JPS6188256A - Preservation of heat developing photosensitive material - Google Patents

Abstract

PURPOSE:To prevent a depression of a photographic performance and to obtain an excellent storage stability by preservating the titled material in the presence of a drying agent and/or an antioxidant. CONSTITUTION:The heat developing photosensitive material is preserved in the presence of the drying agent and//or the antioxidant. The above described drying agent may be a chemical drying agent and a physical drying agent and has <=10 W value and also preferably be a solid material in a service and comprises MgClO4, an active alumina and a silica gel etc. The above de scribed antioxidant is preferably an oxygen absorbent such as a sulfite, a metal or a metal salt etc. The drying agent and the antioxidant are separatly used so as not to directly contact with the titled material, thereby obtaining the prescribed effects. When both reagents are jointly used, a synergistic effect is obtd. and the deterioration of photographic performance is prevented caused by reservation, thus obtaining the excellent storage stability.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving a photothermographic material in which an image is formed by heating in a substantially water-free state. Prior art and its problems Heat-developable photosensitive materials usually contain a developing agent (reducing agent), and the components in the photosensitive material, including the developing agent, change due to the influence of moisture and oxygen during storage. Easy to cause increased fog and fluctuations in sensitivity and gradation. In addition, heat-developable photosensitive materials often contain a base or a base precursor in order to accelerate development by heating. In particular, from the viewpoint of storage stability, base precursors that release basic substances through thermal decomposition are preferably used. ing. However, in this case as well, part of the base precursor decomposes during storage and releases the base, resulting in fog.Moreover, the presence of moisture and oxygen greatly increases fog, and the sensitivity e gradation also decreases. Varies significantly. In order to solve these problems in heat-developable photosensitive materials, inorganic reducing agents such as sodium sulfite and sodium bisulfite, organic reducing agents such as benzenesulfenes, hydroxylamines, borane-amine complexes, and ascorbic acids have been used. It is possible to incorporate a reducing agent into the heat-developable photosensitive material. Furthermore, 3-pyrazolidones described in Japanese Patent Application No. 58-51655 can be contained.
A paper with a smooth surface as described in No. 14731 can also be interposed between the photothermographic materials. However, although these methods can provide some effects, they are not satisfactory for long-term storage, and an excellent storage method to solve this problem is desired. Furthermore, by storing heat-developable photosensitive materials at low temperatures, storage stability can be improved, but there is a drawback that handling is restricted, and a storage method that is easy to handle is desired. (2) Purpose of the Invention The purpose of the present invention is to provide a method for preserving a photothermographic material that prevents deterioration of photographic performance caused by storage and has excellent stability over time. ■Disclosure of the invention That is, the present invention provides a method for treating a heat-developable photosensitive material with a desiccant and/or
Alternatively, there is a method for preserving a photothermographic material, which is characterized in that it is preserved in the presence of an antioxidant. (2) Specific Structure of the Invention The specific structure of the present invention will be explained in detail below. As the desiccant used in the present invention, both known chemical desiccants and physical desiccants can be used. A solid desiccant is preferable for handling reasons. Typical desiccants are listed in the Chemical Encyclopedia, page 657 (Kyoritsu Shuppan 19).
1974 edition). A preferable desiccant has a W value (the number of mg of water remaining in one container of air dried by the desiccant) of 1O or less, more preferably 1 or less. Furthermore, any of neutral, acidic, and basic desiccants can be used, but neutral desiccants are preferred. Preferred drying agents include magnesium perchlorate, activated alumina, anhydrous calcium sulfate, silica gel, magnesium oxide, calcium oxide, calcium carbonate, anhydrous calcium chloride, anhydrous zinc chloride, and the like. In the present invention, the desiccant may have any particle size and shape, but preferably has a large surface area in order to increase the rate of moisture absorption. As the antioxidant used in the present invention, an S absorbent is effective. Oxygen absorbers include sulfite salts (eg, sodium sulfite, sodium bisulfite, magnesium sulfite, etc.), dithionites (eg, sodium dithionite, etc.), and sulfinic acid a! metals or metal salts (e.g. iron, zinc, nickel, ferric acid, etc.), ascorbic acid or its salts (e.g. sodium ascorbate, etc.), and other compounds with reducing power (hydroquinone, etc.). 3-pyrazolidones, hydrazines, hydrazides, borane-amine complexes, aminophenols, catechols, lignins, tannins, erythorubins, p-phenylenediamines, and droxytetronic acids, 4-amino -5-
pyranthrones, etc.). Also, T,)1.
“The theory of the
photo4raphic process “4th,
Reducing agents described in Ed., pp. 291-334 can also be used. The desiccant and/or antioxidant mentioned above (excluding the inert gas described below) are used in such a way that they do not come into direct contact with the photothermographic material. Another type of antioxidant used in the present invention is an inert gas. The inert gas mentioned here is one that does not cause oxidation of the components in the photothermographic material.
Preferred inert gases include gases such as helium, neon, argon, and krypton, nitrogen gas, and carbon dioxide gas. These inert gases are used by being sealed together with the photothermographic material 1 in a packaging material having excellent water vapor and oxygen barrier properties (by a so-called inert gas replacement method). Although the effect of the present invention can be achieved by using only one of the desiccant and the anti-impairment rL agent, it is preferable to use both in combination, as the effect will be greater. The heat-developable photosensitive material of the present invention has at least a photosensitive silver halide, a pineapple compound, and a ρχ agent on a support. Among them, in order to form a color image, a dye-donating substance that releases or forms a mobile dye upon heating is further included. In this case, the dye-donating substance may function as a reducing agent. Another embodiment of the heat-developable photosensitive material of the present invention is one having at least one photographic layer comprising a support and a photosensitive diazo compound, a paint compound, and a coupling component with the diazo compound. In the method using a heat-developable diazo copying material, the photosensitive layer contains a photosensitive diaso compound, a coupling component with the diazo compound, and a substance that generates LIAI upon heating, that is, a base precursor, and these are heated at a temperature of about 100 to 200°C. When heated, a coupling reaction occurs and an aso dye is formed. A method using heat-developable copying materials was developed in Japanese Patent Application Laid-Open No. 1986-
No. 11229, No. 52-109924, No. 57-45094. No. 55-133033, No. 52-150014. Special Publication No. 56-19620, No. 43-24726. No. 51-40455. It is described in No. 48-41202, No. 44-28863, etc. The amount of diazonium, the coupler compound with the diazo compound, the stabilizer, etc. used in the present invention are described in the above-mentioned patent publications. For example, as a diazonium salt, l-thiaso4-N
, N'-dimethylaminobenozene borofluoride 43
Engineering, l-diazo-4-morpholinobenzene fluoride salt, 4-diazo-diphenylamino borofluoride salt, l-diazo-2゜5-shedquin-4-morpholinobenzene borofluoride 11! etc. can be used arbitrarily. Coupler compounds include 4-methoxy-1-naphthol, 4-7minor-1-naphthol, 1,4-hydroxynaphthalene, 4-ethoxy-1-naphthol, resorcinol, phloroglinone, 2,3-dihydroxynaphthalene-6-sulfonic acid. Sodium, acetylacetamide, 2-hydroxynaphthalene-3-carboxylic acid ethanolamide, etc. can be used. Further, as stabilizers, acids for stabilizing diazonium salts, antioxidants, dye fasteners, etc. are used as appropriate. For unreleased Ij+, use a photosensitive material as necessary. Used with a dye-fixing element to fix the color patch. Especially in systems that form images by diffusion transfer of dyes, photosensitive j! A photosensitive element and a dye fixing element are essential, and one typical form is a form in which the photosensitive element and a dye fixing element are coated on two supports separately, and a form in which the light sensitive element and a dye fixing element are coated on the same support. It is broadly divided into Photosensitivity 1j! There are two types of forms in which the element and the dye-fixing element are formed on separate supports H; one is the ``A releasable type'' and the other is the non-releasable type. In the case of the peel-off type, after image exposure or heat development, align the coated surface of the photosensitive element with the coated surface of the dye fixing element, and after forming the transferred image, immediately remove the photosensitive element from the dye fixing element. do. M Depending on whether the final image is reflective or transmissive. The support of the dye fixing element can be selected from an opaque support or a transparent support. If necessary, a white reflective layer may be provided. In the latter type, which does not require peeling, the white reflective layer is interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. This white reflective layer is photosensitive.
It may be coated on either the dye fixing element or the dye fixing element.
The support of the dye fixing element needs to be a transparent support. Hereinafter, when one dye-fixing element is on a support separate from the photosensitive dye, it may be referred to as a dye-fixing material. A typical configuration in which four photosensitive elements and dye fixing elements are provided on the same support is a configuration in which there is no need to peel off the photosensitive element from the image receiving element after the transfer image is formed! It is b. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective layer/photosensitive layer. Another typical form in which a photosensitive element and a dye fixing element are coated on the same support is disclosed in JP-A-56-67840, for example.
．． Canadian Patent No. 674°082, U.S. Patent No. 3,73
As described in No. 0,718, there is a form in which part or all of the photosensitive element is peeled off from the dye-fixed 1p element, and a peeling layer is coated at an appropriate position. When the light-sensitive element and the dye-fixing element are on the same support, they will simply be referred to as light-sensitive materials in the following. The photosensitive element or dye-fixing element may be solid with an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye. In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and red, the light-sensitive element used in the present invention comprises at least three layers of halogenated material each sensitive to a different spectral region. It is necessary to have a silver emulsion layer. at least three molecules sensitive to different spectral regions
Typical combinations of two light-sensitive silver halide emulsion layers include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. A combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and an infrared light-sensitive emulsion layer, a blue-sensitive emulsion layer. Examples include a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer. Note that the infrared light-sensitive emulsion layer is 700n-
The above refers to an emulsion layer that is particularly sensitive to light of 740 nm or more. The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary. Each of the above emulsion layers and/or a non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer. Any of a dye-donating substance that releases or forms a yellow wood-based pigment, a dye-donating substance that releases or forms a magenta wood-based dye, and a dye-donating substance that releases or forms a cyan wood-based dye. It is necessary to contain one kind of each. In other words, each emulsion layer and/or the non-photosensitive woody colloid layer adjacent to each emulsion layer must contain a dye-donating substance that releases or forms woody dyes of different hues. .
If desired, two or more dye-donating substances of the same hue may be mixed and used. In particular, when the dye-donating substance is colored from the beginning, the dye-donating substance may be separated from the emulsion layer. It is advantageous to include it in the layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention can be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a marking agent layer, as required. . In particular, protective J# (PC) contains organic,
Usually, an inorganic matting agent is included. In addition, this protective layer may contain a mordant, a UV absorber, etc.
Each of the protective layer and the intermediate layer may be composed of two or more layers. In addition, the intermediate layer may contain a reducing agent to prevent color mixing, a UV absorber, and a white pigment such as TiO2.The white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity. Good too. Adding the above-mentioned color sensitivities to the silver halide emulsion +7. In order to achieve this, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity. The dye fixing element used in the present invention has at least one layer containing a mordant, and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. Furthermore, a dye transfer aid may be included above if necessary, or a water absorption layer or a layer containing a dye transfer aid may be provided in order to control the dye transfer aid. These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer. The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary. In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary. One or more of the two layers may contain a base and/or base precursor to promote dye transfer, an anticorrosion agent to prevent color mixing of hydrophilic heat-solvent dyes, a UV absorber,
A vinyl compound, optical brightener, etc. may be included in the dispersion to increase dimensional stability. The heid/dar in the bipedal layer is preferably hydrophilic, and a transparent or semi-transparent lignophilic colloid of I is representative. For example, gelatin, gelatin, polyvinyl alcohol, proteins such as cellulose derivatives, starch, natural substances such as polysaccharides such as gum arabic, dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone,
A water-soluble polyvinyl compound of an acrylamide polymer, a polymer material, etc. are used. Among these, gelatin and polyvinyl alcohol are particularly effective. Color These layers may be coated not only in the dye-fixing element but also in the light-sensitive ammonium, the reflective layer described above. The configurations of the neutralization layer and the neutralization timing layer are as described in, for example, U.S. Pat. Nos. 2.983,606 and 3.36
No. 2,819, No. 3,362,821, No. 3,415
, No. 644, Canadian Patent No. 928.559, etc. Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer. The silver halide that can be used in the photosensitive material of the present invention is 1! !
Any of silver oxide, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiobromide may be used. It may also have a multi-haired structure with different compositions on the surface and inside (Japanese Patent Application Laid-Open No. 1987-
No. 154232, No. 58-108533, No. 59-4
No. 8755, No. 59-52237, U.S. Patent No. 4,4
33.048 and European Patent No. 100,984),
In addition, the thickness of one particle is 0.5 gm or less, and the diameter is at least 0.
