of gelatin and 100 mj2 of water were added and the pH was adjusted to 6. .5, pAg was adjusted to 7.8. Thereafter, triethylthiourea and 4-hydroxy-6-methyl-1,3,3a-7-titrazaindene were added to optimally chemically sensitize at 60°C.

The resulting emulsion was a cubic monodisperse emulsion with a grain size of approximately 0.35 μm, and the yield was 650 g.

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

Emulsion (■) Add 498 g of potassium bromide and 10.5 g of sodium chloride to a well-stirred aqueous gelatin solution (20 g of gelatin, 4 g and 0.02 g of sodium chloride dissolved in 100,100 O of water and kept warm at 60°C). An aqueous solution containing 600 mA of silver nitrate and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 mJ2 of water) were simultaneously added at equal flow rates over 50 minutes. Gelatin after washing and desalting 25
g and 200 mJZ of water were added to adjust the pH to 6.4, and triethylthiourea and 4-hydroxy-6-methyl-1,
Optimal chemical sensitization was carried out using 3,3a-7-chitrazaindene, and a cubic monodisperse emulsion (■
) 700g was obtained.

This article describes how to make organic silver salts.

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

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. This solution was kept at 40°C and stirred. 1 silver nitrate in this solution
A solution of 7 g dissolved in 100 mjZ of water was added over 2 minutes.

The pH of the hensitriazole silver emulsion was adjusted and allowed to settle to remove excess salt.

Thereafter, p)1 was adjusted to 6.30 to obtain a hensitriazole silver emulsion with a yield of 400 g.

Organic silver salt (2) 20 g of seratin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed in 10 g of 0.1% aqueous sodium hydroxide solution.
0100O and 200mu of ethanol.

This solution was kept at 40°C and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 mj2 of water was added to this solution over 5 minutes.

The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of organic silver salt (2) in a yield of 300 g.

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

15 g of yellow dye-donating substance (Y), 7.5 g of high-boiling organic solvent (1), reducing agent (110.3 g), and 0.3 g of mercapto compound (1) were added and dissolved in 45 mJ2 of ethyl acetate, and 10% gelatin was added. Solution (100 g and 60 mj2 of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate
After stirring and mixing, use a homogenizer for 10 minutes at 11
Dispersion was carried out at 0000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

15 g of magenta dye-donating substance (M), 7.5 g of high boiling point organic solvent (1), 0.3 g of reducing agent (1) and 0.15 g of mercapto compound (1) were added and dissolved in 25 mA of ethyl acetate to give a 10% After stirring and mixing gelatin i-liquid LOOG and a 2.5% aqueous solution of sodium dodecylbenzenesulfonate at 60m℃, 10D was added for 10 minutes using a homogenizer.
Dispersion was carried out at OOrpm. This dispersion is called a dispersion of a magenta dye-providing substance.

Cyan dye donor X(c)tsg, 7.5 g of high-boiling organic solvent (1), 0.4 g of reducing agent (1), and 0.6 g of mercapto compound (1) were added and dissolved in 40 ml of ethyl acetate, After stirring and mixing 100 g of a 10% gelatin solution and 60 mj2 of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate, the mixture was heated with a homogenizer for 10 minutes at 1100 ml.
Dispersed at 00rp. This dispersion is called a dispersion of a cyan dye-providing substance.

UL; 16833 (n) 0CIl1833 (n) In addition, photosensitive element -2 having the configuration shown in Table 4 was prepared. Note that the additives used are -1 to the photosensitive element unless otherwise specified.
is the same as

Table 4 Table 4 (Continued 1) Table 4 (Continued 2) Support (Polyethylene terephthalate, 100μ) Hard
Film agent (1) 1.2-bis(vinylsulfonylacetamido)ethane High boiling point organic solvent (2) Tricyclohexyl phosphate 1-1":c=e Q=E!8 Emulsion for the first layer We will explain how to make (1).

A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 1000 mλ of water)
A 600% aqueous solution containing sodium chloride and potassium bromide (containing a nitric acid solution kept at 75°C) and a nitric acid aqueous solution (
A monodispersed cubic silver chlorobromide emulsion (bromine 80 mol %) with an average grain size of 0.35 µm was prepared by adding 0.59 mol of silver nitrate dissolved in 600 mj of water at a constant flow rate over 40 minutes. was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a were added.

Chemical sensitization was performed at 60° C. by adding 20 mg of 7-chitrazaindene. The yield of emulsion was 600 g.

Next, let's talk about how to make the emulsion (11) for the third layer.

A well-stirred gelatin aqueous solution (20 g gelatin and 3 g sodium chloride in water looomR)
600 mu of an aqueous solution containing sodium chloride and potassium bromide (containing 600 mol of silver nitrate dissolved in 15 I of water) and the following dye solution (1 ) and 4 at the same time
Added at equal flow rate over 0 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) was prepared in which a dye having an average grain size of 0.35 μm was adsorbed.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a were added.

Chemical sensitization was performed at 60° C. by adding 20 mg of tutetrazaindene. The yield of emulsion was 600 g.
Dye solution (I)...The following sensitizing dye (D-1) 160m
Next, we will discuss how to prepare emulsion (III) for the fifth layer.

Add 1000d of an aqueous solution containing potassium iodide and potassium bromide to a well-stirred aqueous gelatin solution (20g of gelatin and ammonium dissolved in 10100O of water and keep warm at 50°C) and an aqueous solution of nitric acid (1000d of an aqueous solution containing silver nitrate to 5100 of water). mol) was added at the same time while keeping the pAg constant. In this way, a monodisperse octahedral silver iodobromide 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 2 g of sodium periosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1 kg.

