JPH11352639A - Photographic substrate, silver halide photographic sensitive material and heat developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic substrate capable of obtaining a photographic sensitive material hardly having curing tendency and excellent in workability even in the case of a roll type photographic sensitive material such as a printing photosensitive material wound into a relatively large diameter. SOLUTION: In the photographic substrate composed of a biaxially oriented polyester film consisting essentially of polyethylene naphthalate, the substrate is obtained by thermally processing while transporting and cooling the polyester film at a temp. in a range from Tg to Tg+55 deg.C for 5-60 min after an under layer is applied and dried. The substrate for photographic sensitive material, which is a substrate for the silver halide photographic sensitive material and a heat developable photographic sensitive material produced or used by being wound into a roll state, hardly having curing tendency and has excellent workability, is provided by using the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a heat-developable photographic light-sensitive material manufactured or used by being wound into a roll, and a support used for these photographic light-sensitive materials. The present invention relates to a support for photographic light-sensitive materials which is difficult to adhere to and has excellent workability.

[0002]

2. Description of the Related Art When photographic light-sensitive materials are used in various sizes, they are often used by taking out a necessary amount from a rolled form from the viewpoint of easy handling and space saving. Particularly in the printing and plate making industry, they are used in large amounts in the form of roll films. When such a roll-shaped film is used, a problem in operation is curling due to curling of the film. For example, when performing continuous cutting with an automatic roll cutter, the cut film does not overlap well if the winding of the film is strong, or there is a problem such as poor adhesion when performing close exposure with a document. I was

[0003] In recent years, with the miniaturization of the apparatus, the roll film has also tended to be compact, and the core to be wound into a roll has also been reduced in size, and there has been a strong demand for a roll film with less curl.

[0004] As a method for improving the curled curl, for example, a method for reducing the curled curl of a polyester film is disclosed in JP-A-51-16358. 30 ° C
For 0.1 to 1500 hours. Further, JP-A-6-35118 discloses that after a polyester film having a Tg of 90 ° C to 200 ° C is primed,
A method of performing heat treatment at 50 ° C. to Tg for 0.1 to 1500 hours has been proposed.

However, these methods require a long-time heat treatment at a relatively low temperature, which is inefficient in manufacturing.
In addition, when a product is manufactured in a long length, it must be heat-treated for a long time once in a roll state wound as an intermediate product, and a problem occurs in that a winding in a diameter wound in that state is attached in advance. There is. Then, when the silver halide photographic material is subsequently processed into a roll, there is a problem in that a sufficient effect cannot be obtained due to the influence of the winding previously applied by this heat treatment.

This problem is small in the case of rolled silver halide photographic light-sensitive material wound around a relatively small core diameter such as a color negative film, but is relatively large in the case of a printing photosensitive material. In the case of a roll-shaped photographic light-sensitive material wound around a diameter, the influence is large, and this is a particular problem.

Further, when heat treatment is performed in a roll state, there is a problem of deterioration of flatness and sticking between contacting surfaces, and there is a limitation in a heat treatment process.

[0008]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, an object of the present invention is to provide a roll-shaped photographic light-sensitive material having a relatively large diameter such as a printing light-sensitive material and the like. It is an object of the present invention to provide a photographic support which can be used as a photographic light-sensitive material which is hard to stick and has excellent workability.

[0009]

The above objects of the present invention are as follows. In a photographic support comprising a biaxially stretched polyester film containing polyethylene naphthalate as a main component, the support may be coated with an undercoat layer and dried, and the temperature range of Tg to Tg + 55 ° C of the polyester film may be from 5 minutes to 5 minutes. 6
A photographic support obtained by heat treatment while transporting and cooling over 0 minutes,

[0010] 2. The photographic support has an intrinsic viscosity of 0.
2. The resin according to the above item 1, wherein the resin comprises a resin obtained by mixing two or more kinds of the same or different polyesters having 3 to 1.2 and a difference in intrinsic viscosity of 0.2 to 1.0. Photographic support,

3. 3. The photographic support according to the above 2, wherein at least one of the polyester resins is polyethylene-2,6-naphthalate.

