JPH01185630A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material capable of recording information which can be read by IR light by coating photosensitive silver halides, binders and dye-donative compds. which forms dye images having absorption in an IR region on a base. CONSTITUTION:A silver halide photosensitive layer combined with the dye- donative compd. which forms the dye image of, for example, yellow, having the absorption in the IR region is coated on the base such as paper laminated with polyethylene. The silver halide photosensitive layer combined with the dye-donative compd. which forms the dye image of magenta is coated via an intermediate layer which is the binder such as gelatin thereon and the silver halide photosensitive layer combined with the dye-donative compd. which forms the dye image of cyan is coated via the intermediate layer of gelatine thereon. The heat developable photosensitive material capable of recording the information which can be read by IR light is thereby obtd.

Description

[Detailed description of the invention] ■ Background of the invention Technical field The present invention relates to a heat-developable photosensitive material.

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

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

When photosensitive silver halides and/or organic silver salts are reduced to silver by thermal development, they generate or release mobile (diffusible) dyes in response to or inversely to this reaction, and this mobility This is a method in which a dye is transferred to a dye-fixing element.

On the other hand, devices that optically read information, such as optical character readers (OCR) and barcode readers, now use infrared light from infrared light emitting diodes (LEDs) as light sources. It's coming.

Furthermore, in response to demands for information technology, it is often necessary to add information such as barcodes to images obtained by the above-mentioned thermal development method.

A method using a color developer to form a pigment that absorbs in the infrared region is disclosed in JP-A-48-78905 and JP-A-53-
It is described in No. 129036, No. 53-125836, etc. In these examples, movie sound (audio)
Proposed for record use. The methods described in these documents employ wet development processing, and the steps are complicated, and the management of processing liquids is often complicated, and improvements are desired.

For this reason, it is practically preferable if information such as a bar code that can be read using infrared light such as an infrared emitting LED can be recorded on a heat-developable photosensitive material.

II. OBJECTS OF THE INVENTION An object of the present invention is to provide a photothermographic material capable of recording information readable with infrared light.

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

That is, the present invention is a heat-developable photosensitive material characterized by having on a support at least a photosensitive silver halide, a binder, and a dye-providing compound that forms a dye image having absorption in the infrared region.

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

The heat-developable photosensitive material of the present invention has on a support at least a photosensitive silver halide, a binder, and a dye-donating compound that forms a dye image having absorption in the infrared region.

The dye-providing compound that forms a dye image with absorption in the infrared region may be contained in any layer of the heat-developable photosensitive material. It is preferably contained in the combined silver halide photosensitive layer or a layer adjacent thereto, particularly in the silver halide photosensitive layer. Further, a silver halide photosensitive layer in combination with such a dye-providing compound may be separately provided and contained.

The heat-developable photosensitive material of the present invention comprises a support, a silver halide photosensitive layer in combination with a dye-providing compound (yellow dye-providing compound) that forms a yellow dye image, and a dye that forms a magenta dye image. It has a silver halide photosensitive layer combined with a donating compound (magenta dye donating compound) and a silver halide photosensitive layer combined with a dye donating compound (cyan dye donating compound) that forms a cyan dye image. Preferably.

In this case, the dye-donating compound that forms a dye image having absorption in the infrared region may be contained in any of the silver halide photosensitive layers described above, or may be contained in a separate photosensitive layer as described above. good.

Here, the term "combination" includes not only the case where each dye-providing compound is added to the silver halide photosensitive layer, but also the case where it is added to the non-photosensitive layer adjacent thereto.

The absorption in the infrared region of the dye having absorption in the infrared region of the present invention is 680 nm or more, preferably 700 nm.
It is desirable that the wavelength is at least 720 nm, more preferably at least 720 nm. In this case, it is advantageous to read out optically using an LED in the infrared region.

In particular, in the above-mentioned heat-developable photosensitive materials, the dye-donating compound that forms the dye image having absorption in the infrared region is a cyan dye-providing compound because the short wavelength side of the absorption may tail off to cyan. It is preferable to contain it in the same layer as the layer containing.

Specific examples of the dye-donating compound that forms a dye image having absorption in the infrared region used in the present invention include those shown below.

The dye-providing compounds described above for couplers can be easily synthesized by known methods.

As the dye-donating compound that forms a dye image having absorption in the infrared region, in addition to the above-mentioned couplers, any dye-donating compound that releases or forms a diffusible dye can be used.

