JPH0535855B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable photosensitive material, and more particularly to a heat-developable photosensitive material in which the influence of unnecessary ultraviolet rays is reduced. [Background of the Invention] In recent years, heat-developable photosensitive materials whose development process can be performed by heat treatment have attracted attention as photosensitive materials. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication No. 43-4921 and No. 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, a reducing agent, and a binder. It is commercialized by 3M as dry silver. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Pat. Research Disclosure
15108 and 15127, U.S. Pat. No. 4,021,240, etc., a dye image is formed by the reaction of a coupler with an oxidized form of a reducing agent (hereinafter also referred to as a developer or developing agent), which is a sulfonamide phenol or sulfonamide aniline derivative. A method of releasing a dye image on a separately provided image-receiving layer by using an organic imino silver salt having a dye part as disclosed in British Patent No. 1590956, and releasing a dye image on a separately provided image-receiving layer. JP-A-52-10582, No. 52-
105822, 56-50328, and U.S. Pat. No. 4,235,957, etc., methods for obtaining positive dye images by silver dye bleaching methods, as well as U.S. Pat. No. 3,180,731,
Same No. 3985565, Same No. 4022617, Same No. 4452883,
Various methods have been proposed, such as the method of obtaining a dye image using a leuco dye disclosed in Japanese Patent Application Laid-Open No. 59-206831. However, with these proposals regarding the heat-developable color photosensitive materials, it is difficult to bleach and fix the black, white, and silver images formed at the same time, and
It is difficult to obtain clear color images,
Furthermore, it required complicated post-processing, and was not yet satisfactory for practical use. In recent years, as a new type of color image forming method using heat development, Japanese Patent Laid-Open Nos. 57-179840 and 57-
No. 186744, No. 57-198458, No. 57-207250, etc. disclose methods for obtaining color images by transferring diffusible dyes released by heat development. These methods were further improved to produce diffusible dyes by oxidizing non-diffusible reducing dye-donating substances, such as those disclosed in JP-A-58-58453 and JP-A-59-168439. A method of emitting
JP-A No. 58-79247, No. 59-174834, No. 59-
12431, No. 59-159159, No. 60-2950, etc., in which a diffusible dye is released by coupling with an oxidized developing agent; No. 58-149047, 59
−124339, No. 59-181345, No. 60-2950, Patent Application No. 59-181604, No. 59-182506, No. 59-
A method using a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye as disclosed in No. 182507, No. 59-272335, etc.;
JP-A No. 59-152440, No. 59-124327, No. 59-
No. 154445, No. 59-166954, etc., are non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and conversely, non-diffusible dye-donating substances that release diffusible dyes when reduced. Some methods have been proposed, such as a method containing a pigment-providing substance. The basic composition of a color type heat-developable photosensitive material that produces a color image using these emitted or formed diffusive dyes consists of a light-sensitive element and an image-receiving element. It consists of a silver salt, a reducing agent, a dye-providing substance, and a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense, and the image receiving element is referred to as an image receiving member. The above heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto an image receiving layer of an image receiving member provided on the same support or another independent support. , image sharpness,
In terms of stability and other aspects, it has been improved in many respects compared to previous heat-developable color photosensitive materials. However, the above heat-developable photosensitive materials also have the following problems. <Problems with the prior art> Photosensitive silver halide usually has the property of being sensitive to ultraviolet rays, which causes noise in areas other than the desired photosensitive area, causing color turbidity and reducing contrast. I don't like it. When a photosensitive material is exposed to light, a lens is used between the light source and the photosensitive material. Generally, lenses are coated with a UV absorber or a UV absorbing filter is used, but lenses and filters do not necessarily have the same UV absorption characteristics, so differences may appear in the finish of the photosensitive material. do. Furthermore, ultraviolet rays generated by static electricity during the production or use of photosensitive materials can also cause significant damage to photosensitive materials. Therefore, ultraviolet absorbers are essential in photosensitive materials. Now, in the case of heat-developable photosensitive materials as well, the addition of an ultraviolet absorber effectively prevents color clouding, contrast deterioration, and static marks caused by unnecessary ultraviolet rays. However, due to exposure to a high-temperature atmosphere during thermal development, sweat (bleed-out) occurs on the surface of the photosensitive element from the layer containing the ultraviolet absorber.
However, in the case of transfer-type heat-developable color photosensitive materials, it adheres unevenly to the surface of the image-receiving element, contaminating the surface of the image-formed image-receiving layer. There is. <Object of the present invention> Therefore, an object of the present invention is to provide a heat-developable photosensitive material in which sweating of an ultraviolet absorber is prevented. <Structure of the Invention> The above objects of the present invention are achieved by a photothermographic material containing an ultraviolet absorber and an organic fluoro compound. [Specific structure of the invention] In the present invention, an ultraviolet absorber is a compound that has absorption (preferably maximum absorption) in the ultraviolet region, particularly in the region of 250 nm to 400 nm, and preferably has no absorption in the visible region. . In order to absorb ultraviolet rays more effectively, the molecular extinction coefficient at maximum absorption is large, usually 5000 or more, preferably 10000 or more,
Particularly preferably 20,000 or more. All known UV absorbers can be used, but effective ones include benzophenone compounds (e.g., JP-A No. 46-2784, U.S. Pat.
3215530, 3698907), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), 4-thiazolidone compounds (e.g.,
(described in U.S. Pat.
No. 1687, No. 42-26187, No. 44-29620, No. 48-
41572, JP-A No. 54-95233, JP-A No. 57-142975,
U.S. Patent No. 3253921, U.S. Patent No. 3533794, U.S. Patent No. 3754919
No. 3794493, No. 4009038, No. 4220711,
4323633, Research Disclosure No. 22519),
benzoxide compounds (e.g., U.S. Pat. No.