4. 4. The photographic support as described in 2 or 3, wherein a polyester resin having a lower intrinsic viscosity is mixed in an amount of 10% by weight or more and 80% by weight or less.

5. The photographic support according to any one of the above items 2 to 4, wherein both of the polyester resins are polyethylene-2,6-naphthalate.

6. A silver halide photographic light-sensitive material, wherein at least one silver halide photographic emulsion layer is provided on the photographic support according to any one of the above items 1 to 5.

[0015] 7. The problem has been solved by each of the photothermographic materials comprising at least one photothermographic layer provided on the photographic support according to any one of the above items 1 to 5.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The heat treatment according to the invention is carried out by the T
This is different from annealing treatment performed in a roll state in a temperature range of not more than g, and is a method of performing heat treatment while transporting in a temperature range higher than Tg to make it difficult to form a curl.

In the heat treatment of the present invention, the method of performing the heat treatment while transporting is not particularly limited.
The film is conveyed continuously by gripping both ends of the film with pins or clips, or by roll conveyance with a plurality of rolls or air conveyance that blows air to the film and floats it. Heat treatment is performed on one or a combination of (1) a method of blowing heated air from a plurality of slits, (2) a method of using radiant heat from an infrared heater, etc., and (3) a method of contacting with a plurality of heated rolls on both surfaces. Method.

In the heat treatment of the present invention, it is preferable to convey the film while holding it in a flat state. There is no particular limitation, but for example, the above-mentioned conveying method using pins and clips, air conveying method, and roll conveying method. And the like. The roll transport method is not completely flat because the roll is transported with a wrap angle with the film, but the film is in contact with the roll alternately and the winding direction of the film does not become one direction. In general, the film can be regarded as flat.

Further, since the heat treatment of the present invention is carried out while being conveyed, the conveyance distance becomes longer in proportion to the heat treatment time, so that problems in equipment tend to occur. Therefore, it is preferable to use a facility in which several dancer rolls are combined so as to accumulate, and adjust the transport tension appropriately, for the transport mainly performing the heat treatment. Transfer tension is 5kg
/ M to 60 kg / m. More preferably, the transport tension is more preferably 5 kg / m to 30 kg / m.

The transport tension can be adjusted by controlling the torques of the feed shaft and the take-up shaft. If the transport tension is 5 kg / m or less, wrinkling may occur or the surface of the support may be reduced. It is not preferable because the property deteriorates. If it is 60 kg / m or more, the flatness is deteriorated, the effect of improving the curl is not so much improved, and there is a risk of the support being torn.

The time required for the heat treatment of the present invention is 5 minutes to 6 minutes.
0 minutes, more preferably 10 minutes to 40 minutes. The heat treatment time can be controlled by changing the transport speed of the film or changing the length of the heat treatment zone. If the heat treatment time is less than 5 minutes, the resulting support is likely to be curled, and if the heat treatment time exceeds 60 minutes, the flatness and transparency of the support are deteriorated, and the effect of the present invention is not sufficient.

Here, the heat treatment zone means a plurality of heat treatment ovens having different set temperatures or a transfer device having a plurality of heaters along the transfer direction.
This is a transfer device capable of performing heat treatment in which the temperature of the transfer inlet portion is the highest and the temperature of the next oven or heater along the transfer direction is set to be equal to or lower than those of the preceding oven. .

In the present invention, the temperature of the heat treatment zone is set so that the temperature at the inlet is Tg to Tg + 55 ° C. of the support and the temperature at the outlet is lower than the temperature at the inlet. More preferably, the temperature at the inlet is from Tg + 5 ° C. to Tg + 35.
It is preferable to set the temperature in the range of ° C. The inlet portion temperature and the outlet temperature in the heat treatment zone are not particularly limited as long as they are within the above-mentioned temperature ranges.