．． 6 gm, and the average aspect ratio is 5 or more.
No. 9 and OLS No. 3.241,64
6A, etc.) or monodispersed emulsions with a nearly uniform particle size distribution (JP-A-57-178235, JP-A No. 58-1008)
No. 46, No. 58-14829, International Publication 83/0
2338 A+, European Patent No. 64.412A3 and European Patent No. 83.377A, etc.) are also used in the present invention11)
Two or more types of silver halides with different grain size distributions may be used in combination, by mixing two or more monodisperse emulsions with different grain sizes. You can also adjust the gradation. The grain size of the silver halide used in the present invention is preferably one having an average grain size of 0.001 #Lm to 10pm, more preferably 0.001 gm to 5 gm.
These silver halide emulsions may be prepared by any of the acid method, neutral method, or ammonia method.
A back-mixing method in which particles are formed in an excess of silver ions, or a Chondrold double-jet method in which pAg is kept constant, may be employed, such as 1/V1, simultaneous mixing/i, or a combination thereof. Furthermore, in order to accelerate the growth of one grain, the concentration, amount, or amount of 1J1jU and halogen salt to be added may be increased (Japanese Patent Laid-Open No. 55
No. -142329, No. 55-158124. (U.S. Pat. No. 4,650,757, etc.). Epitaxially bonded silver halide grains can also be used (JP-A-56-16124, U.S. Patent No. 4.094,
No. 684). In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, silver chloroiodide, silver iodobromide, silver iodobromide, etc., which exhibit an X-ray pattern of silver iodide crystals, Preference is given to using silver chloroiodobromide. For example, silver bromide grains are prepared by adding a silver nitrate solution to a potassium bromide solution, and by further adding potassium iodide, silver iodobromide having the above characteristics is obtained. In the step of forming silver halide grains used in the present invention, ammonia is used as a silver halide solvent, and Japanese Patent Publication No. 47-1
The organic thioether derivatives described in No. 1386 or the 41-containing compounds described in JP-A-53-144319 can be used. In the process of particle formation or physical ripening. Cadmium salt, zinc salt, lead salt, thallium salt, etc. may be coexisting. Furthermore, for the purpose of improving high-light failure and low-light failure, iridium chloride (m, IT), hexachloro
□Water-soluble idium salts such as ammonium loiridate or water-soluble dium salts such as rhodium chloride can be used. The soluble salts may be removed from the silver halide emulsion after precipitation Form I& or after physical ripening, and thus the Tardel water washing method or the precipitation method can be applied. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, well-known sulfur sensitization methods, -prime 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 nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-Open No. 126526/1983).
No. 58-215644). The silver halide emulsion used in the present invention may be a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside one grain.
It is also possible to use a direct inversion emulsion, which is a combination of a t-emulsion and a nucleating agent. Internal latent image emulsions suitable for this purpose are U.S. Pat.
No. 6, Japanese Patent Publication No. 58-3534 and Japanese Patent Publication No. 57-13
It is described in No. 6641, etc. A preferred nucleating agent for combination in the present invention is U.S. Pat. No. 3,227,552. No. 4,245,037. No. 4,255,511. No. 4,266.013. It is described in 4,276.364 and 0L52,635,316. As a method for forming the halogenated 1M particles used in Unreleased 1!1, a known single jet method or double jet method can be used, and in the latter method, further,
It is also possible to use the so-called Chondral double jet method in which the PAg in the reaction solution is kept constant. Also,
In any of the above-mentioned silver halide emulsion forming methods, any addition method may be used, such as the well-known dashed line addition method or multistage addition method, and the addition rate may be a constant rate. or stepwise or continuous rate changes (for example, by keeping the concentration of soluble silver salt and/or halide constant while changing the addition flow rate of the solution; This can be achieved by changing the degree of soluble silver salt and/or halide in the additive solution while keeping it constant, or by a combination of these. Any stirring method may be used. Furthermore, the temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner. The photosensitive silver halide coating used in this invention ranges from 11 mg to 10 g/rn' of silver conversion. In the present invention, a metal salt relatively stable to light can be used in combination with the photosensitive silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt are in contact! It is necessary to be at a close distance. Among such organic metal salts, organic #i salts are particularly preferably used. When an organic metal salt is used in combination in this way, when the heat-developable photosensitive material is heated to a temperature of 80°C or higher, preferably 100°C or higher, the organic metal oxidant also undergoes redox using the silver halide latent image as a catalyst. It is thought that they are involved. Examples of organic compounds that can be used to form the above organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, compounds containing a mercapto group or a thiocarbonyl group having 1+ α-hydrogen, and compounds containing an imino group. can be mentioned. Silver salts of aliphatic carboxylic acids include behen-ugly, stearic acid, oleic acid, and lauric acid. IIi salts derived from capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furic acid, linoleic acid, lylinic acid, adipic acid, sebacic acid, succinic acid, acetic acid, acetic acid, or camphoric acid. This is a typical example. It is derived from an aliphatic carboxylic acid having a halogen atom or a hydroxyl group, a monosubstituted fatty acid, or a thioether group of these fatty acids. iakM can also be used. Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include benzoyojo, 35-dihydroxybenzoic acid, o-, m- or p-methylbenzoic acid, 2,
4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylben9oic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, saltylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl- A representative example is i-salt derived from 4-thiacillin-2-thione or the like. As the silver salt of a compound having a mercapto or thiocarbonyl group, 3-mercap)-4-2enyl-1.2
．． 4-) Riazole, 2-mercaptobenzimidazole, 2-mercapto-5-7 minothiadiazole, 2-
Mercaptobenzthiazole, S, -furkylthioglycolic acid (alkyl group having 12 to 22 carbon atoms), dithiocarboxylic compounds such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-
phenyl-4-thiopyridine, mercaptotriazine,
2-mercaptobenzoxasol, mercaptooxadiazole or 3-amino-5-pencylthio-1,
2,4-) Rear tools etc. U.S. Patent No. 4,123,27
The mercapto compound described in No. 4 and the like include i-boundaries derived from iA. As a silver salt of a compound having an imino group. Special Publication Showa 44-302701. r or. Penzotriazole B described in No. 45-18416 or its derivatives, such as henotriasol, methylhenttriazole, etc., alkyl 71-substituted 7-sotrianole, and halogen-substituted penzotrianole such as 5-chlorohentrianole. , butylcarpoimitobenzotrianol, nitrohentriazoles described in JP-A No. 58-118639, sulfobenzotriazole and carpoquinhensotriazole described in LV JP-A No. 58-118638. or a salt thereof, or hydroxyhentriazole, etc. 1.2.4- described in US Patent: iS4.220.709
) Representative examples include silver salts derived from lyazole, IH-tetratool, carbazole, and derivatives thereof. Also, Research Disclosure Magazine No. 170, 1702
9 (June 1978), proprietary metal salts other than silver salts such as silver salts and copper stearate, and patent application No. 58-2
Silver salts of carboxylic acids containing alkyl groups, such as phenylpropiolic acid described in No. 21535, can also be used in the present invention. The following organic silver salts can be used in combination in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive/\rogenated tii. Coating of photosensitive silver halide and organic silver salt - total 50 g to log/
rn' is appropriate. Next, the dye-donating substance will be explained. Examples of dye-donating substances that can be used in the present invention include couplers that can react with developing agents. This method of using a coupler, in which the oxidized form of the developer produced by the redox reaction between the silver salt and the developer reacts with the coupler to form a dye, has been described in numerous documents. Specific examples of developers and couplers include, for example, T.I. H. James, “Theth
eor2 of the photography
ic process”4th.Ed., 291-3
Pages 34 and 354-361, written by Makoto Kikuchi, “Photography tpa No. 41 Defeat (Kyoritsu Shuppan) 284-295
It is described in detail on the page. Furthermore, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of a dye-donating gooey substance. Specific examples of dye silver compounds are described in Research Disclosure Magazine, May 1978, pages 54-58, (RD-16966). In addition, athochromes used in the heat-developable silver dye bleaching method can also be cited as examples of dye-donating substances. Specific examples of Ara dyes and bleaching methods are given in U.S. Patent No. 4,235,957.
No., Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433). Also, U.S. Pat. No. 3,985,565. Leuco dyes described in 4,022,617 and the like can also be cited as examples of dye-donating substances. Another example of the dye-donating gooey substance is a compound that has the ability to release or diffuse a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (LI). (Dye-X)n-Y (LI) Dye represents a color Inverse correspondence (Dye-X)n
-Creating a difference in the diffusivity of the compound represented by Y,
Alternatively, Dye is released and the released Dye and (Dye
-X) represents a group that has the property of causing a difference in diffusivity between n and Y, where n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. It's okay. A specific example of the dye-donating substance represented by the general formula (Ll) is, for example, a dye developer in which a hydroquinone developer and a dye component are linked. As described in U.S. Patent No. 3,134,764, U.S. Patent No. 3.362,819, U.S. Patent No. 3.597.200, U.S. Pat. There is. In addition, a substance that releases a diffusible dye by an intramolecular nucleophilic substitution reaction was disclosed in Japanese Patent Application Laid-Open No. 51-63
No. 618, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of an inoxasorono ring is disclosed in JP-A-49-1999.
No. 111,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred. In addition, in these methods, since development and dye release or diffusion occur in parallel, it is very difficult to obtain an image with a high S/N ratio.Therefore, in order to improve this drawback, one dye-releasing method was developed in advance. The compound is made into an oxidized form with no dye release motility, and is combined with a reducing agent or its precursor, and after development,
A method has also been devised in which the reducing agent that remains without acetylation is used to reduce the material and release the diffusible dye, and here are some specific examples of dye-smearing substances that can be used in this method. Japanese Patent Publication No. 53-110,827. No. 54-130,927, No. 56-164.342. It is described in No. 53-35.533. On the other hand, as a substance that releases a diffusible dye in the area where development has occurred, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and a developer solution is disclosed in the British Patent No. 1.330.524, Japanese Patent Publication No. 48-39,165, U.S. Pat.
'Substances that generate diffusible dyes by reaction with infused forms of drugs are described in US Pat. No. 3,227,550 and the like. In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised. Representative examples are shown below along with literature. - Definitions in the general formula are described in each document. U.S. Patent No. 3,928,312, etc. U.S. Patent No. 4,053,312, etc. U.S. Patent No. 4,055,428, etc. U.S. Patent No. 4,336,322, etc. -69839Ba1last JP 53-3819 JP 51-104,343 JP 51-104,343 Ballist JP 51-104,343 Research Disclosure, d 17465 U.S. Patent No. 3 , 725,062 U.S. Pat. No. 3,728,113 Ballist Any of the various dye-providing substances mentioned above in U.S. Pat. No. 3,443,939 can be used in the present invention. The dye-donating substance that can serve as a reducing agent for releasing a mobile dye used in the present invention is preferably represented by the following general formula (Lll
): R-502-D (LII). 1- In the description (L II ), R is cleaved correspondingly or inversely to the photosensitive silver halide having a latent image in image form to release a dye, and the dye thus released and a dye-donating substance Represents a reducing substrate that has the property of causing a difference in mobility between. D is a mobile image-forming dye (including its precursor)
may also include a bypass group connecting the "pure" dye moiety and the SO2 group. The reducing substrate (R) in the dye-donating substance R-502-D has a saponification reduction potential of 1 with respect to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte. .2V or less is preferable. As a specific example of the reducing substrate represented by R,
Various groups described in 17J:Lm page 37 of Publication No. 7-194202 can be mentioned, and among them, a group represented by the following general formula (Lm) is preferable. (LIll) where l(I, l(2, l(3 and R4 are each a woody atom, an alkyl group, a cycloalkyl group, an aryl group,
Alkoxy group, aryloxy group. Aralkyl group, acyl group, acylamino group, alkylsulfonylamino group [arylsulfonylami7 group, aryloxyalkyl group, alkoxyalkyl group, N-Zj
Substituted carbamoyl group N-2! i-substituted sulfamoyl group, halogen atom. It represents a group selected from an alkylthio group and an arylthio group, and the alkyl group and aryl group moiety in these groups can further include an alkoxy, a halogen atom, a hydroxyl group, a cyano group, an anru group, an anruamino group, a substituted carbamoyl group,
2! It may be substituted with an I-substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group or a carbalkoxy group, and the hydroxyl group and amino group in R can be protected by regeneration by the action of a nucleophilic reagent. It may be protected with a group. In a more preferred embodiment, the reducing substrate R has the following formula (
LrV). (LIT) Here, G represents a hydroxyl group or a group that can be converted into a hydroxyl group by hydrolysis, and R10 represents an alkyl group or an aromatic group. Is XIO electronically stable when n=1? When one substituent is used and n=2 or 3, the substituents may be the same or different, and when one of them is an electron-donating group, the second or third one is an electron-donating group or Even if it is a halogen atom and XIO itself forms a condensed ring, Q R1
0 may form a ring, and the total number of carbon atoms of both l(1 and X In is 8 or more. Among those included in formula (LIT), in a more preferred embodiment, R is the following formula (LrV a) OyoC1 (LrV b) Te table t) Sale 6゜ (LrVa) Here, G is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis, R11 and l (+2 are the same or different) each may be an alkyl group, or R
11 and )l 12 may be connected to form a ring, R
represents a hydrogen atom or an alkyl group; l (10 represents an alkyl group or an aromatic group; or represents an alkylthio group, and further R+o and is an alkyl or aromatic group; X2 represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group;
and R10 may be connected to form a ring. (LIV), (LrVa) t-IJ:bi (LIV
b) Specific examples included in: They are described in US Pat. In another more preferred embodiment, the reducing substrate (R)
is expressed by the following formula (LV). (LV) (where the symbols G, XlTl, 1 (10 and n
teeth. It has the same meaning as G, XIO, )In10 in formula (LrV). ) Of those included in (LV), 117 more desirable j
For l+ 4J, the reducibility 2 & quality (IR) is calculated by the following formula %
Formula % where G is a hydroxyl group or a group capable of removing a hydroxyl group by hydrolysis; R21 and R22 may be the same or different,
Each represents a furkyl group or an aromatic group; R21 and R22 may be combined to form a ring; R represents a water atom, an aromatic group, or an aromatic group; R24 is an alkyl group or represents an aromatic group; R represents an alkyl group, an alkokene group, an alkylthio group, an arylthio group, a halogen atom, or an annulamino group; p is 0.1 or 2; R24 and R are bonded to form a fused ring Even if it forms (,
R21 and R24 may combine to form a condensed ring.