3700455), cinnamate ester compounds (e.g., U.S. Pat. No. 3705805, U.S. Pat. No. 3707375)
No. 52-49029), methine compounds (e.g., U.S. Pat. No. 3,629,274, U.S. Pat. No. 3,652,284)
(described in JP-A-54-111826 and JP-A-56-27146) can be used. Furthermore, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. UV-absorbing couplers (e.g., α-naphthol cyan dye-forming couplers) and UV-absorbing polymers (e.g.,
JP-A-58-111942, JP-A No. 178351, JP-A No. 181041,
No. 59-19945, No. 23344, as stated in the official gazette)
etc. can be used. Among these, those particularly effective in the present invention are benzotriazole compounds, benzophenone compounds and methine compounds. The respective general formulas and specific compound examples are shown below, but the invention is not limited thereto. <General formula of benzotriazole compound> General formula () In the formula, R ₁ to _{R 8} are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, butyl group, t-butyl group, sec
-butyl group, t-amyl group, t-octyl group, 2
-ethylhexyl group, n-dodecyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, pentyloxy group, sec-octyloxy group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, etc.), acyl group (eg, acetyl group, heptanoyl group, benzoyl group, etc.), or nitro group. Specific examples of the benzotriazole compound represented by the general formula () are shown below, but the invention is not limited thereto. UV-1 UV-2 UV-3 UV-4 UV-5 UV-6 UV-7 UV-8 UV-9 UV−10 UV−11 UV-12 UV−13 UV-14 UV-15 UV-16 UV−17 UV−18 UV−19 UV−20 UV−21 UV−22 UV−23 UV−24 UV−25 UV−26 UV−27 UV−28 UV−29 UV-30 UV−31 UV-32 UV−33 <General formula of benzophenone compound> General formula () In the formula, R ₉ to _{R 17} are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, butyl group, t-butyl group, sec
-butyl group, t-amyl group, t-octyl group, 2
-ethylhexyl group, n-dodecyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, pentyloxy group, sec-octyloxy group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, etc.), acyl group (eg, acetyl group, heptanoyl group, benzoyl group, etc.), or nitro group. Specific examples of the benzophenone compound represented by the general formula () are shown below, but the invention is not limited thereto. UV−34 UV-35 UV−36 UV−37 UV−38 UV−39 UV-40 UV-41 UV−42 UV−43 UV−44 UV−45 UV−46 UV−47 UV−48 UV−49 <General formula of methine compound> General formula () In the formula, _R18 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
isopropyl group, butyl group, hexyl group, octyl group, etc.), aryl group (eg, phenyl group, chlorophenyl group, tolyl group, etc.), or aralkyl group (eg, benzyl group, phenylethyl group, etc.). _R19 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (e.g., methyl group, sulfoethyl group, carboxyethyl group, hydroxypropyl group, sulfopropyl group, sulfobutyl group, carboxybutyl group,
hexyl group, octyl group, dodecyl group, ethyl group, methylol group, etc.) or substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.). R ₂₀ and R ₂₁ are respectively −CN, −SO ₂ R ₂₂ −
SO ₃ R ₂₃ , −COOR ₂₄ , −CONR ₂₅ R ₂₆ or −
Indicates COR ₂₇ . Here, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₇ each represent an alkyl group or an aryl group having 1 to 18 carbon atoms. R ₂₅ and R ₂₆ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group. Z represents a nonmetallic atomic group necessary to form a nitrogen-containing 5- to 6-membered ring. Examples of the nitrogen-containing 5- to 6-membered ring include thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, thiazoline, thiazolidine, 2-pyridine, 4-pyridine, 2- Quinoline, 4-quinoline, 1-isoquinoline, 3-
The cores include isoquinoline, indolenine, imidazole, benzimidazole, naphthimidazole, pyrrolidine, and oxazoline. m and n represent 1 or 2. Specific examples of the methine compound represented by the general formula () are shown below, but the invention is not limited thereto. UV−50 UV−51 UV−52 UV−53 UV−54 UV−55 UV−56 UV−57 UV−58 UV−59 UV−60 UV−61 UV−62 UV−63 UV−64 UV−65 UV−66 UV−67 UV−68 UV−69 UV−70 In the present invention, two or more different types of ultraviolet absorbers can be used in combination, and it is preferable to use them in combination. In the present invention, the amount of the ultraviolet absorber added is 0.001 parts by weight of the binder in the layer containing it.
~2 parts by weight, preferably 0.01 to 1 part by weight. There are no restrictions on the method of adding the ultraviolet absorber of the present invention, including adding it as a solution in water or an organic solvent, adding it as a powder or suspension by grinding it with a ball mill or sand mill, dissolving it in a high boiling point solvent, There are methods such as adding it as an oil-in-water emulsion. The organic fluoro compound used in the present invention is a compound having at least 1, preferably 3 or more fluorine atoms and at least 1, preferably 3 or more carbon atoms in the molecule, and has a main chain or It also includes polymer compounds having fluorine atoms and carbon atoms in their side chains. For organic fluoro compounds, U.S. Pat.
No. 3589906, No. 3666478, No. 3754924, No.
No. 3775126, No. 3850640, West German Patent Publication No.
No. 1942665, No. 1961638, No. 2124262, British Patent No. 1330356, Belgian Patent No. 742680, Japanese Patent Application Publication No. 46-7781, No. 48-9715, No. 49-46733,
No. 49-133023, No. 50-99529, No. 50-113221
No. 50-160034, No. 51-43131, No. 51-
No. 129229, No. 51-106419, No. 53-84712, No. 53-84712, No.
No. 54-111330, No. 56-109336, No. 59-30536,
No. 59-45441, Special Publication No. 47-9303, No. 48-43130
No. 59-5887, etc., and these can be used. Specific compound examples are shown below.