It should be noted that the heat-treated film of the present invention loses its effect when the film is heated at a temperature of 100 ° C. or more for 30 seconds or more. Therefore, the heat treatment of the present invention is preferably performed after the undercoat layer is applied to the film and dried, and before the photographic photosensitive layer is applied. Specifically, after applying and drying the undercoat layer, it may be performed while being kept flat continuously, or, after winding once, installing necessary transport equipment and heating equipment. The re-transport processing may be performed. Furthermore, after applying and drying various functional layers such as a backing layer, a conductive layer, a slippery layer, and a magnetic recording layer, the same treatment as described above may be performed.

The film heat-treated as described above is cooled from near Tg to room temperature and wound up. In this case, in order to maintain the flatness of the film, it is better to cool the film to room temperature over Tg as soon as possible, and it is preferable to cool the film at a temperature of at least −10 ° C./sec.

The support thus heat-treated and cooled to room temperature and wound up is preferably spread over a core as large as possible when it is stored until it is sent to the next step. Has an outer diameter of 200 mm or more,
More preferably 300 mm or more, further preferably 40 mm or more.
0 mm or more.

The heat treatment of the present invention is more effective when performed in the presence of more water. Specifically, the relative humidity of the atmosphere in the heat treatment zone is 20% RH to 100% R.
H is preferable. More preferably, 50% RH
１００100% RH. In the case of heat treatment exceeding 100 ° C., the heating steam can be blown into the zone. Alternatively, when the heat treatment temperature is lower than 100 ° C., the same heat treatment as described above may be performed in a water bath set at the heat treatment temperature.

When the film is stored, the moisture content of the film is adjusted to 0.1.
Adjusting to 1% or less is preferable because curling during storage can be prevented. The moisture content of the film was measured using a trace moisture meter (for example, CA-05 manufactured by Mitsubishi Kasei).
It is a value obtained by measuring at a drying temperature of 150 ° C.

The polyester constituting the biaxially oriented polyester film of the present invention is not particularly limited, but is preferably a film-forming polyester having a dicarboxylic acid component and a diol component as main components. .

The main dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid,
Examples thereof include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, and phenylindanedicarboxylic acid.

Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyethoxyphenyl) propane. , Bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone,
Cyclohexanediol and the like can be mentioned.

Among the polyesters containing these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and diol components as dicarboxylic acid components from the viewpoint of transparency, mechanical strength and dimensional stability. And polyesters containing ethylene glycol and / or 1,4-cyclohexanedimethanol as main constituents.

Among them, polyesters mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and diesters of these polyesters Polyesters whose main constituent is a mixture of more than one species are preferred. Particularly preferred is a polyester containing polyethylene-2,6-naphthalate as a main component.

The intrinsic viscosity of the polyester to be mixed according to the present invention is preferably from 0.3 to 1.2. Intrinsic viscosity is 0.3
If it is less than 1, the degree of polymerization is low, so that the film formability and strength are not increased. From the above viewpoint, the more preferable intrinsic viscosity of the polyester of the present invention is 0.3 or more and 1.0 or less.

The difference in the intrinsic viscosity of the polyester to be mixed is preferably as large as possible in order to enhance the effect of the present invention. However, in order to increase the intrinsic viscosity difference, one intrinsic viscosity is increased. From the upper limit, there is necessarily a limit to that range. From the above viewpoint, the difference in intrinsic viscosity of the polyester of the present invention is preferably from 0.2 to 1.0, more preferably from 0.2 to 0.7.

The mixing ratio of the polyester resin of the present invention is such that the polyester resin having the lower intrinsic viscosity is 10% by weight or more and 8% or more.
The content is preferably 0% by weight or less, particularly preferably 10% by weight or more and 50% by weight or less.

The polyester constituting the biaxially stretched polyester film of the present invention may be further copolymerized with other copolymer components as long as the effects of the present invention are not impaired, or may be mixed with another polyester. It may be.
When another polyester resin is mixed, it is sufficient that the intrinsic viscosity difference of the present invention is satisfied between at least two of the same or different polyesters. Examples of these include the above-mentioned dicarboxylic acid component and diol component, and polyesters composed thereof.

The polyester of the present invention has an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof in order to prevent delamination during film formation. And a diol having a polyoxyalkylene group.