The amount of the dye-providing compound that forms a dye image having absorption in the infrared region is 0.02 to 2 moles per mole of silver.

As a dye-donating compound for forming a visible image that can be used in the present invention, when silver ions are reduced to silver under high temperature conditions, a dye is formed in response to this reaction or in reverse response. Compounds that release or release are mentioned.

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 is a 2-equivalent coupler that has a diluent-diffusing group as a leaving group and forms a diffusible dye through an oxidative coupling reaction.
Specific examples of developers and couplers can be found in “The Theory of the Photographic Process” by James, Volume 4.
Edition (T, H.

James The Theory of the
PhotographicProcess'')291~
334 pages and 354-361 pages, JP-A-58-12
No. 3533, No. 58-149046, No. 5B-149
No. 047, No. 59-111148, No. 59-1243
No. 99, No. 59-174835, No. 59-23153
No. 9, No. 59-231540, No. 60-2950,
No. 60-2951, No. 60-14242, No. 60-
No. 23474, No. 60-66249, Special Publication No. 52-2
It is described in detail in No. 4849, JP-A-53-129036, etc.

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

(Dye-Y)n-Z (LI)Dy
e represents a dye group, a temporally shortened dye group or a dye precursor group, Y represents a car bond or a linking group, and Z corresponds to a photosensitive silver salt having a latent image in image form or Inversely, a difference is created in the diffusivity of the compound represented by (Dye-Y)n-Z, or Dye is released and there is a gap between the released Dye and (Dye-Y)n-Z. Represents a group having properties that cause a difference in diffusivity, n represents 1 or 2, and when n is 2, two Dye
-Y may be the same or different.

Specific examples of the dye-providing compound represented by the general formula (LI) 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. 3,54
4,545, 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 and others, 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. 22
As described in No. 0.746A2, Technical Report 87-6199, etc., non-diffusible compounds that react with the reducing agent remaining unoxidized during development to release a diffusible dye can also be used.

Examples include the intramolecular after reduction described in U.S. Pat. Compound that releases a diffusible dye by nucleophilic substitution reaction of
4025 (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-1986
-142530, U.S. Patent No. 4.343.893,
Compounds that release diffusible dyes by cleavage of single bonds after reduction, as described in U.S. Patent No. 4,619,884, etc., and diffusible dyes that release diffusive dyes after accepting electrons, as described in U.S. Patent No. 4,450,223, etc. Nitro compounds that release
Examples include compounds that release a diffusible dye after accepting electrons, as described in, eg, No. 609, No. 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. 62-10
A compound having 5o2-X (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 6885, patent application No. 1982-
106895, a po-x bond (X
is synonymous with Examples include compounds having an attractive group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the molecule are particularly preferred.
Compounds (1) to (3) described in No. 20.746A2
, (7) ~ (lO), (12), (13), (15)
, (23) to (26), (31), (32), (35)
, (36), (40), (41), (44), (53)
~ (59), (64), (70), Public Technical Report 87-61
99 compounds (11) to (23).

(2) Compounds (DDR couplers) having a diffusible dye as a leaving group and which release the diffusible dye upon reaction with an oxidized form of a reducing agent can be used. Specifically, British Patent No. 1,330.524, Japanese Patent Publication No. 4B-39165
No. 3,443,940, U.S. Patent No. 4,474
．． There are those described in No. 867, No. 4,483,914, etc.

■ A compound (DR
R compound) can be used.

Since this compound does not require the use of other reducing agents, it is preferable because there is no problem of image staining due to oxidative decomposition products of the reducing agent. Representative examples thereof include U.S. Pat. .312, 4,055,428
No. 4,336,322, JP-A-59-6583
No. 9, US Pat. No. 59-69839, US Pat. No., JP-A-58-116537, JP-A No. 57-179.840, US patent bundle 4,500.
No. 11526, etc. Specific examples of DRR compounds include the compounds described in columns 22 to 44 of the aforementioned U.S. Pat. (
3), (10) to (13), (16) to (19), (
28)~(30), (33)~(:+s); (38)
~(40), (42) ~(64) are preferred. Also useful are the compounds described in US Pat. No. 4,639,408, columns 37-39.

In addition, dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine 1978
May issue, pp. 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Pat. No. 4,235,957,
Research Disclosure Magazine, April 1976 issue, 3
pages 0-32), leuco dyes (U.S. patent bundle 3.985,
No. 565, No. 4゜022.617, etc.) can also be used.