[Table] ｜

C ₂ F ₅

【table】
\

CH ₂ CH ₃

【table】

【table】

[Table] The organic fluoro compounds used in the present invention are, for example, U.S. Pat.
Same No. 2732398, No. 2764602, No. 2806866, Same No.
No. 2809998, No. 2915376, No. 2915528, No. 2915528, No. 2915376, No. 2915528, No.
No. 2934450, No. 2937098, No. 2957031, No. 2934450, No. 2937098, No. 2957031, No.
No. 3472894, No. 3555089, Special Publication No. 1973-37304,
Specifications of JP-A-47-9613, Journal of the British Chemical Society (J.
Chem.Soc.), 1950, 2789; 1957, 2574
Pages and 2640 pages; Journal of the American Chemical Society (J.Amer.Chem.
Coc.), Vol. 79, p. 2549 (1957); and J. Japan Oil Chmist's Soc., Vol. 12, p. 653. In the present invention, the amount of the organic fluoro compound added is 0.1 mg to 10 g, preferably 1.0 mg to 1.0 g, per 1 m ² of the light-sensitive material. In the present invention, two or more organic fluoro compounds may be used in combination. There are no restrictions on the method of adding the organic fluoro compound of the present invention, such as adding it as a solution in water or an organic solvent, adding it as a powder or suspension by grinding it with a ball mill, sand mill, etc., dissolving it in a high boiling point solvent, There are methods such as adding it as an oil-in-water emulsion. In the present invention, the ultraviolet absorber and the organic fluoro compound interact with each other, for example, the ultraviolet absorber is contained in a layer close to the support from the surface, and the photosensitive material is It may be added to any layer as long as it is in a positional relationship such that it comes into contact with the organic fluoro compound before it bleeds out to the surface of the organic fluoro compound, but preferably both are added to the same layer. In addition to the heat-developable photosensitive layer, the layer to be added may be any non-photosensitive layer such as a subbing layer, a backing layer, an intermediate layer, or a protective layer. Among these, the protective layer and the subbing layer are preferable, and A protective layer is most preferred.
The protective layer may be divided into two or more layers, and the ultraviolet absorber of the present invention and the organic fluoro compound may be added in combination to at least one of the layers. The protective layer (hereinafter referred to as the protective layer of the present invention) as the preferred embodiment will be described. Various additives used in the photographic field can be used in the protective layer of the present invention. The additives include various matting agents, colloidal silica, slipping agents, antistatic agents, high boiling point organic solvents, antioxidants,
Examples include hydroquinone derivatives, polymer latexes, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), organic silver salt particles, non-photosensitive silver halide particles, and the like. The matting agent used in the protective layer of the present invention is fine particles of inorganic or organic substances that are incorporated into a heat-developable photosensitive material to increase the roughness of the surface of the photosensitive material and make it matte. It is. The method of using a matting agent to prevent adhesion that occurs during manufacturing, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and peeling between materials of the same or different kind is currently available. Well known in the industry. Specific examples of matte agents include JP-A-50-46316
Silicon dioxide described in JP-A-53-7231, JP-A No. 58
-66937, alkali-soluble matting agents such as alkyl methacrylate/methacrylic acid copolymers described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341, JP-A-58-166341; Akira
58-145935, a combination of two or more types of fine particle powders with different Mohs hardnesses, a combination of oil droplets and fine particle powders as described in JP-A-58-147734, and an average particle size as described in JP-A-59-149356. A combination of two or more types of spherical matting agents with different properties, a combination of a fluorinated surfactant and a matting agent described in JP-A No. 56-44411, and a combination of a matting agent with a fluorinated surfactant described in JP-A-56-44411, as well as
1055713, U.S. Patent No. 1939213, U.S. Patent No. 2221873,
Same No. 2268662, No. 2322037, No. 2376005, Same No.
No. 2391181, No. 2701245, No. 2992101, No.
No. 3079257, No. 3262782, No. 3443946, No. 3079257, No. 3262782, No. 3443946, No.
No. 3516832, No. 3539344, No. 3591379, No.
No. 3754924, No. 3767448, JP-A-49-106821,
Organic matting agents described in No. 57-14835, etc.
West German Patent No. 2529321, British Patent No. 760775,
1260772, US Patent No. 1201905, US Patent No. 2192241,
Same No. 3053662, No. 3062649, No. 3257206, Same No.
No. 3322555, No. 3353958, No. 3370951, No.
No. 3411907, No. 3437484, No. 3523022, No. 3411907, No. 3437484, No. 3523022, No.
No. 3615554, No. 3635714, No. 3769020, No. 3615554, No. 3635714, No. 3769020, No.
Inorganic matting agents described in No. 4021245, No. 4029504, etc., or JP-A-46-7781, No. 49-
No. 106821, No. 51-6017, No. 53-116143, No. 53
−100226, No. 57-14835, No. 57-82832, No.
No. 53-70426, No. 59-149357, Special Publication No. 57-9053
Matting agents and the like having physical properties as described in Japanese Patent Publication No. 1, EP-107378, etc. are preferably used. In the protective layer of the present invention, the amount of matting agent added is preferably 10 mg to 2.0 g, more preferably 20 mg to 1.0 g per ^{square meter} . The particle size of the matte agent is 0.5~
The thickness is preferably 10 μm, more preferably 1.0 to 6 μm. The matting agent may be used in combination of two or more types. Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, examples include French Patent No. 2180465 and British Patent No.
No.955061, No.1143118, No.1270578, No.955061, No.1143118, No.1270578, No.
No. 1320564, No. 1320757, JP-A-49-5017, No.
No. 51-141623, No. 54-159221, No. 56-81841,
Research Disclosure
Disclosure) No. 13969, U.S. Patent No. 1263722,
No. 2588765, No. 2739891, No. 3018178, No. 2588765, No. 2739891, No. 3018178, No.