Among them, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid are preferable in view of polymerization reactivity of polyester and transparency of film. Compounds obtained by substituting acids and their sodium with other metals (eg, potassium, lithium, etc.), ammonium salts, phosphonium salts and the like, or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-
Preference is given to polypropylene glycol copolymers and compounds which have been converted into carboxyl groups by oxidizing the hydroxy groups at both ends thereof. The proportion copolymerized for this purpose is preferably 0.1 to 10 mol% based on the functional dicarboxylic acid constituting the polyester.

For the purpose of improving heat resistance, a bisphenol compound and a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio is preferably from 1 to 20 mol% based on the functional dicarboxylic acid constituting the polyester.

The method for synthesizing the polyester of the present invention is not particularly limited, and it can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first using a dialkyl ester as a dicarboxylic acid component, a transesterification reaction between the dicarboxylic acid component and a diol component, and heating this under reduced pressure. A transesterification method in which polymerization is performed by removing an excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added.

In each step of the synthesis, a coloring inhibitor, an antioxidant, a crystal nucleating agent, a sliding agent, a stabilizer, an anti-blocking agent, an ultraviolet absorber, a viscosity modifier, a defoaming transparent agent, an antistatic One or two or more of various additives such as an agent, a pH adjuster, a dye, and a pigment may be added.

The photographic support of the present invention may contain an antioxidant. The type of the antioxidant to be contained is not particularly limited, and various antioxidants can be used. Examples thereof include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. Can be. Above all, an antioxidant of a hindered phenol compound is preferable in terms of transparency.

The content of the antioxidant is usually from 0.01 to
It is 2% by weight, preferably 0.1-0.5%. By setting the content of the antioxidant in this range, the density of the unexposed portion of the photographic light-sensitive material is increased, so-called fogging phenomenon can be prevented, and the haze of the film can be suppressed low, so that the transparency is excellent. A photographic support is obtained. These antioxidants may be used alone or in combination of two or more.

The photographic support of the present invention may be provided with lubricity as required. The means for imparting lubricity is not particularly limited, but a method of adding external particles to add inert inorganic particles, a method of depositing internal particles to precipitate a catalyst to be added at the time of polymer polymerization, or a method of applying a surfactant to the film surface are used. The method is generally used. Among these, an internal particle precipitation method that can control the particles to be deposited relatively small is preferable because lubricity can be imparted without impairing the transparency of the film.

The thickness of the photographic support of the present invention is not particularly limited. What is necessary is just to set so that it may have required intensity | strength according to the use purpose. In particular, when it is used for medical or printing photographic materials, it is 50 to 250 μm, especially 70 to 250 μm.
It is preferably from 200 to 200 μm.

The haze of the biaxially stretched polyester film of the present invention is preferably 3% or less. More preferably, it is 1% or less. When the haze is more than 3%, when the film is used as a support for a photosensitive material,
The image becomes blurred. The haze is ASTM-D10
It is measured according to 03-52.

The Tg of the biaxially stretched polyester film of the present invention is preferably at least 90 ° C., more preferably at least 110 ° C. Tg is determined as an average value of a temperature measured by a differential scanning calorimeter (DSC) and a temperature at which the baseline starts to be shifted and a temperature at which the baseline returns to a new level.

Next, a method for producing the polyester film of the present invention will be described. A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method. For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled and solidified, and unstretched. Get a sheet. Next, the obtained unstretched sheet is subjected to Tg + 1 from the glass transition temperature (Tg) of the polyester through a plurality of roll groups and / or a heating device such as an infrared heater.
This is a method of heating in the range of 00 ° C. and longitudinally stretching. The stretching ratio is usually in the range of 2.5 to 6 times.

At this time, by making the stretching temperature different between the front and back sides of the support, it is possible to make the winding harder. More specifically, the temperature can be controlled by providing a heating means such as an infrared heater on one side during the longitudinal stretching. The temperature difference during stretching is preferably 10
C. to 40C, more preferably 15C to 30C. If the temperature difference is larger than 40 ° C., the film cannot be stretched uniformly, and the flatness of the film tends to deteriorate.