; f121 and R may combine to form a condensed ring, and the total number of carbon atoms of H21゜1(22, RZl, 1li24 and R, is greater than 7. (LV b) However, G is a hydroxyl group , or a group that gives a hydroxyl group by hydrolysis; 1 (31 represents an alkyl group or an aromatic group; R32
represents an alkyl group or an aromatic group; R represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or a 7-nylamino group. q is 0.1 or 2; R) and R may be combined to form a condensed ring, and 1(3
1 and R12 may combine to form a condensed ring (,1(3
1 and R may be combined to form a condensed ring; and
1 (total bed of 31, R32, Rq; the number is greater than 7. (LV c) In the formula, G represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis; 11i41 represents an alkyl group or an aromatic group. Representation R4
2 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom, or an anluamino group; or its precursor) mother nucleus - a carbon atom in the condensed ring that participates in this bond (---, C-) is a tertiary carbon atom constituting one of the key points of the condensed ring, and some of the carbon atoms in the hydrocarbon ring (excluding the tertiary degree 1 atoms mentioned above) are substituted with oxygen atoms. Alternatively, the hydrocarbons may have a substituent, or the aromatic ring may be fused -111, -'. Next, some preferred specific examples will be shown. (R-1) (R-2) (R-3) (R-4) (R-5) (R-6) (R-7) (R-8) (R-9) (R-10) (R-11) (R-12) In addition, the dye moiety represented by D includes azo dye, asomethine dye, anthraquinone dye, naphthoquinone dye,
The color emitted from the dye-donating compound is derived from styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalonani/dyes, etc., and this dye moiety may be temporarily shortened in wavelength. For a specific example of # part, see the above-mentioned patent application No. 57-1942029.
Examples include those described on page 59 of WS37 jt. As a specific example of the dye-donating substance that can be used in the present invention, the above-mentioned patent application No. El/157-194202 includes: JS6
List the compounds described on pages G to 91! 1°C, especially the compounds (1) to (3) described in the above page range.
, (10)-(13). (16] ~ (19), (28) ~ (30). (33), (35), (38) ~
(40). (42) to (64) are preferred. In addition, the following cyan and yellow dye-donating substances are also suitable for A1. The dye-donating substance can be used within a certain concentration range. Generally useful concentration ranges are: Approximately 0.01 dye donating substance per mole of silver halide
That's 4 moles. A particularly useful concentration in the present invention is about 0.03 per mole of silver halide.
It's 1 mole. Various types of Kabuchi are known that can combine with an oxidized form of a developer to release a dye. For example, T, )1. By James, 'Ding he th
I! ory of the photography
process”4thE4..354-361 pages; Makoto Kikuchi, “Photochemistry” 4th edition (Kyoritsu Shuppan) 2
Any of the couplers described on pages 84 to 295 can be used in the present invention. The present invention includes a 4-valent coupler whose bonding site with the oxidized form of a developer is a hydrogen atom, and a 2-valent coupler substituted with a degI group.
Both equivalent couplers are available. Further, the coupler has both a hydrophilic group and a hydrophobic diffusion-resistant group. So-called Agfa dispersion couplers and oil-protected dispersion couplers containing only hydrophobic diffusion-resistant groups can also be used. Among the couplers having a diffusion-resistant group, there are couplers having a hydrophobic parast group in the leaving group as described in 4￥Kokai No. 58-149,046, etc.; JP-A-58-149;
Coupler in which a leaving group is frequently linked to a polymer as described in U.S. Patent No. 3,370,952, 3.45, etc.
1.1120, 4,080,211;, 4,215
, No. 195, No. 4,409,320 and the like. Also, British Patent No. 1,330,524. Special Publication No. 48-39,165, JP-A-57-186.7
No. 44, No. 57-207, 250, No. 58-79, 247
Colored couplers containing a dye component in the leaving group described in No. 1, etc. are also useful in the present invention. Couplers preferably used in the present invention are active methylene and active methino compounds, phenols, naphthols, pyrazoles and condensed pyrazole compounds, and particularly preferred ones are represented by the following general formula. In the general formula 1-Ashiguchi, R, , R2, R3 and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an alkyl group, or an aralkyl group. Alkenyl group, aryl group, alkokene group, aryloxy group, acyl group, anruamino group. Alkoxyalkyl group, aryloxyalkyl group, carbamoyl group, substituted carbamoyl group. Sulfamoyl J, E, substituted sulfamoyl group, alkylamino group, arylamino 7 group, anruokine group,
acyloquine alkyl group, substituted ureido group, n-ano group,
Represents a substituent selected from multiple X-ring residues, and these substituents further include an alkyl group, an alkoxy group, a halogen group, a hydroxyl group, a carboxyl group, a sulfo group, an a/group, a nitro group, Calhemoyl group, substituted car/hemoyl group, sulfamoyl group, substituted sulfamoyl group, anruamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, aryluoquine group, aralkyl group or acyl group;! 1 may be exchanged. X is a water leak atom, halogen D (, Ashiluokinno,
A substituent selected from a sulfonyloquine group, an alkoxy group, an aryloquino group, an alkylthio group, an arylthio group, an alkoxycarbonyloxy group, a dialkylcarbamoyloxy group, an imide group, an N-multiple J ring residue, and a pyridinium group. Also, R,, R2, R3. It may be linked to the polymer main chain from either R4 or X. In Unfinished No. 191, it is preferable that the photosensitive material contains P1 substance (1).Reducing substances include those generally known as reducing agents, as well as dye-donating substances having the above-mentioned reducing properties. In addition, although it does not have reducing properties itself, it exhibits one-dimensionality by the action of nucleophilic reagents and heat after developing f1''; it also includes the base agent precursor. An example of a χ agent used in k civilization is % quinary agents such as sodium sulfite and sodium hydrogen sulfate, henzhen/sulfinic acids, hydroxyl amino acids, hydrazides, hydrazides, 10-amino complexes, amines, phenols, catechol Examples include p-phenylene/aminos, 3-pyranrinnones, hydroquinotetronic acid, ascorhinic acid, 4-amino-5-pyranolones, etc. Ding H, James7.."Theoryofth
ephotographic process14t
The pentanants described in Ed., 291-334 Peno can also be used. Also, JP-A IIIJ 56-138, No. 736. Reducing agent precursors such as those described in US Pat. No. 57-40.245, US Pat. Examples of more preferable reducing agents include those listed below. 3-Bilanlide 7 and its precursor [for example!
-phenyl-3-virasolitono, l-phenyl-4,4
-Tmethyl-3-vilanridone 4-Hydroquinemethyl-4-methyl-1-phenyl-3-vilanridone, 1-
m-) true 3-bilanridone t-p-tolyl-3-
Pyranolidone l-phenyl-4-methyl-3-bilanlide/, l-phenyl-5-methyl-3-bilanlide, ■-phenyl-4゜4-his-(hydroquinomethyl)
-3-pyrasolidore, 1.4-cymethyl-3-vilanridone, 4-methyl-3-vilanridone 4.4=dimethyl-3-vilanridone (.), 1-(3-chlorophenyl)-4-methyl-3-vilanridone , 1-(4-chlorophenyl)-4-noty1L-3-pyranlide 7.1-(
4-tolyl)-4-methyl-3-birasoliton, ■-(
2-methyl)-4-methyl-3-virazolidore, 1-
(4-trill) -3-biraso
trill, 1-(3-trill)
-3-Biranlit / , l
-(3-tolyl)-44-dimethyl-3-biratuno
Lito 7.1-(2-tri) Le o lo etil)-4, 4-;'me-mi-ru-3-biranlid/5-me-ma-ru-3-pyranlidone 1,5-nophenyl-3-pyranolidone, ■-Phenyl-4-methyl-4-stearoyl-oquinemethyl-3-birasoliton, 1-phenyl-4-methyl-4-lauroyl-oquinemethyl-3-vilanridone, l-phenyl-4,4-bis-(lauroylleoquinemethyl )-3-Biratsuritono,
■-2enyl-2-acetyl-3-virasoliton, 1-
Phenyl-3-7setki/pyran 1 nod7), /X itoquinono and its precursors [e.g. \ itoquinone, tolu / \ itoquinone, 2゜6-dimethylhytroquinono, t-butyl / \ itoquinono 2.5- No 1-butyl/\itoquinono, -octylhydroquinone, 2゜5-no, one-octylhydroquinone, penotadenolhydroquinone/), 5-penotadenol\iteσ
Sodium quin/en-2-sulfonoate, p~ha/soyloquinophenol 2-methyl-4-he/soyloquinophenol, 2-t-butyl-4-(4-chloro-7tsoyloquino)phenol] In the present invention, the U.S. Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869. (In the present invention, the amount of the reducing agent added is 0.01 to 20 mol, particularly preferably 0.1 to 1 mol, per 1 mol of silver.) The binder used in the present invention may be used alone or in combination. (The binder of the invention may be either a hydrophilic polymer or a hydrophobic polymer.) Sexual colloids are typical, such as gelatin, 1. Serratia, A4, cellulose conductors, etc., 2.PIT, and natural substances such as polysaccharides such as starch and aradoa gum, and polyhinylpyrrolito/ Other synthetic compounds, including water-soluble polyhydric compounds such as acrylamide and other synthetic compounds, particularly in the form of latex, increase the dimensional stability of true materials. (An image formation accelerator can be used in the heat-developable light-sensitive material or dye fixing material in the invention. The image formation accelerator includes oxidation of a silver salt acetylating agent and a reducing agent; Acceleration of the original reaction 1 Acceleration of the reaction 11 of the dye from the dye-donating substance or decomposition of the dye or release of mobile dye It has functions such as promotion, and from a physicochemical function, it is 1!4
It is classified into group or base precursors, nucleophilic compounds, oils, heat solvents, surfactants, and compounds that have a phase 11 action with silver or silver ions. However, these substance groups generally have multiple functions, and θ has some of the promoting effects listed in 1- above. Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound has multiple functions. There are many things. Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates +Q acids 1!!, Ki, Norin Examples of Jill's salts include aliphatic aconates (
trialkylamines, hydroxylaminos, li1
7 aromatic amines (N-acyl-substituted aromatic amide 7, N-hydroxylalkyl-substituted aromatic amide 7, and his(p-(noalkylamino)phenyl) methano), Kf J t = shaped amines, amidinos, cyclic amidines, guaninones, and cyclic guanidinos, with pKa of 8 or more being particularly preferred. Compounds that decompose by charcoalization (salts of organic acids and bases, intramolecular nucleophilic substitution reactions, Rossen rearrangement, Cuman rearrangement, etc.) and release amines, and some other compounds that undergo some kind of reaction when heated. Preferably used are those that release m) and ( when raised. 11! Preferred IQ precursors include trichloroacetic acid salts described in British Patent No. 998.949 and the like. Described in Ueda Patent No. 4,060,420. α-sulfonyl M-ugly salt of , salt of propiolic acids described in Japanese Patent Application No. 58-55,700. (+ In addition to machine j8J, salts with thermally decomposable acids using alkali metals and alkaline earth metals (Patent application 1986-69.597!;), Patent application 1986-43 using Rossen rearrangement Q Examples include hydroxa t and carbamates described in Japanese Patent Application No. 1986-31-614, which produce nitriles by heating. I11 Patent No. 3.z2o, s46"-. Japanese Patent Application Laid-Open No. 50-22.625-.