No. 3042522, No. 3080317, No. 3082087, No.
No. 3121060, No. 3222178, No. 3295979, No. 3295979, No.
No. 3489567, No. 3516832, No. 3658573, No.
Those described in No. 3679411, No. 3870521, etc. can be preferably used. The protective layer of the present invention contains a high boiling point organic solvent [for example, US Pat.
No. 2322027, No. 2533514, No. 2882157, Tokko Akira
46-23233, British Patent No. 958441, British Patent No. 1222753
No. 2,353,262, U.S. Pat. No. 3,676,142, U.S. Pat.
No. 3700454, Japanese Patent Publication No. 50-82078, No. 51-27921,
51-141623 etc., esters (e.g. phthalate esters, phosphate esters, fatty acid esters, etc.), amides (e.g. fatty acid amides,
(sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ] may contain oil droplets obtained by emulsifying and dispersing a water-soluble oily compound in water. Furthermore, these oil droplets may contain photographic additives for various purposes. Binders used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate,
One or more synthetic or natural polymeric substances such as cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, polyacrylamide, gelatin, and phthalated gelatin can be used in combination. In particular, gelatin (including gelatin derivatives),
Polyvinylpyrrolidone (preferably molecular weight 1000-400000), polyvinyl alcohol (molecular weight 1000-400000)
100,000) and polyoxazoline (molecular weight is preferably 1,000 to 800,000) alone or in combination of two or more of these binders are preferred, and gelatin alone or gelatin is compatible with gelatin such as polyvinylpyrrolidone, polyvinyl alcohol, and polyoxazoline. Particularly preferred is a binder in which a hydrophilic polymer with good properties is used. The gelatin may be lime-treated, acid-treated, or ion-exchange treated, and may be ossein gelatin, pitguskin gelatin, hyde gelatin, or modified gelatin obtained by esterifying, phenylcarbamoylating, etc. Also good. The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers. Further, in order to increase film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using it in the protective layer, only the degree of hardness of the protective layer can be made greater than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners, such as those disclosed in US Pat. Nos. 3057723 and 3396029.
Hardeners described in JP-A No. 4161407, JP-A No. 58-50528, etc. can be used. Another way to control the degree of hardening for each layer is to include a diffusible hardener (for example, a vinyl sulfone hardener) only in the protective layer, or to make the content of the protective layer higher than that of the photosensitive layer. The hardness of the protective layer can be made higher than that of the photosensitive layer by quickly drying the protective layer after simultaneous multi-layer coating. The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) in one heat-developable photosensitive layer.
It is preferable to contain a reducing agent, (3) a dye-providing substance, (4) a binder, and further contain (5) an organic silver salt if necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example,
The heat-developable photosensitive layer is divided into two layers, and the above (1), (2), (4),
The component (5) is contained in the heat-developable photosensitive layer on one side,
The dye-providing substance (3) may be contained separately in two or more constituent layers as long as they can react with each other, such as by containing the dye-providing substance (3) in the layer on the other side adjacent to this photosensitive layer. In addition, the heat-developable photosensitive layer is divided into a high-sensitivity layer and a low-sensitivity layer.
It may be divided into two or more layers, such as a high concentration layer and a low concentration layer. The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, it generally has three heat-developable photosensitive layers with different color sensitivities, and each photosensitive layer forms or releases dyes with different hues upon heat development.
Typically, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer. The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. There is a structure in which a green-sensitive layer, a red-sensitive layer is formed, or a structure in which a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer are sequentially formed on a support. In addition to the heat-developable photosensitive layer, the photothermographic material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied. That is, there are methods and apparatuses for the dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method, bead method, extrusion method, stretch flow method, curtain method, and the like. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as a single jet method or a double jet method. For example, JP-A-54-48521
By applying the method described in the above publication, monodisperse silver halide grains can be obtained by a double jet method while keeping pAg constant. At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, PH, pAg, temperature, etc. According to a further preferred embodiment, silver halide emulsions having silver halide grains with shells can be used. Silver halide grains having shells can be obtained by sequentially growing shells on a core of silver halide grains having good monodispersity using the method described above. The monodisperse silver halide emulsion referred to in the present invention is
An emulsion having a particle size distribution in which the variation in size of silver halide grains contained in the emulsion is not more than a certain ratio with respect to the average grain size as shown below.
Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with a uniform grain morphology and small variation in grain size is almost a normal distribution, the standard deviation can be easily determined. When the width of the distribution is defined by the relational expression standard deviation/average grain size x 100 = width of distribution (%), the width of the distribution of the silver halide grains used in the present invention is 15% or less. The monodispersity is preferably 10% or less, and more preferably 10% or less. Also, for example, JP-A-58-111933, JP-A No. 58-111933;
As described in No. 111934, No. 58-108526, Research Disclosure No. 22534, etc.
A particle that has two parallel crystal planes, and each of these crystal planes has a larger area than other single crystals of this particle, and its aspect ratio, that is,
Silver halide emulsions comprising tabular silver halide grains having a grain diameter to thickness ratio of 5:1 or more can also be used. Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. Regarding internal latent image type silver halide whose surface is not fogged in advance, for example, US Pat. No. 2,592,250, US Pat.
No. 3317322, No. 3511662, No. 3447927,
As described in No. 3761266, No. 3703584, No. 3736140, etc., it is a silver halide grain in which the sensitivity inside the grain is higher than the sensitivity on the surface of the grain. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above-mentioned patent, for example, by first preparing AgCl grains and then adding bromide or a small amount of iodide thereto. A method in which a central core of chemically sensitized silver halide is coated with non-chemically sensitized silver halide, or a chemically sensitized coarse grain emulsion and a chemically sensitized coarse grain emulsion are used. Alternatively, many methods are known, such as a method in which a fine grain emulsion that is not chemically sensitized is mixed and the fine grain emulsion is deposited on a coarse grain emulsion. Furthermore, silver halide emulsions having silver halide grains containing polyvalent metal ions as described in U.S. Pat. No. 3,271,157, U.S. Pat.