As described above, the effect of the film formed by stretching the film longitudinally at a temperature difference and forming the film so that the surface stretched at a higher temperature becomes the inside of the roll becomes more effective. .

Next, the polyester film uniaxially stretched in the machine direction obtained as described above was subjected to Tg-Tg +
In a temperature range of 120 ° C., the film is stretched in the transverse direction and then heat-set. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched film and appropriately adjusting the film to have preferable characteristics. The heat setting is then carried out at a temperature above its final transverse stretching temperature, Tg + 18
Heat fixing is usually performed within a temperature range of 0 ° C. or lower for 0.5 to 300 seconds.

Next, the undercoat layer used for the support of the present invention will be described. In general, when a hydrophobic polymer film is used as a photographic support, a necessary adhesive strength cannot be obtained even if a hydrophilic photographic emulsion layer is directly applied to the polymer film. Therefore, polymer films usually require surface treatment. Examples of such surface treatments include corona discharge treatment, ultraviolet treatment, glow discharge treatment, plasma treatment, flame treatment, and other surface activation treatments, resorcinol treatment, phenols treatment, alkali treatment, amine treatment, and trichloroacetic acid treatment. And the like. These surface treatments may or may not be performed. However, in the support of the present invention, one or more subbing layers are coated and dried, and then subjected to a specific heat treatment during coating of the emulsion layer. Is what you do.

The material which can be used in the method for applying the undercoat layer is not particularly limited, but for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride are used as starting materials. Including copolymers, polyethylene imine, polyester, polystyrene, polyurethane, epoxy resin,
Examples include grafted gelatin, nitrocellulose and the like, and mixtures thereof. Surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, ultraviolet absorbers, ultraviolet light One or more of various additives such as a stabilizer, an etching agent, a magnetic powder, and a matting agent may be contained.

Further, an antistatic layer, an easily active layer, a barrier layer, an antihalation layer, a crossover cut layer,
An ultraviolet absorbing layer, a magnetic recording layer and the like may be laminated. The method of applying these undercoat layers is not particularly limited,
Various conventionally known methods can be used. For example, air knife coater, dip coater,
Examples include a coating method such as a curtain coater, a wire bar coater, a gravure coater, and an extrusion coater, and a method of co-extrusion or lamination at the time of melt-forming a polyester film.

It is preferable that the undercoat layer of the present invention is provided with conductivity. In the present invention, the surface resistivity (23 ° C., 20% RH) on the side having the conductive layer is preferably 1 × 10 ¹² Ω or less, more preferably 5 × 10 ¹¹ Ω or less.
More preferably, it is 1 × 10 ¹¹ Ω or less.

In the support of the present invention, the conductive layer may be any layer as long as it is present on at least one side of the photographic light-sensitive material, but may be a silver halide emulsion layer or
A conductive layer may be present in the protective layer, the intermediate layer, and the photothermographic layer in the backing layer. Alternatively, at least one layer in a silver halide emulsion layer or an undercoat layer between a backing layer and a support may be a layer having conductivity.

Next, the photographic material using the support of the present invention will be described. -Photosensitive layer-The halogen composition of the silver halide in the silver halide emulsion used in the present invention is not particularly limited, but when processing is carried out with a small replenishment amount or when rapid processing is performed, pure silver chloride, 6
It is preferable to use a silver halide emulsion having a composition of silver chlorobromide containing 0 mol% or more of silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of the silver halide is 1.2 μm.
m or less, particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photochemistry and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ses), Third Edition, pp. 36-43 (1966, published by McMillan "Mcmillan").

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, a narrower particle size distribution is preferable, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles fall within a particle size range of ± 40% of the average particle size is particularly preferable.

The light-sensitive material used in the present invention comprises a silver halide emulsion of at least one silver halide emulsion layer,
Tabular grains containing tabular grains, and preferably 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used, are tabular grains having an aspect ratio of 2 or more, particularly the proportion of tabular grains. Is more preferably increased to 60% to 70%, and further to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December, 1978).