Hydrophobic additives such as the dye-providing compounds described above and the imaging promoters described below are disclosed in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 7. In this case, JP-A-59
No. -83154, No. 59-178451, No. 59-1
No. 78452, No. 59-178453, No. 59-17
No. 8454, No. 59-178455, No. 59-178
A high boiling point organic solvent such as that described in No. 457 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. Also, 1 cc or less, or even 0 cc per 1 g of binder.
．． 5 cc or less, particularly 0.3 cc or less is suitable.

Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

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

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

The heat-developable photosensitive material of the present invention 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 back 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 can be monodisperse or polydisperse (
A mixture of monodispersed emulsions may be used.

Particle sizes of 0.1 to 2μ, especially 0.2 to 1.5μ are preferred. 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, Research Disclosure (hereinafter abbreviated as RD) 17029 (1978), and U.S. Patent No. 4.62.
No. 8,021, JP-A-60-196748, JP-A-60-196748
Any of the silver halide hexide emulsions described in No. 192937, No. 60-2585357, 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 58-126526, JP 58-215644).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m 2 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. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Furthermore, 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.
/rr? is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD1
7643 (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.

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 (page 241).

The silver halide used in the present invention may be spectrally sensitized with methine dyes or 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 and JP-A No. 60-14
No. 0335, RD17029 (1978) 12-13
Examples include the sensitizing dyes described in JP-A-60-111239 and JP-A-62-32445.

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 US Pat. No. 933.390, No. 3,635,
No. 721, No. 3,743,510, No. 3,615
．． No. 613, No. 3,615,641, No. 3,61
No. 7,295 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 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used in the heat-developable photosensitive material of the present invention. The wood-philic binder is preferably transparent or semi-transparent, and includes natural compounds such as gelatin, proteins such as gelatin conductors, cellulose derivatives, starch, polysaccharides such as acacia, dextran, pullulan, and polyvinyl alcohol. , polyvinylpyrrolidone, partially saponified copolymers of vinyl alcohol and acrylic acid, acrylamide polymers, and other synthetic polymer compounds such as the water-soluble polyvinyl compounds described in JP-A-62-245260. These binders can also be used in combination of 2 f1 or more. In addition to these, it is also possible to use dispersed vinyl compounds which are used in latex form and increase the dimensional stability of the photographic material.

In the present invention, the amount of binder applied is 20 per tm'.
The amount is preferably 10 g or less, more preferably 7 g or less. Also, 2 g/layer per layer
m2 or less, preferably 1g7m2 or less.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used.

Further, the dye-donating compound having the above-mentioned reducing property 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.
．． Columns 49-50 of No. 500,626, No. 4,483 of the same
, No. 914, columns 30-31, same No. 4,330,617
No. 4.590.152, JP-A-60-1403
No. 35, pages (17) to (18), 57-40245
No. 56-138736, JP-A-60-12843
No. 8, No. 60-128436, No. 60-128439
No. 60-128437, No. 62-131253 to No. 62-131256, European Patent No. 220.
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. 746A2.

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

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

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent Nos. 4 and 5.
No. 00,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye fixing element is used together with a heat-developable photosensitive material as a photosensitive element. The dye fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. Regarding the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can be applied 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. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500,626 No. 58-59
Mordants described in columns and pages (32) to (41) of JP-A-61-88256, JP-A-60-118834, and JP-A-60-118834.
-119557, 60-235134, patent application No. 6
Examples include those described in No. 1-87180 and No. 61-87181.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing element can be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

As the binder for the constituent layers of the dye fixing element, natural or synthetic polymeric substances similar to those of the photosensitive element can be used.

One or more of the constituent layers of the photosensitive material and the dye fixing element may contain a heat solvent, a plasticizer, an antifading agent, a UV absorber,
A slippery agent, a matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, a surfactant, a fluorescent whitening agent, etc. may be included. Specific examples of these additives are described in JP-A-61-88256, pages (22) to (32). In addition, especially 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 for the dye fixing element to contain a base and/or a base precursor, which will be described later, in order to improve the storage stability of the photosensitive material. .

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing element. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive material layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40.

In the present invention, the heat development process is performed for a substantially short time, that is, 180
It is desirable to complete the process within seconds, preferably within 60 seconds, or even more quickly. For this purpose, it is preferable to contain a base or a base precursor.

The preferred addition amount is 1+vt% to 50% of the total coating amount.
wt%, preferably from 5wt% to 35wt%.