A silver halide emulsion in which the grain surface of silver halide grains containing a doping agent is weakly chemically sensitized as described in No. 3761276, or as described in JP-A-50-8524 and JP-A-50-38525, etc. These include silver halide emulsions consisting of grains having a layered structure, and other silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm,
More preferably, it is about 0.01 μm to about 0.5 μm. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an _NH4 group, or a metal atom, and X represents Cl, Br). or represents I,
n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. As a metal atom,
Lithium, sodium, potassium, rubidium,
cesium, copper, gold, beryllium, magnesium,
Calcium, strontium, barium, zinc,
cadmium, mercury, aluminum, indium,
Lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium,
Examples include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g.
K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ , (NH ₄ ) ₂ IrCl ₆ ,
(NH ₄ ) ₃ IrCl, (NH ₄ ) ₂ RuCl ₆ , (NH ₄ ) ₃ RuCl,
(NH ₄ ) ₂ RhCl ₆ , (NH ₄ ) ₃ RhBr, etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium) Bromide-like 4
ammonium halides, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform , bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide,
N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo- 4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amounts used are as ^follows :
The amount is preferably 0.001 g to 50 g, more preferably 0.1 g to 10 g. The heat-developable photosensitive material of the present invention has blue light, green light,
It is also possible to have a multilayer structure including each layer having sensitivity to red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. In addition, two or more photosensitive layers of the same color (for example, a high-sensitivity layer and a low-sensitivity layer)
It can also be divided into two. In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with alkyl groups, alkylene groups, phenyl groups, carboxyalkyl groups, sulfoalkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, alkylamine groups or heterocyclic nuclei. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat.
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these sensitizing dyes added is 1×10 ^-4 per mole of photosensitive silver halide or silver halide forming component.
mol to 1 mol. More preferably, 1×10 ⁻⁴
The amount is from 1×10 −1 mol to 1×10 ⁻¹ mol. In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publication No. 43-4921 and Japanese Patent Application Laid-Open No. 49-52626.
No. 52-141222, No. 53-36224 and No. 53
Publications such as −37610 and U.S. Patent No. 3330633
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle as described in the specifications of No. 3794496, No. 4105451, etc.
For example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, α-(1-phenyltetrazolthio)
Silver aromatic carboxylates such as silver acetate, such as silver benzoate, silver phthalate, etc.,
No. 45-12700, No. 45-18416, No. 45-22185,
JP-A-52-137321, JP-A-58-118638, JP-A-58
There are silver salts of imino groups described in publications such as No. 118639 and US Pat. No. 4,123,274. Examples of silver salts of imino groups include silver benztriazole. The benztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include:
For example, alkyl-substituted benztriazole silver (preferably substituted with a _C22 or less alkyl group, more preferably a _C4 or less alkyl group, such as methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.) ), silver alkylamidobenztriazole (preferably substituted with an alkylamide group of up to _C22 , e.g. silver acetamidobenztriazole, silver propionamidobenztriazole, silver iso-butylamidobenztriazole,
silver laurylamide benztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably substituted with an alkylsulfamoyl group of C ₂₂ or less, for example, silver 4-(N,N-diethylsulfamoyl)benztriazole) , 4-
(N-propylsulfamoyl)benztriazole silver, 4-(N-octylsulfamoyl)benztriazole silver, 4-(N-decylsulfamoyl)benztriazole silver, 5-(N-octylsulfamoyl) benztriazole silver, etc.),
Silver salts of halogen-substituted benztriazoles (for example, silver 5-chlorobenztriazole, silver 5-bromobenztriazole, etc.), silver alkoxybenztriazole (preferably an alkoxy group of C ₂₂ or less, more preferably an alkoxy group of C ₄ or less) silver 5-methoxybenztriazole, silver 5-ethoxybenztriazole, etc.), silver 5-nitrobenztriazole, silver 5-aminobenztriazole, silver 4-hydroxybenztriazole, silver 5-carboxybenztriazole, 4-Sulfobenztriazole silver, 5
-silver sulfobenztriazole, and the like. Examples of other imino group-containing silver salts include imidazole silver, benzimidazole silver, 6
- nitrobenzimidazole silver, pyrazole silver,
urazole silver, 1,2,4-triazole silver,
Silver salts of other mercapto compounds such as 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, satucalin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzoxazole silver, mercaptooxadi Azole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-
Mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,
Examples include 3,3a,7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4.6-pentazaindene silver. In addition, a silver complex compound having a stability constant of 4.5 to 10.0 as described in JP-A-52-31728, a silver salt of imidazolinthion as described in US Pat. No. 4,168,980, and the like can be used. Among the above organic silver salts, imino group silver salts are preferable, particularly silver salts of benzotriazole derivatives,
More preferred are 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives. The organic silver salts used in the present invention may be used alone or in combination of two or more. Further, a silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated salt may be dispersed in a binder by an appropriate means and used. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like. In addition, the method for preparing organic silver salts is generally to dissolve silver nitrate and raw organic compounds in water or an organic solvent and mix them, but if necessary, a binder may be added or a solution such as sodium hydroxide may be added. Adding alkali to promote the dissolution of organic compounds,
It is also effective to use an ammoniacal silver nitrate solution. The amount of the organic silver salt used is usually 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol of photosensitive silver halide. More preferably, it is 0.3 to 30 mol. As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used. The dye-providing substance used in the heat-developable photosensitive material of the present invention is, for example, JP-A-57-186744;
No. 58-79247, No. 58-149046, No. 58-149047
No. 59-124339, No. 59-181345, No. 60-
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent such as that disclosed in No. 2950, it may be used as a reducing agent in the present invention. For example, US Pat. No. 3,531,286, US Pat. No. 3,761,270,
3764328 specifications, RD No. 12146, and the same No.