1A precursors are also useful. The 1!1 precursor glue body, which is particularly useful in the present invention, is shown below. F guanine acetate, trichloroacetic acid M methylguanidine, trichloro MM potassium. Phenylsulfonyl acetic acid resistant guanine, p-chlorophenylsulfonylbutyrate guanidine, p-metalesulfonylphenylsulfonyl Ml? 1 Guaninone Potassium phenylpropiolate, Cesium phenylpropiolate,
Phenylpropiolic acid guanidine, p-chlorophenylpropiolic acid guanidine, 2,4-dichlorophenylpropiolic acid guanidine, p-phenyle7-hisobropiol diguanidine, phenylsulfonylacetate tetramethylammonium, phenylpropiolic acid tetramethylammonium. (. -4p Compound 1 &f Examples of desirable nucleophilic compounds are listed below. 1 Water and water-releasing compounds (ammonium alum,
Iron alum, etc.) 2 amines (octylamine, todenylamine, ophtadenolamine, chlorhequinylamine, aniso/P)
-toluidine, p-anidino, 2,4-ki-norizine, etc.) 3 amidines (acetamidine, p/guanidino, N-
4 guanines 7 (guanidino, methylguanine, N,
N-dimethylguanine, 2-aminoinigrin, 2
-7minotetrahydrovirimidino, 2-ami/benosimignol, etc.) 5-Hytroquinylamine 7 (hytroxolamine, N-methylhytroquinylamine, 0-methylhytroquinylamine, etc.) 6. Hydrazines (methylhydrazine, N, N-7 methyl hydrazine, phenyl hydrazine 7, etc.) 7 hydranotos (acetohydrazide, henz hydrazide, isonicotinic acid hydrazine, p-toluenesulfonylhydrazine, etc.) 8 Oquines (ace) + Sim2 to/zaltoquinome Salicyl altoquinome etc.) 9゛Hydroxamic acids (acetohydroxam resistance, henzenosulfonamide resistance, p-)luenesulfohytoloxam m, etc.) 1 (lj sulfonamides (henzenosulfonamide)
p-Chlorobenzenesulfonamide, 7zenesulfonamide ktF) sulfamide, N
, N-methylsulfamito, N,N-7propylsulfamito, etc.) 11 active methylene compounds (malononitrile, acetoacetanilide, 1-phenyl-3-methyl-5-pyrazolo/
etc.) Alcohols (dodecanol, glycerin, p-taerythritol, p-quinrylene glycol, etc.) 1τ thiols (hexadecanethiol, todenol, etc.)
(Senothiol, etc.) Furthermore, compounds or precursors of the compounds listed above can also be used. (In civilization, the compounds described in JP-A-57-194.202 and JP-A-59-680.521 are particularly useful.) Phthalic acid alkyl ester (mptylphtha L--)
, octyl phthalate, etc.), phosphorus-ugly esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl citric acid tributyl), benzoic acid esters (anboyojo octyl),
Alkylamides (e.g. diethyl laurylamide) io
lt costalic acid esters (e.g. dibutquin ethylsacn 2)
esters, dioctyl azelate) trimene heptacid esters (for example, trimene tributyl), and the like. -L and "-C" L week f Ureas (urea, N-methylurea, N, N-dimethylurea, N-2-butyl urea, etc.) 1 Urethanes (N-phenyl urethane, N-diphenyl (urethane, etc.) j) Amides (N-methylformanilide, acetamide, benozamide, N,N-dimethyl-\nozamide, etc.) 4Pyridine! 1 (2-hydroquinpyridine, 4-hydroxypyridine, 4-hydroxymethylpyridine 7)'9) 5 sulfo/amides (in addition to the compounds listed below, N. N-diethyl-P-) luenesulfonamide, N-ethylbenzenesulfonamide F, etc.) 6 sulfones, sulfoxides (phenylmethylsulfo/, diphenylsulfone,
diphenylsulfokimeto, etc.) 7 esters (dimethyl terephthalate, glycerinotribennoate, be/taerythritol tetrabenzoate, etc.) 3 ketonos (hensopheno/, notrilkato7, noanisylketono'V-) 9 ethers (hydroquinone Dimethyl ether β-
naphthyl methyl ether kIr)fl+1

[°Pyrinnium salts (compounds described in Japanese Patent Application No. 184.298r'f of 1984)"
tr) 2゛Ammonium JulAC triethylhenodylammonium chloride, trimethyltodecyl ammonium t-bromide, etc.) 3゛Phosphonium salts (triphenylphosphonium bromide, tributylbenzylphosphonium chloride, etc.) 4. Polyalkylene oxides (patent application) 57-168,186) l-imides (phthalimide, succinimide, hydantoin, phthalazinone, etc.) 2-nitrogen-containing heterocycles (compounds T described in Japanese Patent Application No. 58-51,657) ) ・3″ thiols (compounds described in Japanese Patent Application No. 57-222.247, etc.) 4. Thiocarboxylic compounds (tetramethylthiourea, N-dimethylethylenethiourea, etc.) 5″ thioethers (N-( (β-hydroxyethyl) sulfite, β-hydroxyethylbenzyl sulfite, etc.) The image formation accelerator is incorporated into either the photosensitive material or the dye fixing material that fixes the dynamic dye formed in the image form in the photosensitive material. It may be built into both.
The incorporated layer may also be incorporated in the emulsion layer, intermediate layer, protective layer, dye fixing layer, or any layer adjacent thereto.The same applies to forms in which the photosensitive layer and the dye fixing layer are on the same support. It is. The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination. Especially when combined with bases or base precursors and other promoters! A remarkable promoting effect on GL is expressed. Imaging promoters can be used in a wide variety of ways. For example, bases or base precursors can be used to modify coatings of light-sensitive materials (or dye-fixing materials). 0.01 to 11
50 modified 1% range, nucleophilic compound 0.1-20 tonpu%
, oil and heat solvent 0.1 to 75%, surfactant 1 to 50 IT+,' :+! %
Hereinafter, the amount of the compound having phase 1j action with silver or silver ions is preferably in the range of 10-'' to 1 mol per mol of silver.
In the case of compounds that have a phase q action with silver or silver ions,
Since both a promoting effect and a suppressing effect may appear depending on the amount added, it is desirable to appropriately adjust the amount added depending on one compound. In the present invention, various development stoppers can be used in the light-sensitive material and dye-fixing material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development. The development stop agent mentioned here is a compound that immediately neutralizes the base or reacts with the base to lower the base concentration in the film and stop the development after proper development, or a compound that interacts with silver or silver salt to develop. It is a compound that inhibits Specific examples include acid precursors that release acid when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, mercapto compounds, and nitrogen-containing double ring compounds. For acid precursors, for example, Japanese Patent Application No. 58-216.9
28- and oxime esters described in No. 59-48,305, and Ronsen rearrangement as described in Japanese Patent Application No. 59-85.834. Examples include compounds that release acids, and examples of electrophilic compounds that undergo a substitution reaction with bases when heated are described in Japanese Patent Application No. 59-85.
, No. 836, and the like. It is preferable that the development stopper F agent described below is used together with a base precursor. In that case, the value of the base precursor/acid precursor ratio (mole ratio) is preferably 1/20 to 20/1, more preferably 115 to 5771. . In the present invention, various antifogging IE agents can be used. As anti-fog 11 and two agents. Nitrogen-containing carboxylic acids and phosphoric acids described in Japanese Patent Application No. 58-43862, or Japanese Patent Application No. 57-222247
The mercapto compounds and metal salts thereof described in the above are used. These antifoggants contain o, o for 51 mol.
It is used in a concentration range of ot to 10 molar. The silver halide emulsion used in the present invention may be spectrally sensitized with methine dyes or other dyes. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex meroflurofluoride dyes, and holopolar cyanine dyes. , ha-micyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful pigments are cyanino, merocyanine, and complex merocyanine pigments. These pigments contain Nani7 as a basic heterocyclic nucleus.
Any of the nuclei commonly used for color charts can be applied.
That is, pyrrolino nucleus, oxanephosphorus nucleus, cyanophosphorus nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, and selenazole nucleus. Imitazole nucleus, tetrasol nucleus, pyridine mallet, etc.; nucleus in which aliphatic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, hengui/drenin nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, henzothiazole nucleus, naphthothianol nucleus, henzoselenanol nucleus,
Henzimidazole core, quinoline core, etc. can be applied. These nuclei may be substituted on carbon atoms. The complex melonanine pigment also contains pyranolin-5-one nucleus, thiohida-7toine nucleus, 2-thioxazolidine-2 as a nucleus with ketomethylene bridges.
, 4-dio/nuclear, 7-2,4-dionucleus, 5-6 negative heterocyclic nuclei such as rhodanine nucleus, thiobarbic acid nucleus, etc. can be applied. Useful sensitizing dyes include, for example, German Patent No. 929.080; +F Permit No. 2,231.658, No. 2,493,748. Same No. 2.503.776, Same No. 2
．． No. 519.001, No. 2,912.3
No. 29. Same No. 3,656,959. Same No. 3,672,897, times: jS 3, 69 4, 2
1 No. 7. Same No. 4,025. No. 349, No. 4,046,572, British Patent No. 1.242.58
No. 8, Special Publication No. 44-14030. Examples include those described in No. 52-24844. Specific examples of useful sensitizing dyes include the following compounds. Specific examples of sensitizing dyes such as E group include the following compounds. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization. A typical example is: U.S. Patent No. 2.688.545, No. 2. 977. No. 229, same.
No. 3,397,060. 3,522,052, 3,527, 641. Same No. 3,617,293. Same No. 3.828.964. Same No. 3,688,480. Same No. 3,672,898, Same No. 3,679,428. Same 3rd. 703. No. 377. Same No. 3,769,301. i3.814,609, i3.814,609, i3.814,609,
No. 837,862, No. 4,026,707, British Patent No. 1,344,281, No. x, 5o7. ao3s;. Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12,375, and Japanese Patent Publication No. 110,618/1982. It is described in No. 52-109,925. Along with the sensitizing dye, the emulsion may also contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits monochromatic sensitization. For example, a nitrogen-containing dye Aminostyl compounds substituted with partial ring groups (e.g., U.S. Pat. No. 2,933,39
No. 0, US Pat. No. 3,635,721), aromatic organic acid formaldehyde condensates (for example, US Pat.
743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent Nos. 3,615,613 and 3,615,641. Same No. 3,617,295. The combination of 11 described in No. i3,635,721 is particularly useful. In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be mixed with water, methanol, ethanol, 7 setone,
They may be dissolved in a single or mixed solvent such as methyl cellosolve and added to the emulsion, or they may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol and then dispersed in water or parent wood colloid. . This dispersion may be added to the emulsion, or the sensitizing dye may be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. In addition, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved.Also, when added to an emulsion, They may be added at the same time as a mixture, they may be added separately, or they may be added at the same time as other additives.They may be added to the emulsion during or before chemical ripening, or It may be carried out before or after nucleation of silver halide grains according to Japanese Patent Nos. 4,183,756 and 4,225,666. The amount added is generally about 10-6 to 10-' mol per mol of silver halide. The hydrophobic compound such as the dye-donating substance used in the present invention can be introduced into the photosensitive material 1 by various known dispersion methods.
Typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling organic solvents are described in US Patent: JS 2.322.027. Dispersion may be accompanied by transfer, and depending on the packaging, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use in li+. Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate) , tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dotecylbenzoate, 2-ethylhexyl-p-hydroxy) benzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctylase, etc.) rate, glycerol tributyrate, instearyl lactate,
trioctyl citrate, etc.), aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene 5-diisopropylylnaphthalene, etc.),
In addition, as an auxiliary solvent, the boiling point is about 30°C to about 160°C.