The silver halide emulsion may or may not be chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499, JP-A-50-713
No. 25, JP-A-60-150046 and the like can be preferably used.

The photographic material used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles such as benzothiozolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a37-tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. .

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion used in the present invention, but other hydrophilic colloids can also be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth)
Acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used.

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer used in the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds ( 2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin , Carboki Le group activated hardeners, etc., may be used alone or in combination. These hardeners are available from Research Disclosure.
Closure) 176, 17643 (December 1978)
Monthly issue), page 26, paragraphs A to C.

The photographic material used in the present invention contains various other additives. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

In the present invention, the compounds described below are preferably contained in the constituent layers of the photographic material. (1) Solid dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (11) SPS support Compound described in JP-A-3-54551

The above-mentioned additives and other known additives are described in, for example, Research Disclosure No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The compound types and locations described in these three research disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 page Classification page Classification page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surface activity Agents 26-27 XI 650 right 1005-6 XI antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 003~4 IX support 28 XVII 1009 XVII

-Photothermographic Photosensitive Layer- For details of the photothermographic material, see, for example, US Pat.
No. 2,904, No. 3,457,075, and D.C. "Dry Silver Photographic" by Morgan
Material) "and D.M. Morgan
n) and B. "Thermal Proc Silver System" by Shelly
essedSilver Systems) ”(Imaging Processes and Materials (Im)
aging Processes and Mater
ials) Neblette Eighth Edition, Sturge (St
urge), V.I. Walworth
h), A. Shepp Editing, Page 2, 19
1969). Among them, the present invention is characterized in that an image is formed by thermally developing a photosensitive material at 80 to 140 ° C., and no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, after the heat development processing,
The optical transmission density of the light-sensitive material containing the support at 400 nm is preferably 0.2 or less. A more preferable value of the optical transmission density is 0.02 or more and 0.2 or less.
If it is less than 0.02, the sensitivity may be too low to use.

The silver halide grains used in the present invention function as an optical sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm or less.
m to 0.1 μm, particularly preferably 0.02 μm to 0.08 μm. The term "grain size" as used herein means the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. More preferably, 3
0 or less, particularly preferably 0.1% or more and 20% or less. Monodispersity = (standard deviation of particle size) / (average value of particle size) × 1
In the invention, the silver halide grains have an average grain size of 0.1
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but it is preferable that the ratio occupied by the Miller index [100] plane is high, and this ratio is 50% or more, further 70% or more, particularly 80% or more. It is preferred that The ratio of the [100] plane of the Miller index is determined by the T.V. method using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term “tabular grains” as used herein means that the thickness in the vertical direction is h when the particle size of the square root of the projected area is r μm.
The aspect ratio = r / h in the case of μm is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958, and the desired tabular grains can be easily obtained. When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains ions or complex ions of a metal belonging to Groups 6 to 10 of the periodic table. The above metals include W, Fe, Co, Ni, Cu, Ru, Rh, P
d, Re, Os, Ir, Pt, and Au are preferred.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula. In the formula [ML ₆ ] _m , M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, -1, -2 or-.
3 is represented. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M include rhodium (Rh), ruthenium (Ru), rhenium (Re),
Iridium (Ir) and osmium (Os).

The following are specific examples of the transition metal coordination complex. _{^{1: [RhCl 6] 3- 2}} : [RuCl 6] 3- 3: [ReCl 6] 3- 4: [RuBr 6] 3- 5: [OsCl 6] 3- 6: [IrCl 6] 4- 7: _{^{[Ru (NO) Cl 5]}} 2- 8: [RuBr 4 (H 2 O)] 2- 9: [Ru (NO) (H 2 O) Cl 4] - 10: [RhCl 5 (H 2 O)] _{^{2- 11: [Re (NO)}} Cl 5] 2- 12: [Re (NO) CN 5] 2- 13: [Re (NO) ClCN 4] 2- 14: [Rh (NO) 2 Cl 4] - _{15: [Rh (NO) (} H 2 O) Cl 4] - 16: [Ru (NO) CN 5] 2- 17: [Fe (CN) 6] 3- 18: [Rh (NS) Cl 5] 2 _{^{- 19: [Os (NO)}} Cl 5] 2- 20: [Cr (NO) Cl 5] 2- 21: [Re ( ^{_{O) Cl 5] - 22:}} [Os (NS) Cl 4 (TeCN)] 2- 23: [Ru (NS) Cl 5] 2- 24: [Re (NS) Cl 4 (SeCN)] 2- 25: ^{_{[Os (NS) Cl (SCN}} ) 4] 2- 26: [Ir (NO) Cl 5] 2- 27: [Ir (NS) Cl 5] 2-