15108, No. 15127 and JP-A-56-27132, p-phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenol type, sulfonamide phenol type developing agents, sulfonamide aniline type developing agents A developing agent, a hydrazone color developing agent, etc. can be used. Also, U.S. Patent No. 3342599, U.S. Patent No. 3719492
Color developing agent precursors described in Japanese Patent Application Laid-Open Nos. 53-135628 and 54-79035 can also be advantageously used. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (1) described in No. General formula (1) In the formula, R ¹ and R ² each have a hydrogen atom or a carbon atom number of 1 to 30 (preferably 1), which may have a substituent.
-4) represents an alkyl group, and R ¹ and R ² may be ring-closed to form a heterocycle. R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, halogen atoms, hydroxy groups,
Represents an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R ³ and R ¹ And R ⁵ and R ² may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming an inorganic salt and a salt, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, sulfate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxide compounds of nitrogen compounds having a tetravalent covalent bond. Next, preferred specific examples of the reducing agent represented by the general formula (1) are shown below. (R-1) (R-2) (R-3) (R-4) (R-5) (R-6) (R-7) (R-8) (R-9) (R-10) (R-11) (R-12) (R-13) (R-14) (R-15) (R-16) (R-17) (R-18) (R-19) (R-20) (R-21) (R-22) (R-23) The reducing agent represented by the above general formula (1) can be prepared by a known method, for example, Heuben-Beil, Methodology, Band XI/2.
(Houben-Weyl, Methoden der Organischen
Chemie, Band XI/2), pages 645-703. Furthermore, it is also possible to use two or more of the above-mentioned reducing agents at the same time, or to use a black and white developing agent described below in combination for the purpose of increasing developability. Moreover, the dye-donating substance used in the present invention is
-152440, 59-154445, etc., compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc. (or In the case where only a silver image is simply obtained, a developing agent as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1′ -dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-
tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-5
-methylphenyl)-4-methylphenol, α
-phenyl-α,α-bis(2-hydroxy-3
-tert-butyl-5-methylphenyl)methane,
1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,
5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy- 3,5
-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. These developing agents mentioned above can also be used alone or in combination of two or more. The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide, the type of organic acid silver salt, and the type of other additives used, but usually is in the range of 0.01 to 1500 mol, preferably 0.1 to 200 mol, per 1 mol of photosensitive silver halide. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-59-229556. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including graft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1000
~400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates, vinyl imidazoles, (meth)acrylamides, Examples include vinyl monomers such as vinyl carbinols and vinyl alkyl ethers, but at least
It is preferable that 20% (weight %, same hereinafter) is polyvinylpyrrolidone. Preferred examples of such copolymers have a molecular weight of 5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pitgskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances used include polyvinyl alcohol,
polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol,
Examples include proteins such as polyethylene glycol esters or cellulose derivatives, and natural substances such as polysaccharides such as starch and gum arabic. These may be contained in an amount of 0 to 85%, preferably 0 to 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05 g to 50 g per layer per m ² of support, preferably
It is 0.1g to 10g. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of the dye-providing substance. Examples of the support used in the heat-developable photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coated paper. Examples include paper supports, and supports obtained by coating and curing an electron beam curable resin composition on these supports. When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, various heat solvents are preferably added to the photothermographic material and/or the image receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. These compounds are described in, for example, US Pat. No. 3,347,675, US Pat. No. 3,667,959, Research Disclosure No.
Examples include organic compounds having polarity such as those described in Japanese Patent Application No. 59-229556 and Japanese Patent Application No. 59-47787, and those particularly useful in the present invention include, for example, urea derivatives (e.g., dimethylurea, diethylurea, etc.). , phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-pentanediol,
1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycols. Among the above thermal solvents, water-insoluble solid thermal solvents described below are more preferably used. A water-insoluble solid thermal solvent is a compound that is solid at room temperature but becomes liquid at high temperatures (60°C or higher, preferably 100°C or higher, particularly preferably 130°C or higher and 250°C or lower), and is an inorganic/organic compound. The ratio of
3.0, preferably 0.7 to 2.5, particularly preferably 1.0 to
It is a compound in the range of 2.0, and the solubility in water at room temperature is less than 1. Specific examples of water-insoluble solid thermal solvents are shown below.
Not limited to these.

【table】

【table】

【table】

[Table] Many compounds used as water-insoluble solid heat solvents are commercially available, and can be easily synthesized by those skilled in the art. The method of adding the water-insoluble heat solvent is not particularly limited, but
There are methods such as adding by pulverizing and dispersing using a ball mill, sand mill, etc., adding by dissolving in a suitable solvent, and adding by dissolving in a high boiling point solvent and adding as an oil-in-water dispersion. It is preferable to pulverize and disperse the solid particles using a sand mill or the like and add them while maintaining the solid particle shape. Layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image-receiving layer of an image-receiving member, and the like, so that the respective effects can be obtained. The amount of water-insoluble heat solvent added is usually 10% to 500% by weight, preferably 50% to 50% by weight of the binder amount.
It is 300% by weight. In addition, even if the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the heat development temperature, the melting point will be lowered by being added to the binder.