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 addition to the above, combinations of poorly soluble metal compounds and compounds that undergo complex formation reactions with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds), as described in European Patent Publication No. 210.660, and special Compounds that generate bases by electrolysis, such as those described in JP-A No. 61-232451, 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 material and the dye fixing element separately.

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

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, as described in U.S. Pat. No. 4.670.373, No. 4,656,126, No. 4,610,957 or No. 4.626.499, No. 4,678,735
No. 4.639,408, JP-A-61-1472
No. 49, No. 61-147244, No. 81-18453
No. 9, No. 61-185743, No. 61-185744
No. 61-188540, No. 61-269148, No. 61-269143, etc.).

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

Specific examples of hardening agents include those described in U.S. Pat. No. 4,678.739, column 41 and Japanese Patent Application Laid-open No. 116655/1982, and these can be used alone or in combination.

The support used in the light-sensitive material and/or dye-fixing element of the present invention is one that can withstand processing temperatures. - As supports for boat fishing, not only glass, paper, polymer films, metals and their analogues are used, but also the supports described in JP-A-61-147244, page 25. Can be used.

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

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements.
As a resistance heating element, there are two methods: a method of using a thin film of an inorganic material exhibiting semiconductivity, and a method of using a thin film of an organic material by dispersing conductive fine particles in a binder. Materials that can be used in these methods include those described in JP-A-61-145544 and the like. Note that these conductive layers also function as antistatic layers.

In the present invention, the method of coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers is described in U.S. Pat. No. 4,500,626, columns 55-56. method can be applied.

As a light source for image exposure for recording an image on a photosensitive material, radiation including visible light can be used. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc., are used in U.S. Patent No. 4.50.
The light sources described in column 56 of No. 0,626 can be used.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. The dye diffusion transfer process may be performed simultaneously with the heat development or after the heat development process is completed. In the latter case, the heating temperature in the transfer process can range from the temperature in the heat development process to room temperature. However, it is particularly preferable to use a temperature of 50° C. or higher and about 10° C. lower than the temperature in the heat development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 61-2380
As detailed in No. 56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is preferably at least 50°C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least 50°C and at most 100°C.

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

These solvents can be used in a method of applying them to a dye fixing element, a light-sensitive material, or both. The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244 (page 261). Alternatively, it can also be used by incorporating it into the dye fixing element or both.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing element. The hydrophilic thermal solvent may be incorporated in either the photosensitive material or the dye fixing element, or in both.The layer in which it is incorporated may also be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer. It is preferable to incorporate it into the dye fixing layer and/or its adjacent layer.

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

Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the light-sensitive material and/or the dye fixing element.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a method described in No. 7244, pages (26) and (27).

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 61-1472.
The method described in No. 44 (page 271) can be applied.

Any of a variety of thermal development devices can be used to process the photographic material in the present invention. For example, JP-A-59-752
No. 47, No. 59-177547, No. 59-18135
No. 3, No. 6o-18951, Utility Model Application No. 62-25944
Preferably, the devices described in No. 1, etc. are used.

In addition, in systems that do not perform dye diffusion transfer, the heat-developable photosensitive material is bleached and fixed after heat development, or bleach-fixed (Blix processing) is performed to remove residual silver halide and silver images, resulting in a dye image. You can also make it only. This is particularly useful in systems in which a coupler is used as a dye-providing compound and is subjected to a coupling reaction with an oxidized color developing agent to form a dye.

In this case, the color developing agent may be incorporated into the above-mentioned photothermographic material. Further, the color developing agent may be supplied during thermal development from a color developing agent supply sheet having a layer containing the color developing agent on a support. Specifically, the following steps can be considered.

^) When using a heat-developable photosensitive material containing a color developing agent and a base precursor.

■ Image exposure - Thermal development - Immersion in a bleach-fixing bath or a stabilizing bath ■ Image exposure - Thermal development - Immersion in a bleaching bath A constant washing or a stabilizing bath ■ Image exposure - Thermal development - Layering with a bleach-fixing sheet - Peeling off In the case of (2) above, the light-sensitive material or the bleach-fixing sheet may be moistened with water and then the two may be laminated.

B) When using a heat-developable photosensitive material that contains a base precursor but does not contain a color developing agent.