C. organic solvents can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. Examples of latex dispersion process steps, effects, and latex for impregnation can be found in U.S. Pat. No. FF 14,199,383. OLS No. 2,541,274, and OLS
No. 2,541,230, etc. Photographic additives that are poorly soluble in wood are dissolved in a suitable high-boiling organic solvent and dispersed in a solution of hydrophilic organic colloids, especially gelatin, in the presence of a surfactant (usually an anionic surfactant). , a wood-philic organic colloid layer (for example, a photosensitive emulsion layer, a filter layer, a hack layer, an intermediate layer of the antihalation layer 5, a protective layer, etc.). For example, the following methods of emulsifying and dispersing oil-soluble photographic additives are known. Namely. U.S. Patent No. 2,739,888. Same No. 3.352.681. Same No. 2,360,290, Same: JS 2. 728. No. 659, same
No. 3.700.453. It is described in JP-A-51-129,229 and the like. According to one embodiment of the invention, a high-boiling organic solvent (e.g., dibutyl phthalate) with a boiling point of about 175°C or higher, or a low-boiling organic solvent (such as dibutyl phthalate) with a boiling point of about 30°C to about 150"C
After dissolving the photographic additive (e.g. coupler) in a solvent (e.g. acid-resistant ethyl) or a mixed solvent of both, it is mixed with a solution of a wood-philic colloid (e.g. gelatin) containing a surfactant, and then a high-speed rotary mixer or colloid Emulsify and disperse with an emulsifying machine such as a mill, and add this to photographic coating 1 (liquid J) containing wood-philic colloids. Alternatively, remove low-boiling organic solvents by degassing under reduced pressure. The emulsified dispersion may be cooled, set, shredded, and the low-boiling organic solvent removed by washing with water, etc., and then added to the photographic coating solution containing the wood-philic colloid. The light-sensitive material of the present invention can be produced by applying the prepared photographic coating solution to support E. The support used for the material in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. No. 3,634,089, U.S. Pat. No. 3,725.0.
The polyester described in No. 70 is preferably used. In the present invention, the photographic emulsion layer or other wood-loving colloid layer of the light-sensitive material contains coating aids, antistatic agents, slippery improving agents,
Various surfactants may be included for various purposes such as emulsification dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, contrast enhancement, and sensitization). For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: alkyl carpone ugly salt, alkyl sulfonate,
Alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-furkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxene Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups such as ethylene alkyl phosphates; amino acids 4 aminoalkyl sulfonic acids, aminoalkyl sulfates or Amphoteric surfactants such as phosphorus-resistant esters, alkyl betaines, and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts. Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyrinidium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. ” Among the two types of surfactants, patent application No. 57-168186
It is preferable that the photosensitive material contains a polyethylene glycol type nonionic surfactant having ethylene oxide repeating units in the molecule as described in the above-mentioned No. 1, particularly preferably those having 5 or more ethylene oxide repeating units. is desirable. The light-sensitive material of the present invention can contain a cationic compound having a pyridinium salt. Examples of cationic compounds with pyridinium groups include PSA Journal, SL! ction
8 3G (1!+53), US IN patent wS2,
64B, 604Q. It is described in U.S. Patent No. 3,671,247, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 44-9503, Japanese Patent Application Laid-Open No. 59-74547, etc. In the present invention, Japanese Patent Application No. 58-5165715)
Nitrogen-containing heterocyclic compounds described in US Pat. No. 8-189628, US Pat. No. 58-193541, US Pat. No. 4,137,079, US Pat. By containing an appropriate amount of the heterocyclic compound, fogging is suppressed and development is promoted, which is advantageous. It is also preferable to contain mercaptans and thiophenols described in Japanese Patent Application No. 57-222247. In the present invention, in/knee/ 1 +ya/・re/:
To prevent 1 no +h L, special public Sho 4 to improve sharpness
No. 8-3692 and U.S. Pat. No. 3,252,921,
2,527,583ν) It is possible to incorporate filter dyes described in various specifications such as 2,956,8794, and light-absorbing substances such as carhonobra and lily into the lumber. In addition, it is preferable that these dyes are thermally decolorizable. For example, U.S. Pat. No. 376,901
No. 9, No. 3745009, No. 36154325;
Preferably, dyed Fl as described in . Further, in the present invention, a compound that stabilizes the image can be used in the activation and development steps. Among them, U.S. Patent No. 3,301゜678-Part 2-
Intiuroniums represented by hydroquinoethyl isothiuronium Φ trichloroacetate US patent: tS
Hisinthiuroniums such as 1,8-(3,6-nooxaoctano)his(intiuronium trichloroacetate) described in 3,669゜670''+'li German Patent No. 2,162.714''-!f Thiol compounds disclosed in the public domain, U.S. Pat.
-amino-2-thiaturium trichloroacetate,
Thiatulium compounds such as 2-amino-5-bromoethyl-2-thiazolium trichloroacetate, bis(2-7minor-2-thiathurium)methylenebis(sulfonylacetate) described in U.S. Pat. No. 4,060,420, 2-amino Compounds having α-sulfonylacetate as the m-group such as -2-thiazolium phenylsulfonylacetate 3. ! , National Fraud No. 4,08
Compounds having 2-carboquinecarhoki7 amide as the acidic moiety described in No. 8,496 are preferably used. In addition, the triarylphosphoph/compound described in Un-114 Tokusho No. 4,411,985, No. 4,351.896 and JP-A-57-154173 Ginki, Sei no Mesoiono 1,2.4-) Lianliu t, -3-thousand oleate compound is also used (IIll). When using a dye-donating substance in the present invention, it is advantageous to use a water-releasing compound because it accelerates the color-releasing reaction. What is a water-releasing compound? , refers to compounds that decompose and release water during thermal development. These compounds are particularly known in transfer printing of textiles and are described in U.S. Pat. No. 50-88386 K
;NH4Fe (504)2 -12H described in the published publication
20 etc. are for A1. In the present invention, the photographic light-sensitive material and the dye fixing material It may contain an inorganic or organic hardening agent in the photographic hole n1 layer and other paving layers. For example, chromium 111 (chromium 111, chromium 1I11 acid, etc.), aldehydes (formaldehyde, glyoxal, tartar fulldehyde, etc.), N-methylol compounds (methylol urea, methylol methylhigantoi 7, etc.), N-oxane derivatives (2,3-dihydroquinone oxane, etc.), active vinyl compounds (1°3.
5-triacryloyl-hexahydro-S-triacin, 1,3-vinylsulfonyl-2-propatol, etc.)
, if, sexual halogeno compound (2,4-dichloro-6
- human quinone S - trianno), mucohalogen M
Ml can be used alone or in combination (such as Mucochlor alcohol, Mucophenox/chloroacid, etc.). The photosensitive material used in the present invention may contain an ultraviolet absorber in the wood-philic colloid layer, such as a hentriazole compound substituted with an aryl group, a 4-thiasolitone compound, a henonphenono compound, a cinnamic acid ester compound,
Butashev compounds, oxazole compounds, ultraviolet absorbing polymers, and the like can be used.
These ultraviolet absorbers may be fixed in the wood-philic colloid layer. The photographic emulsion of the present invention and the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention include coating aids, antistatic properties, shearing property improvement, emulsification dispersion, MR prevention, and photographic property improvement ( For example, various surfactants may be contained for various purposes such as development acceleration, high contrast, and sensitization. For example, saponins (steroids), alkylene/oxide conductors (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alcohol ethers or polyethylene glycol alkyl ethers, etc.
! ethylene glycol esters, polyalkylene glycol alkylamino or amides, polyethylene oxide adducts of polyethylene glycol), Glintol jA conductor (
Nonionic surfactants such as alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), and furkyl esters such as fatty acid esters of polyhydric alcohols; alkyl carbocates, alkyl sulfonates, alkyl/containing/zea Sulfonic acid salts, alkylnaphthalene/sulfone salt resistance, alkyl sulfate esters, alkyl phosphate esters, N-unru N-furkyltaurifs, sulfosuccinimate esters, sulfoalkylpolyoquine ethylene alkylphenyl esters, polyoxynoethylene Carboxy groups, sulfo groups, phospho groups, sulfate ester groups such as gyleate esters,
Anionic surfactants containing acidic groups such as phosphate esters, (amino acids, aminoalkyl sulfonic acids, ampholytic/alkyl sulfuric acids or phosphorus-resistant esters, alkylhetaias, amine oxins, etc.); amphoteric surfactants such as alkylamino Use of cationic surfactants such as salts, aliphatic or aromatic quaternary ammonium salts, complex quaternary ammonium salts such as pyridinium and imidathulium, and aliphatic or heterocyclic phosphonium or sulfochloram salts. A metal complex is effective as an anti-fading agent for a dye lI!Il image. As a metal complex, a chelate complex having at least one ligand selected from l to tetradentate ligands is preferable. Examples of the rod-like embodiments of complexes include those in which two 2-diagonal ligands are coordinated, one in which 3-diagonal ligands and one 1-diagonal ligand are coordinated, and those in which 4-diagonal ligands are coordinated. One piece is coordinated. Ligand atoms include nitrogen atom, oxygen atom, sulfur atom,
A halogen atom (eg, chlorine atom, bromine 1!I<f, iodine atom) is preferred. The key metals of the metal chain are transition metals, from Sc with 21 atoms to Zn with 30 atoms. From 39(7)Y to 48+7)Cd, 57 no La
From 80 to 80 Hg, gold-11 having an atomic number of 7 to 89 Ac is particularly effective, especially Cu. Co, Ni, Pd, and Pt are preferred. The metal chain preferably forms an anion as a whole complex (complex), 0, or is electrically neutralized within the complex. When forming a metal chain anion, its counter cation is 1 to 2. valent cations are preferred. Examples of mono- to divalent cations include alkali 11 metal t7CL+'', Na'', K''), alkali 1.+
l: jf1 metal ion (Mg”, Ca”, S r2
°. Examples include bisonium ion (his-ammonium ion/, his-phosphonium ion), and onium ion (quaternary ammonium ion/, quaternary phosphonium ion, tertiary sulfonium ion))9. The complex itself has absorption in the visible wavelength region II (+
1y maximum and 41 colors, but colored dyes cause staining in the dye-fixing layer, so the anti-fading agent contained in the dye-fixing layer is colorless or mostly colorless. Preferably. The anti-fading agent with a deep-colored or almost tone tone has the following general formulas (1-I), (2-I) to (2-rV), and (3-
1) and (3-II). In the above formula (1-I), 1M1 is Cu or Co'. Ni, Pdt or PL, X haOt TahaS, R11 is an alkyl group, arylno^, alkoxy/
or aryloquine group, and the same P 16j 1
R II bonded to may be linked to each other to form a 26-membered ring with the P atom. For details of this metal complex, see U.S. Pat.
1,155%11111/117)'IS3 column-E
R6a, and specific examples include the following compounds. (M=Ni, Co, Cu, Pt or Pt)
(2-■)
1. In Ashishiro (2-1) to (2-TV), M2 is the same person as Ml. R12, R22, R32 and R42
each represents a hydrogen atom, a halogen atom, (, alkyl group, aryl group, (or multiple ring)), and these atoms or S represent a direct or divalent IJ. !7v! is bonded to the carbon atom of the xeno ring through the group R12 and R22, R22 and 32, or R32 and R
42 may be connected to +1−;l· to form 6 C1+=. R52 and R82 each represent a hydrogen atom, an alkyl group, or an aryl group. R62 represents a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group. R72 represents an alkyl group or an aryl group, Z is 5
Or represents a nonmetallic atomic group necessary to form a 6-negative ring. For more information on this metal complex, see U.S. Patent No. 4.245.
, No. 018 Specification S, columns 3 to 36, and specific examples include the following compounds. 1'' to L descriptions (3-I) and (3-II), M3 is the same as M] in general formula (1-1), and R13.R
23, R33 and R43 are each a general formula (2% formula % synonymous with R42. R53 and R83 are each a hydrogen atom, an alkyl group, a 7-aryl group, an anru group. an alkoxycarbonyl group, an aryloxycarbonyl group,
Represents an alkylsulfonyl group or an alkylsulfonyl group. For more information on this metal complex, see U.S. Patent No. 4.254.
, No. 195 Specification iI? It is described in the 3rd column to the 8th column, and the following compounds can be mentioned as the body side. Other metal rust bodies that can be used as skin color inhibitors include U.S. Patent Nos. 4.050.938 and 4.241,154.
No., MS No. 4,239,843, No. 4.242.4
No. 30, same: fS4, 242.431t;, same No. 4.