It can be effectively used as a thermal solvent. The photothermographic material of the present invention may contain various additives in addition to the above-mentioned components, if necessary. For example, melt formers such as acetamide and succinimide described in U.S. Patent No. 3,438,776, compounds such as polyalkylene glycols described in U.S. Pat. There are non-aqueous polar organic compounds having a melting point of 20°C or higher, such as lactones having -CO-, _-SO2- , and -SO- groups. Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829, JP-A-53-
Phenol derivatives described in No. 60223, JP-A-Sho
Carboxylic acids described in No. 58-118640, JP-A-Sho
Examples include polyhydric alcohols described in No. 58-198038 and sulfamoylamide compounds described in JP-A No. 59-84236. Further, a color toning agent known in heat-developable photosensitive materials may be added as a development accelerator to the photothermographic material of the present invention. As a coloring agent,
For example, JP-A No. 46-4928, No. 46-6077, No. 49-
No. 5019, No. 49-5020, No. 49-91215, No. 49-
No. 107727, No. 50-2524, No. 50-67132, No. 50
−67641, No. 50-114217, No. 52-33722, No.
No. 52-99813, No. 53-1020, No. 53-55115, No. 53-55115, No.
No. 53-76020, No. 53-125014, No. 54-156523,
No. 54-156524, No. 54-156525, No. 54-156526
No. 55-4060, No. 55-4061, No. 55-32015
Publications such as No. 2140406 and West German Patent No. 2140406,
No. 2141063, No. 2220618, U.S. Patent No. 3847612,
No. 3782941, No. 4201582 and JP-A-57-
No. 207244, No. 57-207245, No. 58-189628, No. 58-189628, No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,
3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, aminomercaptotriazole, acylaminomercaptotriazole, phthalic acid, naphthalic acid, phthalamic acid, etc.
A mixture of one or more of these and an imidazole compound, a mixture of at least one acid or acid anhydride such as phthalic acid or naphthalic acid, or a phthalazine compound, furthermore, a mixture of phthalazine and maleic acid, itaconic acid, or quinoline. Examples include combinations of acids, gentisic acid, and the like. As an antifoggant, for example, US Pat.
Higher fatty acids (e.g. behenic acid, stearic acid, etc.) described in Japanese Patent Publication No. 3645739, mercuric salts described in Japanese Patent Publication No. 11113-1983, N-halogen compounds described in Japanese Patent Application Laid-open No. 47419-1983 (e.g. -halogenoacetamide, N-halogenosuccinimide, etc.), mercapto compound-releasing compounds described in U.S. Pat. oxidants (e.g. perchlorates, inorganic oxides, persulfates, etc.), sulfinic acids or thiosulfonic acids described in No. 53-19825, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, 51- No. 42529, No. 51-81124, No. 42529, No. 51-81124, No.
Disulfide and polysulfide compounds described in No. 55-93149, rosins or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxyl groups or sulfonic acid groups described in No. 51-104338. 1,2,4-triazole or 5-triazole as described in JP-A-54-51821 and U.S. Pat. No. 4,137,079;
Mercapto-1,2,4-triazole, 55-
Thiosulfinate esters described in No. 140833,
1,2,3,4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-57233,
Examples include dihalogen compounds or trihalogen compounds described in No. 59-57234, and thiol compounds described in No. 59-111636. In addition, as other anti-fogging agents,
Hydroquinone derivatives described in No. 56506 (e.g.
di-t-octylhydroquinone, dodecanylhydroquinone, etc.), hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole,
-carboxybenzotriazole, etc.) can be preferably used in combination. As a silver image stabilizer, U.S. Patent No. 3707377
5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768071, JP-A No. 768071; Monohalo compounds (e.g., 2-bromo-2-tolylsulfonylacetamide, etc.) described in JP-A-50-119624, bromine compounds described in JP-A-50-120328 (e.g., 2-bromomethylsulfonylbenzothiazole, 2, 4-bis(tribromomethyl)-6-methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, various monohalogenated organic antifoggants for silver halide emulsions described in JP-A-50-119624 can be used. Other image stabilizers include U.S. Pat.
No. 3220846, No. 4082555, No. 4088496, JP-A-Sho
50-22625, Research Disclosure (RD) No. 12021, RD No. 15168, RD No. 15567, RD No.
Compounds called activator precursors that release basic substances by heat, such as guanidinium, which releases a base by decarboxylation with heat, described in No. 15732, No. 15733, No. 15734, No. 15776, etc. Compounds such as trichloroacetate, aldnamide compounds such as galactonamide, amine imides, 2-carboxycarboxamide, etc.
In addition, phosphoric acid soda base generators described in JP-A-56-130745 and JP-A-56-132332, compounds that generate amines through intramolecular nucleophilic reactions described in British Patent No. 2079480, and JP-A-56-130745 and JP-A-56-132332 Aldoxime carbamates described in No. 59-157637, No. 59-
Hydroxamic acid carbamates etc. described in No. 166943, No. 59-180537, No. 59-174830, No. 59-174830,
Examples include base releasing agents described in No. 59-195237 and the like. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444, U.S. Patent No.
No. 3324103, No. 3844788, No. RD12035, No. 3324103, No. 3844788, No. RD12035, No.
Illithiuronium compounds, s-carbamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in US Pat.
No. 4012260, No. 4060420, No. 4207392,
Activator stabilizer and nitrogen-containing organic base called activator stabilizer precursor described in RD15109 and RD17711, etc., such as α-sulfonylacetate or trichloroacetate of 2-aminothiazoline, acylhydrazine compound, etc., are developed. It can be used for the purpose of promoting or for stabilizing the image. Also, for example, JP-A-56-130745, JP-A No. 59-
Development may be carried out in the presence of a small amount of water as described in No. 218443, or water may be supplied by spraying a small amount of water or applying a certain amount of water before heating.
As described in US Pat. No. 3,312,550 and the like, development may be performed using hot steam, hot air containing moisture, or the like.