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

Add and dissolve 13 g of yellow dye-donating substance (1), 6.5 g of high-boiling organic solvent (1) and 6.5 g of electron donor in 37 m9 of cyclohexanone, add 100 g of 10% gelatin solution and dodecylbenzenesulfonic acid. 2.5 of soda
% aqueous solution with 60% soap, and then dispersed with a homogenizer at 110,000 rp+ for 10 minutes. This dispersion is called a yellow dye-providing substance dispersion.

Magenta dye-donating substance (2) 16.8 g.

8.4 g of high-boiling organic solvent (1) and 6.3 g of electron donor
g was added and dissolved in 37 g of cyclohexanone, mixed with 100 g of a 10% gelatin solution and 60 g of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate, and then dispersed with a homogenizer for 10 minutes at 110,000 rpm.

This dispersion is called a dispersion of a magenta dye-providing substance.

15.4 g of cyan dye-donating substance (3), 7.7 g of high boiling point organic solvent (1) and 6.0 g of electron donor were added and dissolved in cyclohexanone 3rd, and 10% gelatin solution 1 was added.
00g and 2.5% of sodium dodecylbenzenesulfonate
Water soluble? After stirring and mixing with I60mQ, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion is called a dispersion of a cyan dye-providing substance.

Thereafter, the following treatments were performed using the photosensitive element and dye fixing element.

-1 to the photosensitive element using a xenon flash tube
Exposure was made for 4 seconds. At that time, the concentration of G changes continuously.
, R% IR through a three-color separation filter.

12 al. 17 m'' of water was supplied to the emulsion surface of the exposed light-sensitive element using a wire bar, and then the elements were superimposed on the dye fixing elements 101 to 105 and 111 to 113 described above so that their film surfaces were in contact with each other.

Using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed film is 90°C, it is heated for 25 or 35 seconds and then peeled off from the dye-fixing element.
Yellow, corresponding to the 3 color separation filters of %R and IR.
Magenta and cyan images were obtained.

On the other hand, photosensitive element -2 was exposed using a tungsten bulb at 5000 lux for 1/10 second through continuously varying density B, G, R and gray color separation filters. This exposed photosensitive element was processed at a linear speed of 20 I1.
While feeding at m/sea, 15sit /
s'' of water was supplied using a wire bar, and immediately thereafter, the dye fixing elements 101 to 105 and 111 to 113 were superimposed so that their membrane surfaces were in contact with each other.

The film was heated for 20 or 30 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C. When it was then peeled off from the dye-fixing element, blue, green, red, and gray images corresponding to the B, G, R, and gray color separation filters were obtained on the dye-fixing element.

The occurrence of transfer unevenness was investigated for images obtained using each dye fixing element. Transfer unevenness is Icm2
The number of hits was counted at 10 locations, and the minimum and maximum values were determined. The results are shown in Table 5.

Table 5 Dye-fixing element Internal bonding force Rp Transfer unevenness (paper support) Occurrence and settling (Kg-
c+s) (door) (pieces/cm”) 101 (invention) !, 43 5.5 2-3102 (
present invention) 1.65 6.7 2-310
3 (present invention) 1.05 4.9 2-3
104 (present invention) 0.88 4.1 2
~3105 (present invention) 1.35 5.2
2-3111 (comparison) 3.15 1
5.1 10-12112 (comparison) 2.
36 10.5 4-7113 (Comparison>
2.85 12.3 7 to 10 Example 2 In the dye fixing element 102.103 of the present invention in Example 1, except that the following coating layer was formed on the paper support to a thickness of 20μ by a cast coating method. Similarly, dye fixing element 2
01.202 was produced. Therefore, polyethylene will be laminated on the coating layer.

Coating I (Si 1) Composition Photography”! Saka Kaolin 10g/■2 Casein 1 g7m”S B R1g/
s' After storage in the same manner as in Example 1, the same treatments and operations were performed, and the occurrence of transfer unevenness was examined.

The results are shown below.

201 1.65 3.5 320 1~2
202 1.05 2.3 300 1~2
The above results show that the provision of the coating layer improves smoothness and further suppresses the occurrence of transfer unevenness.

Further, in the photosensitive element prepared in Example 1, -1-101 and K-1 were prepared in the same manner except that paper supports of dye fixing elements 101 and 102 shown in Table 1 were used as supports for -1 and K-2.
-1-102, K-2-101, and -2-102 were made.

Then, after storage in the same manner as in Example 1, the dye fixing element 101.
102, the same treatments and operations were performed, and the occurrence of transfer unevenness was investigated.

The results are shown below.

-1-1011012-3 -1-1021022-3 -2-1011012-3 -2-1021022-3 From the above results, the occurrence of uneven transfer is suppressed even when the paper support is used for the photosensitive element. I understand that.

Claims (1)

[Claims] (1) At least a photosensitive silver halide on a support, a binder, and when the photosensitive silver halide is reduced to silver under high temperature conditions, a diffusible dye is produced or released in response to or inversely to this reaction. heating the photosensitive element having the dye-donating compound in the presence of water and a base and/or base precursor after or simultaneously with the imagewise exposure;
In an image forming method in which a generated or released diffusible dye is transferred to a dye fixing element having a dye fixing layer on a support, at least one of the two supports has an internal bond strength of 0.5. An image forming method characterized in that the paper support is formed from a base paper of ~2.0 kg/cm.