No. 246,329 No. 1 No. 4,256.817 No. 1 No. 17
s4,248°949, s4,246,330,
It is described in 4.301,223, 4,242,429 and 4.343,886. As the matting agent added to the protective layer of the material used in the present invention, conventionally known matting agents can be used. Matting agents are well known in the photographic arts and can be defined as discrete solid particles of inorganic or organic material that can be dispersed in a hydrophilic organic colloid paint. Examples of inorganic matting agents include oxides (e.g. silicon dioxide,
Titanium oxide, magnesium oxide, aluminum oxide
r), alkaline earth metal i! ! (For example, @a salt or charcoal Ml
! ! (Specifically, barium sulfate, carbonate carbonate, magnenium sulfate, carbonate carbonate, etc.) 1 Halogenated fM grains (silver chloride, silver bromide, etc., and further halogen components such as iodine, carbonate, etc.) - may be added, albeit slightly), crows, etc. In addition, examples of organic matting agents include soap powder, cellulose esters (e.g. cellulose acetate pyrovionate, etc.),
These include cellulose ether (for example, ethyl cellulose, etc.), synthetic resins, and the like. Examples of synthetic resins include dispersions of water-insoluble or poorly soluble synthetic irimers, such as alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, and vinyl esters (such as acetic acid). vinyl), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate
A polymer having a combination of acrylate, styrene sulfone 11it, etc. as a heavy component can be used.
Among them, polymethyl methacrylate is preferred. The average particle size of these matting agents is suitably about 0.1 to 10 g, preferably 0.5 to 8 #LL, more preferably 1 to 6 #L. The thickness of the a-retaining layer containing the matting agent is preferably about 1/10 to 1/3 of the average particle size (average diameter) of the matting agent from the viewpoint of improving releasability. The protective layer may be multi-layered, in which case the matting agent is contained in the outermost layer, and in the case of a two-layered structure, for example, oil droplets may be dispersed in at least one of these layers. preferable. The size of the oil droplet is approximately 0. O1-20 pot layer is a mistake, 0
．． 05-1o ILs are preferred. As the substance that forms these oil droplets, a high-boiling organic compound that is usually used for dispersing photographic couplers is useful.
℃ or less, preferably 1, e.g., U.S. Pat. No. 2,322
, No. 027, phthalic acid argyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl 7 phosphate, triphenyl phosphate, tricresyl phosphate,
Dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), ben9oic acid esters (e.g. Anohm, Yojo octyl), alkyl amides (
For example, noethyl lauryl amide), fat-resistant esters (
Examples include dibutoxyethyl succinate, diethyl azelate), trimesine/acid esters (eg, trimesine tributyl), and the like. Examples of the slippery agent include higher alkyl sulfurized soda, higher fatty acid higher alcohol ester, carpo wax, higher alkyl phosphate ester, and silicone-based compounds. In particular, U.S. Patent No. 2,882,157;
The compounds described in No. 121.060, No. 3.850.640, and JP-A-51-141623 are particularly effective for use in cars or in combination of two or more. ]/IT j4 of the slippery agent is approximately 5 to 200 g/-
2 is unreasonable. The organic fluoro compound includes a chain or cyclic compound containing at least three fluorine atoms and at least three carbon atoms, and any type of cationic, anionic, anionic, or betaine type is preferred. ? Can be used. Representative organic fluoro compounds used in the present invention include, for example, US Pat. No. 3,589,906 and US Pat. No. 3,666,47B. Same No. 3,754.924. Same No. 3,775,126, Same No. 3,8
No. 50,640, British Patent No. 1.330.356, JP-A-51-
It is described in No. 106419. Representative examples of these organic fluoro compounds are described in columns 8 to 17 of Japanese Patent Publication No. 57-9053. A particularly preferred organic fluoro compound is an anionic organic fluorine-containing surfactant. The amount of organic fluoro compound added is 1rn of the protective layer to be coated.
0.1 to 500 mg per ', preferably 1 to 20 mg
It is 0 mg. One layer for dye fixation may contain an anti-fading agent to improve the light fastness of the transferred dye image. This anti-fading agent may be, for example, a photographic antioxidant or an ultraviolet absorber. What is used is valid. Specific examples of photographic antioxidants include hindered phenols (e.g. 2,6-di-t-butyl-4-methylphenol, 2,2'-butylidene-bis-(-6-
tert-butyl-4-methylphenol), 4.4'
-thiobis(3-methyl-6-t-butyl-phenol)7], phenyl-β-naphthylamine, N. N'-di-sec butyl p-phenylene diamino, phenothiazine, N, N'-diphenyl-p-7 enylene diamine, d, l-α-tocopherol, 2.5
-t-hexyl-4-methquinphenol and 6.6
'-dihydroxy-4,4,4', 4'', 7.
Examples include 7'-hexamethyl-bis-2,2'-spirochroman. In addition, as ultraviolet absorbers, benzotriazoles (
For example, 2-(3',5''-ditershariamil-2'
-hydroxyphenyl)be/citriazole, 2-(2
'-Hydroxy-3',5'-ditertiarybutylphenyl)-5-chlorobenzotriazole,2-(3'
. 5'-ditertibutyl-2-hydroquinphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(
hydroxy-5'-tertbutylphenyl)benzotriazole, etc.], benzophenones (e.g. 2-hydroquine-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy- 2'-hydroxybensophenone/, 2-hydroquino-4-n-octoxybenzophenone, 2-hydroxyhensophenone, etc.), 2-ethylhexyl-2-anor 3.3'- diphenyl acrylate, p-octylphenyl salyl, 1-(2,
Examples include 4-sheet-t-butyl-3,5-di-t-butyl-4-hytroquine benzoate. A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixing layer. As the dye transfer aid, a liquid or a hot solvent that can dissolve the dye to be transferred at least in a heated state can be used. That is, if the pigment to be transferred is a wood-based pigment, a hydrophilic liquid or a hydrophilic hot solvent is used, and in the case of a lipophilic pigment, an organic solvent, an oil-lipophilic hot solvent, etc. that can dissolve the pigment is used. can be used. Further, depending on the degree of wood-philicity and lipophilicity of the dye, appropriate amounts of a wood-philic liquid, a wood-philic heat solvent, a lipophilic solvent, and a lipophilic heat solvent may be mixed and used. The dye transfer aid may be used in the dye fixing layer and/or the photosensitive layer, preferably with a force θ of wetting the dye fixing layer with a solvent, or it may be directly incorporated in this layer in advance, or it may be added to the polymer or crystal. It may be adsorbed or incorporated as crystal water or as microcapsules. Hydrophilic or lipophilic solvents used as dye transfer aids include water or basic aqueous solutions containing inorganic alkali metal salts such as caustic soda, caustic potash, and soda carbonate, methanol, ethanol, propatool, butanol, and benzyl alcohol. Monohydric alcohols such as ethylene glycol, diethyleglycol, polyethylene glycol, propylene glycol, polyhydric alcohols such as glycerol, ethers with alcoholic OH groups such as furyl alcohol, methyl cellosolve, cellosolve, acetone,
Acetylacetone, methyl ethyl ketone, hexanone. Examples include ketones such as cyclohexanone, esters such as methyl acetate, ethyl acetate, 1% tyl acetate, methyl benzoate, n-butyl phosphate, and nitrogen-containing solvents such as diethylamine, dibutylamine, pyridine, and quinoline. . In photosensitive materials in which the dye to be transferred is lignophilic, 1
When a dye transfer aid is incorporated into a photosensitive material and/or a dye fixing material, a hydrophilic thermal solvent is used as the dye transfer aid, and by heating in the presence of the dye transfer aid, the hydrophilic dye is transferred to the dye fixing material. can be transferred and fixed. In an image forming method in which one dye is transferred to a fixed layer by heating in the presence of a wood-philic thermal solvent, the transfer of mobile dyes starts at the same time as the release of the dye, but after the release of one dye is completed. Therefore, the heating for transfer may be performed after the heat development or at the same time as the heat development. Heating for dye transfer is from 60°C to 250°C from the viewpoint of storage stability and workability of the photosensitive material.1 In the present invention, the temperature range is 60°C to 250°C. You can choose one as appropriate. It goes without saying that an aqueous thermal solvent must be able to quickly aid the movement of dyes when heated, but if we also consider the heat resistance of the photosensitive material, the melting point required for a hydrophilic thermal solvent will be is 40°C to 250°C. Preferably 40°C to 200°C, more preferably 40°C
~150°C. The wood-friendly heat solvent is in a solid state at room temperature,
A compound that becomes liquid when heated, (inorganic/
It is defined as a compound with an organic property value>l and a water solubility at room temperature of 1 or more. Herein, "inorganic" and "organic" are general terms for predicting the normality of a compound, and the details can be found in, for example, the field of chemistry, page 719 (19
57). As a hydrophilic heat solvent, (
It is an essential condition that the (inorganic/organic) value is 1 or more, preferably 2 or more. On the other hand, from the viewpoint of the size of a single molecule, it is considered preferable that molecules that can move by themselves exist around the moving dye without causing Mi to impair its movement. Therefore, it is preferable that the molecular weight of the hydrophilic heat solvent is small, and IJ2
00 or less. A more preferred molecular weight is about 100 or less. It is sufficient that the wood-philic thermal solvent can substantially assist the movement of the wood-philic dye generated by heat development to the dye-fixing layer, so it can not only be included in the dye-fixing layer, but also in the photosensitive layer. The wood-philic thermal solvent can be contained in the photosensitive material, in both the dye fixing layer and the photosensitive layer, or in the photosensitive material or in an independent dye fixing material having the dye fixing layer. You can also submerge one layer of solitude. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, the hydrophilic thermal solvent is preferably contained in the dye fixing layer and/or its adjacent layer. The wood-philic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols such as methanol, ethanol, etc. Examples of usable hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oxidims, and other heterocycles. Specific examples of this wood-philic heat solvent and particularly preferred examples include No. 14 of JP-A No. 58-42092.
The compounds described on pages 9 to 158 are listed below. These hydrophilic heat solvents can be used alone or in combination of two or more. This wood-philic thermal solvent is added to the photosensitive material or dye-fixing material in an amount equivalent to the total coating film thickness excluding the wood-philic thermal solvent, converted into weight.
0 to 300% by weight, preferably 20 to 200% by weight,
Particularly preferably, it can be used in a range of 30 to 150%. The image-receiving layer in the present invention includes a dye-fixing layer used in the heat-developable color photosensitive material No.1. Any mordant can be selected from commonly used mordants, but polymer mordants are particularly preferred.
Here, the polymer mordant includes a polymer containing a secondary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like. The mordant used in the present invention has the general formula (LXI)
A polymer containing a donyl monomer center having a tertiary amino group or a quaternary ammonio group represented by ~(LXrV) is preferred. -・General formula (LXI) ■ +CH2-C+ (L) n [In the formula, R1 represents a water leak atom or lower alkyl having 1 to 6 carbon atoms), li, L represents 1 to 20 carbon atoms] & Z R Represents a divalent linking group that controls the number of molecules, E
represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a number of carbon atoms; n is 0 or 1; ] General formula (L represents an alkyl group having 12 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, R4 and R5 may be interconnected to form a cyclic structure with a nitrogen atom, n is O or It is 1. ] General formula (LXIII) +CH2-C+ (L) n! Ge , X9 represents a monovalent anion, n is O or l. ] General formula (LXff) MoCH2-C+ (L) n R4-Ne-Ra Representing the same thing, R6 is selected from the same thing as R4, Rh. Xe represents the same thing as the general formula (txm). R4, R5, R, may be interconnected to form a cyclic structure together with a nitrogen atom; n is 0 or l; ] General formula (L X I ) −(L X rV ) TeR
+ is a hydrogen atom or a lower alkyl group having 1 to 6 IXJ numbers, such as a methyl group, an ethyl group, an n-propyl group, an n-
It represents a -butyl group, an n-7mil group, an n-hexyl group, etc., and a hydrogen atom or a methyl group is particularly preferred. L is a divalent linking group having 1 to about 20 carbon atoms, such as an alkylene group (e.g. methylene group, ethylene group, trimethylene group, hexamethylene group, etc.), a phenylene group (e.g. O-phenylene group, p-phenylene group) group, m-phenylene group, etc.), arylene alkylene group (e.g. 0
R2-1 or etc., where R2 represents an alkylene group having 1 to about 12 carbon atoms), -co2-1-002-R3 (wherein R3 represents an alkylene group, phenylene group, or arylene alkylene group), -CON H-R3- (wherein R3 represents the same as above). -CON-13- (however, R3 represents the same as above), -CO2-, -CONH-1-CO2-CH2C) (2
-1-CO2-CH2CH2CH2. -CONHCH2+, -CONHCI(2CH2-, -
CON HCH2CH2CH2- and the like are particularly preferred. In the general formula (LXI), E is a heterocycle 1 containing a nitrogen atom having a double bond with a carbon atom as a constituent, such as an imidazole ring (e.g., etc.), a triazole ring (e.g., etc.), a pyrazole ring (e.g., etc.) ), a pyridine ring (for example, etc.), a pyrimidine ring (for example, etc.), and imidazole rings and pyridine rings are particularly preferred. Preferred specific examples of polymers containing units include U.S. Pat.