Compounds that release water into the heat-developable photosensitive material, such as compounds containing water of crystallization as described in Japanese Patent Publication No. 44-26582, such as sodium phosphate dodecahydrate,
Ammonium alum 24 hydrate salt or the like may be included in the photothermographic material. In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used. In the heat-developable photosensitive material of the present invention, colloidal silica may be used in the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving film properties. can. The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main components are:
It is SiO ₂ (silicon dioxide). Regarding colloidal silica, for example, JP-A-56-109336, JP-A No. 53-
It is described in No. 123916, No. 53-112732, No. 53-100226, etc. The amount of colloidal silica used is
The dry weight ratio to the binder of the layer to be mixed and coated is preferably in the range of 0.05 to 2.0. In the heat-developable photosensitive material of the present invention, an antistatic agent can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). Antistatic agents used in the present invention include British Patent No. 1466600, Research Disclosure No. 15840, British Patent No. 16258
No. 16630, U.S. Patent No. 2327828, U.S. Pat.
No. 2861056, No. 3206312, No. 3245833, No.
No. 3428451, No. 3775126, No. 3963498, No.
No. 4025342, No. 4025463, No. 4025691, No. 4025342, No. 4025463, No. 4025691, No.
Examples include compounds described in No. 4025704, and these can be preferably used. In the heat-developable photosensitive material of the present invention, a hardening agent can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). Hardeners used in the present invention include aldehyde-based and aziridine-based hardeners (for example, PB Report
19921, U.S. Patent No. 2950197, U.S. Patent No. 2964404,
2983611, 3271175, Japanese Patent Publication No. 46-40898, and JP-A-50-91315), isoxazole type (for example, US Pat. No. 331609) ), epoxy systems (e.g. U.S. Patent No. 3047394, West German Patent No.
1085663, the specifications of British Patent No. 1033518, those described in Japanese Patent Publication No. 1983-35495), vinyl sulfones (for example, PB Report 19920, West German Patent No. 1100942, West German Patent No. 2337412, West German Patent No. 2545722, same
No. 2635518, No. 2742308, No. 2749260, British Patent No. 1251091, Patent Application No. 1974-54236, No. 48-
110996, U.S. Patent No. 3539644, and U.S. Patent No. 3490911), acryloyl type (e.g., those described in Japanese Patent Application No. 1983-27949 and U.S. Patent No. 3640720) , carbodiimide type (e.g., U.S. Pat. No. 2,938,892, U.S. Pat. No. 4,043,818,
4061499, those described in Japanese Patent Publication No. 46-38715, and Japanese Patent Application No. 15095/1983), triazone series (for example, West German Patent No. 2410973,
2553915, U.S. Patent No. 3325287, and JP-A-12722), other maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardeners are used alone. Or they can be used in combination. As a useful combination technique, for example, West German Patent Nos. 2447587 and 2505746
No. 2514245, U.S. Patent No. 4047957, U.S. Pat.
Specifications of No. 3832181 and No. 3840370, Japanese Unexamined Patent Application Publication No. 1973-
Examples include combinations described in Japanese Patent Publications No. 43319, No. 50-63062, No. 52-127329, and Japanese Patent Publication No. 32364-1983. In the heat-developable photosensitive material of the present invention, a polymer hardener can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). Examples of the polymeric hardening agent used in the present invention include polymers having aldehyde groups (e.g., acrolein copolymers) described in US Pat. No. 3,396,029, US Pat. No. 3,362,827, and Research Disclosure No. 17333. (1978), etc., polymers having dichlorotriazine groups, U.S. Patent No.
Polymers having epoxy groups as described in No. 3623878,
Research Disclosure No. 16725 (1978),
U.S. Patent No. 4161417, Japanese Patent Application Publication No. 54-65033, No. 56
Examples include a polymer having an active vinyl group or a group that can be a precursor thereof, as described in Japanese Patent Application Laid-open No. 142524, and a polymer having an active ester group, as described in JP-A-56-66841. The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.) for the purpose of improving film properties, etc.
Polymer latex can be used for this purpose. Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, poly-n-butyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of vinylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acetate and ethyl acrylate, copolymers of ethyl acrylate and 2-acrylamide, and the like. The preferred average particle size of the polymer latex is
It is 0.02 μm to 0.2 μm. The amount of polymer latex used is preferably 0.03 to 0.5 in dry weight ratio to the binder of the layer to which it is added. The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.) for the purpose of improving coating properties.
Various surfactants can be used. The surfactant used in the present invention may be any of anionic, cationic, amphoteric and nonionic surfactants. Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N- Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Those containing an acidic group are preferred. Examples of cationic surfactants include alkylamine salts, fatty acid or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. is preferred. Examples of amphoteric surfactants include amino acids,
Aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines,
Amine oxides and the like are preferred. Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl sugars Esters and the like are preferred. The heat-developable photosensitive material of the present invention includes, for the purpose of improving developability, improving image dye transferability, improving optical properties, etc.
Non-photosensitive silver halide grains can be contained in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.). The non-photosensitive silver halide grains used in the present invention may have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Can be used. The preferred particle size of the non-photosensitive silver halide grains is about 0.3 μm or less. In addition, the amount added is calculated in terms of silver amount for the layer to be added.
A range of 0.02 to 3 g/m ² is preferred. In the heat-developable photosensitive material of the present invention, for the purpose of improving film properties, a heat-developable photosensitive layer and/or a non-photosensitive layer (subbing layer, intermediate layer, protective layer, etc.) may be added, for example, to JP-A No. 51-104338. It is possible to contain vinyl polymers having carboxyl groups or sulfo groups as described in the above. The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in terms of dry weight ratio to the binder of the layer to which it is added. When the heat-developable photosensitive material of the present invention is a color type, a dye-providing substance is used. Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on its reaction form, negative-acting dye-donors that act in a positive function (i.e.
A positive dye-donor acting on a negative function (i.e., a positive dye image when using a negative-working silver halide) ) can be classified as Negative dye-donating substances are further classified as follows.

[Table] Compounds that form diffusible dyes

Claims (1)

[Claims] 1. A photothermographic material characterized by containing an ultraviolet absorber and an organic fluoro compound.