■ Image exposure - Overlap the heat-developable photosensitive material and the color developing agent supply sheet and heat development → immerse in a bleach-fixing bath or wash with water or immerse in a stabilizing bath ■ Image exposure - Overlap the heat-developable photosensitive material and the color developing agent supply sheet Thermal development - Soak in a bleaching bath.Immerse in a constant bath.Image exposure - Overlap the heat-developable photosensitive material and the color developing agent supply sheet, then heat development - Overlap with the bleach-fixing sheet -> Peel off. In the case of (2), the light-sensitive material or the bleach-fixing sheet may be moistened with water and then the two may be superimposed.

C) When a color developing agent and a basic metal compound are incorporated into the photothermographic material.

■ Image exposure - overlapping with complex-forming compound supply sheet →
Thermal development - Peel off - Immerse in a bleaching constant bath - Wash with water or soak in a stabilizing bath ■ Image exposure - Overlap with the complex-forming compound supply sheet - Heat development - Peel off - Immerse in a bleach bath - Immerse in a constant bath - Wash with water or Immerse in stabilizing bath ■ Image exposure - overlap with complex-forming compound supply sheet - heat development - peel off - overlap with bleach-fixing sheet →
In the above procedure, when a hydrophilic solvent such as water is used, the photothermographic material and/or the complex-forming compound supply sheet after imagewise exposure are moistened with the wood-philic solvent. Further, when a hydrophilic thermal solvent is used, the woodphilic thermal solvent is incorporated into the photothermographic material and/or the complex-forming compound supply sheet.

Furthermore, instead of using the complex-forming compound supply sheet in the above, the complex-forming compound may be dissolved in a hydrophilic solvent such as water, and the photothermographic material may be moistened with this solution.

D) When a color developing agent and a complex-forming compound are incorporated into a heat-developable photosensitive material.

■ Image exposure - Overlap with basic metal compound supply sheet 1 heat development 1 pull Peel 1 immersion in bleach-fix bath 1 wash or stabilizing bath ■ Image exposure - Overlap with basic metal compound supply sheet 1 heat development 1 pull Peel off - Immerse in a bleaching bath - Immerse in a constant washing or stabilization bath - Image exposure - overlap with basic metal compound supply sheet -> heat development - peel off - overlap with bleach-fix sheet - peel off In the above, When a hydrophilic solvent such as water is used, the photothermographic material and/or the basic metal compound supply sheet after imagewise exposure are moistened with the hydrophilic solvent. When a hydrophilic thermal solvent is used, the wood-philic thermal solvent is incorporated into the photothermographic material and/or the basic metal compound supply sheet.

In the above, instead of incorporating the complex-forming compound into the photothermographic material, the complex-forming compound may be dissolved in a hydrophilic solvent such as water, and the photothermographic material may be moistened with this solution. .

Examples of bleaching agents include iron (III) and cobalt (I).
Compounds of polyvalent metals such as II), chromium (■), copper (II), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (! ■) or organic complex salts of cobalt (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitriwatriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, or citric acid, tartaric acid, malic acid, etc. complex salts of organic acids; persulfates; manganates; nitrosophenols, etc. can be used.

Examples of the fixing agent include thiosulfate, thiocyanate, thioether compounds, thioureas, and a large amount of iodide, but thiosulfate is commonly used.

(2) Specific Effects of the Invention According to the present invention, a photothermographic material capable of recording information such as barcodes in addition to image information can be obtained. Information such as barcodes can be obtained by forming a dye image that absorbs in the infrared region.
It can be read using infrared light such as ED and is practical.

In this case, recording of images and recording of information such as barcodes may be performed simultaneously or separately.

(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 color photosensitive material having a multilayer structure as shown in Table 1 was prepared.

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

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 liters of water and keeping it warm at 75°C) contains an aqueous solution of sodium chloride and potassium bromide in a well-stirred gelatin aqueous solution of 600 liters of silver nitrate (water a o o mu
0.59'mol of silver nitrate dissolved in
Added at equal flow rate over 0 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

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

Next, the method for preparing the emulsion for the third layer will be described.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 mu of water and keeping it at 75°C) was mixed with 600 TQIQ, an aqueous solution containing sodium chloride and potassium bromide, and a silver nitrate aqueous solution (600 mu of water).
A solution prepared by dissolving 0.59 mol of silver nitrate in 100 ml of water) and the following dye solution (I) were simultaneously added at equal flow rates over 40 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 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene were added to perform chemical sensitization at 60°C. The yield of emulsion was 600 g.