The following may be mentioned, including the mordants described in No. 15,124 and No. 3,148,061. In the general formula (LXII), R4 and R5 are an alkyl group having 1 to 12 carbon atoms, for example, an alkyl group without 2i substitution (
Methyl group, ethyl group, n-propyl group, n-butyl group,
Q-7 Mil group, hexyl group, n-nonyl group, n-tecyl group, n-dodecyl group, etc.), substituted alkyl group
A (methoxyethyl group, 3-anoprobyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydroxyethyl group, 2-butenyl group, etc.), or 7-
Aralkyl groups having 20 carbon atoms 5 e.g. pio-substituted 7-ralkyl groups, (benzyl, phenethyl, diphenylmethyl, naphthylmethyl, etc.) 8-substituted aralkyl groups (4-methylbenzyl, 4-isopropylbenne, etc.) 4
-methoxybeny/zyl group, 4-(4-mesiphenyl)benzyl group, 3-chloroben- group, etc.). :TaR4. As an example where R5 is linked to each other to form a cyclic structure with the nitrogen atom and -fl, for example, - represents a number). -N]. Preferred examples of the polymer containing one vinyl nitrate unit having seven tertiary amide groups represented by the general formula (LX■) include the following. (Number: mol%) In the general formula (LXm), G represents a heterocycle that is quaternized and contains a nitrogen atom having a double bond with carbon as a constituent, examples of which include imidazolium, etc. ), doriazoum salts (e.g., etc.), pyridinium salts (e.g., etc.), among which ichmidazolium salts and pyridinium salts are particularly preferred, where R4 has the general formula (
It represents the same as L X 11 ), and methyl, ethyl, and benzyl groups are particularly preferred. -fii (LXm), (Lx■), xe represents an anion, such as halogen ion (e.g. chloride ion, bromide ion, iodine ion), alkyl sulfate ion (e.g. methyl sulfate ion, ethyl WtfI# ion), alkyl or Examples include arylsulfonic acid ions (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-) luenesulfonic acid), acetate ions, sulfuric acid ions, and especially chloride ions, p-) luenesulfonic acid ions. preferable. Preferred specific examples of the polyamide containing one unit of a vinyl monomer having a quaternary ammonio group represented by the general formula (LX [[I)] are as follows. British Patent No. 2,056.101. Same No. 2,093,041, Same No. 1.
No. 594.961, U.S. Pat. No. 4,124,386. Same No. 4,115,124, Same No. 4
．． The following may be mentioned, including the mordants described in No. 273.853, No. 4,450,224, and JP-A-48-28225. 01e Ut+ C1 (9 p-T(i)e - ni7■ 100-dノ・General formula (LXrV) As an example where R,, R5 are connected to each other to form a cyclic structure with the nitrogen atom. Examples of 1 include (where m represents an integer of 4 to 12), and examples of R4, R5, and R forming a cyclic structure include 1.In the general formula (LX1'V), Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary ammonia group include U.S. Pat. No. 3,709,690, U.S. Pat. The following may be mentioned, including the mordants described in U.S. Patent Nos. 2.548.564 and 2.4.
No. 84,430, No. 3,148°061, No. 3.
Vinyl pyridinobolyphs disclosed in No. 756,814 and the like. and vinylpyridinium cationic polymer; U.S. Pat. No. 3,625.694, U.S. Pat. No. 3.859.096,
British Permit No. 4N28.538 No. 1.277.453
Fe polymer mordants for crosslinking with gelatin etc. disclosed in US Pat. No. 3.958.995, US Pat. No. 2.721.852, US Pat.
Aqueous sol-type mordant disclosed in JP-A-54-115228, JP-A-54-145529, JP-A-54-126027'N+ specification, etc.: Water-based mordant disclosed in U.S. Pat. No. 3,898,088. Insoluble mordant: U.S. Patent No. 4
．． 168.978 (Japanese Unexamined Patent Publication No. 54-137333), etc. Reactive mordants capable of covalent bonding with dyes disclosed in the specification, etc.: Further US patents: jS3.709.690, JS3.788.855 No. 3,642,482
No. 3.488.706, No. 3.557.06
No. 6 5 times: fS3.271.147, fS3.271
．． No. 148, JP-A No. 50-71332, No. 53-30
328, No. 52-155528, No. 53-125, and No. 53-1024. Others include U.S. Patent No. 2,675.316. Mention may also be made of the mordants described in the same specification No. 2.882.156. The mixing ratio of the uninvented polymer mordant and gelatin and the coating amount of the polymer mordant depend on the amount of dye to be mordanted, the type and composition of the polymer mordant. Furthermore, depending on the image forming process used, etc., the mordant/gelatin ratio may be 2, although it can be easily determined by Person X.
0/80 to 80/20 (modification ratio), mordant coating I5t is 0
．． It is preferable to use 2-15 g/m2, preferably 0.5 g/m2 to 8 g/m2.The proportion Yh1 of the polymer used in the mordant is preferably 1000-1000000°, especially 10000-200000. When the above polymer is used as a mordant in the present invention, the transfer density of the dye can be increased by using metal ions in the photosensitive material or dye fixing material. The metal ions are added to the mordant layer containing the mordant, or to the adjacent upper or lower layer. The metal ion used here is desirably colorless and stable against heat and light, ie Cu2+. Z n 2+ , N i 2+ ,
p j 2+ , pd2+ ,
Polyvalent ions of transition metals such as Co3+ ions are preferred, and Zn2+ is particularly preferred; this metal ion is usually in the form of water-soluble compounds, such as ZnSO4, Zn
(CH3CO2)2, and the added U is 0.01 to 5 g/m2. Preferably 0.1-1.51/
It is m2. In the present invention, a conventionally known method can be used as a heating method for development. For example, it is also possible to transport the photosensitive material using a reheat roller in which the photosensitive material is brought into contact with a hot plate such as a hot plate or a tram. It is also possible to use air heated to the product temperature, or to heat by high frequency heating or a laser beam. Depending on the photosensitive material, it can also be heated using an infrared heater. Furthermore, it is also possible to apply a method of heating using eddy currents generated by 'If&i induction. Alternatively, the photosensitive material may be heated in a path in which a liquid inert to the photosensitive material, such as a fluorine-based liquid, is heated. Furthermore, the photosensitive material may be heated by providing a heating source separate from the above-mentioned heating means. You can use heat. Various patterns can be applied as the pattern for heating the photosensitive material. The most common method is to heat at a constant temperature, but depending on the characteristics of the photosensitive material, multi-stage heating, for example, a method in which the temperature is gradually lowered after υ and temperature shortening time 1111 is effective. If the photosensitive material is susceptible to air oxidation during heating, it is effective to deaerate the area around the heating section or replace it with an inert gas. In addition, the surface of the photosensitive material may be brought into direct contact with the heated part or exposed to the air. When developing the surface of the photosensitive material on the air side, it is necessary to prevent moisture and volatile components from evaporating from the photosensitive material. It is also effective to attach a cover for heat retention purposes. In the present invention, heat generation in transparent or opaque I when electrical heating is employed as the developing means! The element can be made using conventionally known technology as a resistance heating element. As the resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting semiconductivity, and the other uses an organic M film in which conductive fine particles are dispersed in paint. Materials that can be used in the 4i1 method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide. A membrane can be created. In the latter method, a resistor having desired temperature characteristics can be produced by dispersing NiX conductive particles such as gold 111i particles, carbon black, and graphite in rubber or synthetic polybogelatin. These resistors may be in direct contact with the photosensitive element or support. An example of the positional relationship between the photosensitive element and the photosensitive element, which may be separated by an intermediate part or the like, is shown below. Heat generating element/support/photosensitive element support/heat generating element/photosensitive element support/heat generating element/intermediate R/photosensitive element support/photosensitive element/heat sensitive element support/photosensitive element/intermediate layer/Raturing 1! ! Radiation including visible light can be used as a light source for image fog light for recording an image on the photosensitive material. In general, various light sources such as tungsten lamps, halogen lamps such as mercury lamps and iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light emitting diodes (LEDs) are used for normal color printing. Can be used. It is also possible to use an exposure means that combines a micro-shutter array using an LCD (liquid crystal) or PLZT (lanthanum-topped lead titanium zirconate) with a linear light source or a planar light source. 'y-When using an LED as a pitching device, it is difficult to obtain blue light using the LED, so to reproduce a color image, 1. For example, the LED must emit green, red, and infrared light.3 The heat-developable photosensitive material can be designed in such a way that it can be exposed to light using seeds, and yellow, magenta, and cyan dyes 1 are released from the respective photosensitive layers that are exposed to these lights. However, it is sufficient that the red-sensitive portion (layer) contains a yellow dye-donating substance, the red-sensitive portion (layer) contains a magenta dye-donating substance, and the infrared-sensitive portion (layer) contains a cyan dye-donating substance. Generation characteristics of LEDs and spectral sensitivity characteristics of photosensitive materials. Furthermore, the generation characteristics of the photosensitive material are not necessarily limited to this combination, and various combinations are possible. Examples of methods for exposing the heat-developable photosensitive material include the following methods. The first method is to use an i-drawing such as a line image from a drawing or a photographic image with gradation, and then contact-print it with the original image. In addition, we can also send electronic transmissions of images taken by video cameras, images sent from television stations, or original drawings to Hikari 1! The image signals read by a light receiving element such as a tube or COD and stored in the memory of a computer, etc. are subjected to so-called image processing, in which the image signals are added as necessary, and then directly transferred to a CRT or FOT (7 eye bar optics cathode ray tube). , and image this image onto the heat-developable photosensitive material 1 with v, :It or with a lens.
It is also possible to burn it (for example, Japanese Patent Application Laid-Open No. 52-14
No. 8302). Further, the operation exposure may be performed by performing the operation in the following manner and controlling the light emission of an LED or a semiconductor laser light source or the like using the processed image signal, or by modulating the laser beam or the like. 1) For example, JP-A-57-151933. Alternatively, as described in Japanese Patent Application No. 57-226555, light sources such as LEDs and semiconductor lasers are arranged in the circumferential direction of a disc-shaped rotor, and the rotor is rotated and moved in the direction of the axis of one rotation. How to operate. 11) As is known in so-called scanners, a photosensitive material is wound around a drum, the drum is rotated, and a light source is provided, or the light from the light source is first guided to an optical fiber. A method of operating the drum by moving the head in the direction of the drum's rotation axis. 1) Galvano mirror the light beam from a laser light source, etc.
A method in which the photosensitive material is operated by vibrating it using a light deflector such as a one-turn multifaceted TA and moving the photosensitive material perpendicular to the changing direction. Furthermore, as described in Japanese Patent Application No. 58-142229, both image signals are applied to the liquid crystal in a matrix or array form,
Exposure can also be performed by controlling the light from the light source. A dye transfer aid (for example, wood) is applied between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. It is also possible to apply a dye transfer aid to the dye fixing layer or both, and then superpose the two layers. As a method for applying a dye transfer aid to a photosensitive layer or a dye fixing layer, for example, Japanese Patent Application Laid-Open No. 58-5590
Law as described in No. 7. Color coating method or wire bar coating method, patent application 1982-
A method of applying water to a dye-fixing material using a water-absorbing member as described in No. 55908, Japanese Patent Application No. 58-5590
As described in No. 6, a method of forming beads between a heat-developable photosensitive material and a dye fixing material to impart a dye transfer aid, as described in Japanese Patent Application No. 58-55910,
A method of applying the dye transfer aid by forming a bead between the water-repellent roller and the dye fixing layer, a dipping method, an extrusion method, a method of applying the dye by ejecting it as a jet from pores, and a method of applying the dye transfer agent by forming a bead between the water-repellent roller and the dye fixing layer. Comes in a crushable format!
Various methods can be used, such as the method of The dye transfer aid may be measured in advance and given in an amount within the range described in Japanese Patent Application No. 58-37902, or it may be given in sufficient quantity and then squeezed out with pressure using a roller or the like or heated. The amount can be adjusted by adding and drying. For example, a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out by passing it between pressurized rollers, and then the photothermographic material is superimposed. There is. The heating means in the transfer process is heated by passing between hot plates or by contacting the hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635).