Dye solution (1) Next, a method for preparing a silver halide emulsion for the fifth layer will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin and ammonia dissolved in 1000 mλ of water and kept at 50°C) contains an aqueous solution tooomU containing potassium iodide and potassium bromide, and an aqueous silver nitrate solution (silver nitrate in water tooomU). (1 mol dissolved) was added at the same time while keeping the pAg constant. In this way, a monodispersed silver iodobromide octahedral emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, 5 mg of chloroauric acid (tetrahydrate) and 2 mg of sodium thiosulfate were added to perform gold and sulfur sensitization at 60°C. The yield of emulsion was 1.0 kg.

This article describes how to make benzotriazole silver emulsion.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 m51 of water. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in water was added to this solution over a period of 2 minutes.

The p)I of this benzotriazole silver emulsion was prepared and precipitated to remove excess salt. Then the pH was adjusted to 6.3.
0, yielding 400 g of benzotriazole silver emulsion.

Next, we will discuss how to make a gelatin dispersion of couplers.

Weighed 10 g of a cyan coupler having the structure shown below, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and the required amount of triisononyl phosphate (listed in Table 1), ethyl acetate 3o
mU was added and dissolved by heating to about 60°C to form a homogeneous solution.

After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated at 10,000 g for 10 minutes using a homogenizer.
rpm to prepare a cyan coupler dispersion.

A magenta coupler dispersion and a yellow coupler dispersion were prepared in the same manner as above using a magenta coupler and a yellow coupler having the structures shown below, respectively.

(Cyan coupler) (Magenta coupler) (Yellow coupler) The photosensitive material thus produced is called sample 101.

On the other hand, when making the first layer of cyan coupler dispersion,
Sample 102 was prepared in the same manner as Sample 101 except that 3 g of compound (7) was added.

OCR characters were printed on these samples using a tungsten electrode. These samples were heated at 140°C for 30
Heated for seconds. Black OCR characters were obtained for both samples.

With the naked eye, the difference was hardly noticeable. This OCR character was read with an OCR reader (Sumitomo Electric PS-2001). In sample 101, there were 3 misreadings out of 10 times, but in sample 102, there were no misreadings out of 10 times. This confirmed the superiority of the present invention.

These samples were then immersed in the following bleach-fix solutions.

Bleach-fix solution〉 Water
400mλ ammonium thiosulfate 15
0 relatives (70% solution) Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (I summer) Ammonium 55g Ethylenediaminetetraacetic acid/2Na 5g Add water
After washing with 1000ml 100O6,70 water, these samples were dried.

Other than the white background becoming transparent, no major changes were observed in the letters with the naked eye.

The OCR characters were read in the same manner as above.

In sample 101, there were -5 misreadings out of 10 times, but in sample 102, there were no misreadings out of 10 times.

The increase in misreadings in sample 101 is thought to be due to silver having absorption in the infrared region being desilvered.

Example 2 In sample 101, the base precursor was changed to zinc hydroxide, and the first layer was coated at a rate of 200 mg/m', the second layer was coated at a rate of 200 mg/rn'', and the third layer was coated at a rate of 200 mg/rn''. It was added at a rate of 7omg/go.

Next, an active sheet RI O1 having the structure shown in Table 2 was made.

Table 2 Silicone oil 1 Surfactant *2 Aerosol OT Surfactant material 1 (n: approx. 4) 5 in polymer Vinyl alcohol-sodium acrylate copolymer (75/25 molar ratio) Polymer $7 Dextran (molecular weight 7 10,000) Mordant 1 Hardener 9 L O in matting agent Benzoguanamine resin (ratio of particles exceeding 10μ is 1
After baking OCR with tungsten light using Samples 101 and 102 (8 vou%), at room temperature (20 ~
(25°C) water for 3 seconds, squeezed out excess water, overlapped with active sheet R101, heated at 90°C for 15 seconds, and then peeled off active sheet R101.

For samples 101 and 102, black OCR characters with a slightly less cloudy white background than in Example 1 were obtained.

The sample was read using an OCR reader in the same manner as in Example 1.

In sample 101, there were 2 misreads out of 10,
In sample 102, there was no misreading out of 10 times.

As in Example 1, it was immersed in a bleach-fix solution to perform a desilvering operation.

This was similarly read using an OCR reader.

In sample 101, there were misreadings 4 out of 10 times,
In sample 102, there was no misreading out of 10 times.

Claims (1)

[Claims] (1) A heat-developable photosensitive material comprising, on a support, at least a photosensitive silver halide, a binder, and a dye-providing compound that forms a dye image having absorption in the infrared region.