), heating by contacting a heated drum or heated roller while rotating (for example, Japanese Patent Publication No. 43-10791), heating by passing through hot air (for example, Japanese Patent Publication No. 53-327)
No. 37), ・Heating by passing through an inert liquid kept at a constant temperature, or heating by passing it along a heat source using a roller, belt, or guide member? For example, Japanese Patent Publication No. 44-2546) can be used.
In addition, a layer of conductive material such as graphite, carbon black, or metal is applied to the dye fixing material, and an electric magic is passed through this conductive layer. Direct heating may also be used. The heating temperature for applying +I in the transfer step can be in the range from the temperature in the heat development step to room temperature, but
Especially at 60°C or higher, 10°C higher than the temperature in the heat development process.
A temperature lower than ℃ is preferred. The pressure when the heat-developable photosensitive material and the dye-fixing material are overlapped and brought into close contact with each other varies depending on the materials used in Embodiment 5, but is 0.1 to 100 Kg/C-2. Preferably 1-50
Kg/c fat 2 is suitable (for example, patent application 1986-55
691). 1. Applying force to the written name can be done using various methods, such as passing through a pair of rollers 11i, pressing using a plate with good smoothness, etc.
The temperature of the roller, plate, etc. when applying pressure can be in the range from room temperature to temperatures in the range of -100 to 100 degrees for thermal development. The preservative strength method of the present invention is effective for heat-developable photosensitive materials on which images are formed by these methods. Since the film was stored in the presence of a protective agent, deterioration of photographic properties caused by storage was prevented. A heat-developable photosensitive material with excellent stability over time can be obtained. (1) Specific Example of 1g1 The present invention will be explained in more detail by showing a practical example of the present invention. Example 1 Preparation of photosensitive silver bromide-containing hensitriazole silver emulsion 6.5 g of benzotriazole and 1 gelatin. g is dissolved in wood 1000+n11. Add this solution to 5
Keep at 0°C and stir. Next, add 8.5 g of silver nitrate to 1 portion of water.
Add the solution dissolved in 00m to the solution in 1- for 2 minutes. Next, a solution of 1.2 g of Mihi potassium dissolved in 50 mJL of wood was added over 2 minutes. The prepared emulsion is precipitated by pH adjustment to remove excess 1 u. Thereafter, the pH of the emulsion was adjusted to 6.0. The amount kept was 200g. Preparation of gelatin dispersion of dye-donating substance Log a dye-donating substance with the following structure. As a surfactant, we weighed 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 4 g of trire resin phosphate (TPO), added 20 mff1 of cyclohexanone, and dissolved them by heating to about 60°C to form a uniform mixture. Make a solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated to 1100 g for 10 minutes using a homogenizer.
Disperse at 00 rpm. Next, the g45a method for photosensitive coatings will be described. (a) I+! Silver benzotriazole emulsion containing photosensitive silver bromide 10g (b) Dispersion of dye-donating substance 3.5g (C) Base precursor: guanidine phenylpropiolate 0.20g (d) Gelatin (10% aqueous solution) 5g (e ) 2
, a solution of 0.2 g of 6-dichloro-4-aminophenol dissolved in 2 m of methanol (f) 1 m of a 10% aqueous solution of a compound with the following structure: 09 Hlqoo (CH2CH20)A
After mixing a) to (f) and heating and melting, the thickness is 180 mm.
30 on a 1Lm polyethylene terephthalate film.
The coating was applied to a weight of 2 mm thick. Furthermore, the following composition was applied as a protective layer thereon. b) Gelatin 10% aqueous solution 30m intersection) Water
A mixture of solutions a) to c) in which 0.8 g of guanidine phenylpropiolate was dissolved in 20 m of water was applied to a wet film thickness of 30 pm and dried to prepare a photosensitive material A. This photosensitive material A is placed in a stainless steel container and sealed as is, as sample I, and silica gel is placed in the stainless steel container and sealed as sample 2. Hydroquinone, sodium nitrite, carbonate, and A mixture of sodium (weight ratio 1:1:2) was added and sealed, and this was designated as sample m. Sample 1 is a stainless steel container that was replaced with nitrogen gas and then sealed, and Sample V is a container that was filled with silica gel and further replaced with nitrogen gas. Next, a method for forming an image receiving material having an image receiving layer will be described. Poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) Dissolve 10g in 200m of water and treat with 10% lime. Mixed uniformly with gelatin loog. This liquid mixture was uniformly applied to a wet film thickness of 90 pm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample was used as an image receiving material. Immediately after producing photosensitive material A, and after storing samples ~V for one month under a temperature condition of 40"C, they were imagewise exposed to light at 2000 lux for 10 seconds using a tungsten bulb. Thereafter, 140" The material was heated uniformly for 30 seconds on a heat block heated to 80°C. The 1m-heated photosensitive material was placed on top of the image-receiving material soaked in water so that the film surface was in contact with the film surface. The material was heated for 6 seconds on a heat block heated to 80°C. After that, when the image-receiving material was peeled off from the photosensitive material, a negative magenta color image was obtained on the image-receiving material.The density of this negative image was measured using a Macbeth reflection density, 1L (HD-519), and is shown in the table below. −
The results shown in 1 were obtained. Table 1 From Table 1, it can be seen that the close-up fI' photographic material containing the drying agent and/or antioxidant of the present invention has good storage stability. Example 2 Preparation of gelatin dispersion of dye-donating substance 5 g of a reducible dye-releasing agent having the following structure. 0.5g of sodium tsusuccinate-2-ethyl-hexyl ester sulfonate (TC)
P) Add 20m of cyclohexanone to the log, approximately 6
The mixture was heated and dissolved at 0°C. lO% of this solution and gelatin
After stirring and mixing 100g of the solution,
Disperse at 110,000 rpm for 0 minutes. Next, a method for preparing a photosensitive coating liquid will be described. (a) Benzotriazole silver emulsion containing photosensitive silver bromide (
10 g (b) Dispersion of dye-donating substance 3.5 g (C) Base precursor: 4-methylsulfonylphenylsulfonylacetate guanidine 0.20 g (d) 5% of the following compound Mix (a) to (d) of 1.5m aqueous solution (C9H + 90C) C-CHZ CH20)a H and above, heat and dissolve, and apply on polyethylene terephthalate film to a wet film thickness of 30m, Dry. Furthermore, as a protective layer on top of this, 30% of the following composition was added.
Coat to a wet film thickness of #Lm and dry to form photosensitive material B.
It was created. a) Gelatin (1G% aqueous solution) 30g) Base precursor: 4-methylsulfonylphenylsulfonylacetate guanidine 1.0g c) Water
Immediately after preparation of this photosensitive material B, and after storing a sample in the same manner as IV in Example 1 for one month at a temperature of 40°C, images were taken for 10 seconds at 2000 lux using a tungsten light bulb. exposed to light. Thereafter, it was heated uniformly for 40 seconds on a heat block heated to 140°C. The image-receiving material used in Example 4p41 was used and processed in the same manner to obtain a positive magenta color image on the image-receiving material. The density of this positive image is determined by the 2 Macbeth reflection densitometer (RD).
-519), and the results shown in Table 2 were obtained. Table 2 Table 2 shows that the heat-developable photosensitive material containing the desiccant and/or antioxidant of the present invention has good storage stability. Example 3 A method for preparing a benzotriazole silver emulsion will be described. 28 g of gelatin and 13.2 g of benzotriazole are dissolved in 300 m of water. Add this solution to 4
Keep at 0°C and stir. Add 17g of silver nitrate to this solution and add 1g of water.
Add the solution dissolved in the 00m sentence for 2 minutes. The pH of the hensitriazole silver emulsion is adjusted and allowed to settle to remove excess salt. After that, reduce the pH to 6.30.
A benzotriazole silver emulsion with a yield of 400 g was obtained. This article describes how to make silver halide emulsions for the 5th and 1st layers. A well-stirred gelatin aqueous solution (20 g of gelatin and 3 parts of sodium chloride in 100 100 O
600 mfL of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution ($1R0.59 mole of nitrate dissolved in 800 ml of water) were simultaneously added over a period of 40 minutes. Added at flow rate. In this way, a cubic silver chlorobromide emulsion (odor J: 50 mol %) having an average grain size of 0.404 m was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a. Chemical sensitization was performed at 60° C. by adding 20 mg of 7-chitrazaindene. The yield of the emulsion was 600 g.Next, we will explain how to make the silver halide emulsion for the third layer. A well-stirred gelatin aqueous solution (20 g of gelatin and 3 g of sodium chloride in 1000 mQ of water)
600 ml of an aqueous solution containing sodium chloride and potassium bromide (containing water and kept at 75°C) and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously mixed over 40 minutes. Added at flow rate. In this way, a monodisperse cubic silver chlorobromide emulsion (!2-element 80 mol %) with an average grain size of 0.35 gm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 4- and droxy-6-methyl-1,3,3a. Chemical sensitization was performed at 60° C. by adding 20 mg of 7-chitrazaindene. The weight of the emulsion was 600 g. Next, we will describe how to make a gelatin dispersion of a dye-donating substance. 5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant,
LOgel+ value, add 30 ml of 1!1 acidic chloride, and heat to dissolve at about 60"C to make a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, min, 110000r
Disperse at p. This dispersion is called a yellow dye-providing substance dispersion. A dispersion of a magenta dye-donating substance was prepared in the same manner as in step 1 according to method E, except that the magenta dye-donating substance CB) was used and 7.5 g of tricresyl phosphate was used as a high-boiling melting agent. Ta. A cyan dye-donor XrJ(C) was used in the same manner as the yellow dye dispersion. With these, a color issue with a multilayer structure as shown in the first table! - Created a light material. Work, Zuku≦8 cQ Rework Convex υ −Noe
Next, I will explain how to make the color and fixing material 1. Dissolve 10 g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbennolammonium chloride is 1:1) in 200 mfl of water,
The mixture was evenly mixed with 100 g of 10% lime-treated gelatin.
This mixed solution was uniformly applied to a 90 pm wet film H on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material having a mordant layer. 1.2 G, R, IR three-color separation filter with continuously changing density (G is 500-600 nm, R is 600 nm) using a tungsten bulb in a color photosensitive material with an east layer configuration
-700 nm punt pass filter, IR is 70
(constructed using a filter that transmits at least 0 nm). Exposure was performed for 1 second at 500 lux. Thereafter, it was heated uniformly for 30 seconds using a heat block heated to 140°C. Next, apply 20m1 per 1rr1' on the film side of the dye fixing material.
After supplying water, the heat-treated photosensitive coatings were superimposed on the fixing material so that the IIQ surfaces were in contact with each other. After heating for 6 seconds on a heat block at 80°C, peel off the dye fixing material 1 from the photosensitive material 1. Place the dye fixing material 1 on top of the fixing material 1.
Yellow, magenta, and cyan color images were obtained corresponding to the three color separation filters of G, R, and IR, respectively. The maximum density (D saw, ) and minimum density (Dln,
) was measured using a Macbeth reflection densitometer (RD-519). Further, this light-sensitive material was stored at 40°C for one month under the following storage conditions, and then processed in exactly the same manner, and the density of the resulting color image was measured. The results are shown in Table-3. Sample I: Enclose the photosensitive material in a polyethylene bag and store it protected from light. Sample: 1lllj (a mixture of ferrous acid and iron powder (Tohoku ratio 2:1) was wrapped in paper, sealed in a polyethylene bag with photosensitive material, and stored in a light-shielded manner. Sample■ Wrap ferrous acid and iron powder in paper. Then, seal it in a polyethylene bag with the photosensitive material and store it protected from light.Sample■ Sulfuric acid: A mixture of iSl iron, iron powder, and warp gel (
@φ ratio 2:l:1) was wrapped in paper and sealed in a polyethylene bag along with the photosensitive material, and stored protected from light. Table-3 Magenta (R) 2.35 0.13n7 (
IR) 2.50 0.15 77 (IR)
2,51 0.65 Schiff 7 (IR) 2,
48 0, 35 cyan (IR) 2.52
0.26 Shin7 (IR) 2.52 0.21 From Table 3, it can be seen that the desiccant or catalytic protection agent of the present invention is effective also in the heat-developable color photosensitive material No. 1 having the same layer structure. I understand.

Claims (1)

[Claims] A method for preserving a photothermographic material, which comprises storing the photothermographic material in the presence of a desiccant and/or an antioxidant.