One kind of these metal ions or complex ions may be used, or two or more kinds of the same kind and different kinds of metals may be used in combination. The content of these metal ions or complex ions is generally from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, preferably from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol. × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening , May be added at any stage before and after chemical sensitization, particularly preferably at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, most preferably Is added at the stage of nucleation. During the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added, as disclosed in JP-A-63-29603.
JP-A-2-306236, JP-A-3-167545, JP-A-4-76534, JP-A-6-110146, and JP-A-5-27
As described in, for example, No. 3683, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds are
It can be added by dissolving in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). For example, an aqueous solution of a metal compound powder or a metal compound and NaCl ,
A method in which an aqueous solution in which KCl is dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or as a third aqueous solution when the silver salt solution and the halide solution are simultaneously mixed. Adding silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method of preparing a metal ion or complex in advance during silver halide preparation. There is a method in which another silver halide grain doped with ions is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the surface of the particles, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, and P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te
Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used for the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, British Patent No. 618,061 and the like. Can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . When the pH of the emulsion is 7 or more or pAg
Is maintained at 8.3 or less to effect ripening, whereby reduction sensitization can be performed. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a hetero organic acid containing a reducible silver ion source, particularly a long chain (10 to 30, preferably 15 to 25, And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
And salts thereof: organic acid salts (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (Eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid ( For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5
-Dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-
Carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thioene and 3-carboxymethyl-
4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H
-Tetrazole, 3-amino-5-benzylthio-1,
Complexes or salts of silver and a nitrogen acid selected from 2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, arachidic acid and / or stearic acid.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver.
The controlled double jet method described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.) is prepared by adding an alkali metal salt (eg, sodium hydroxide, potassium oxide, etc.) to an organic acid, and then controlled by a double jet. Then, the soap and silver nitrate are added to form crystals of the organic silver salt. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the organic silver salt particles are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm.
m to 0.5 μm is preferred. The term “monodisperse” has the same meaning as in the case of silver halide.
0. In the present invention, the organic silver salt has an average particle size of 1 μm.
It is more preferable that the particles be monodisperse particles having a particle size of m or less. Further, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the term “tabular grains” refers to a ratio of an average particle diameter to a thickness, that is, an aspect ratio (AR) represented by the following formula.
Abbreviation) means three or more. AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystal can be obtained by dispersing and pulverizing a binder, a surfactant and the like with a ball mill or the like.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g or more and 2.2 g or less per m ² in terms of silver. . With this range, a favorable image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,592,863 and Research D
No. 17029 and 29996, and include the following: Aminohydroxycyclohalken compounds (for example, 2-hydroxypiperidino-
2-cyclohexenone); aminoreductone esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N-hydroxyurea derivatives (eg, Np-methylphenyl-N-) Hydrazones of aldehydes or ketones (e.g., anthracenaldehyde phenylhydrazone); phosphamide phenols; phosphamide anilines; polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and ( 2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid);
Sulfonamidoanilines (for example, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (Eg, 1,2,3,4-tetrahydroquinoxaline); amideoxins; azines (eg, a combination of an arylcarboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzenetohydroxylamine, reductone and / Or hydrazine; hydroxanoic acids; combinations of azines and sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; Phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-
Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t)
-Butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 4,5-ethylidene, bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0091]

Embedded image In the formula, R represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms _(e.g., -C ₄ H 9, 2,4,4-trimethyl pentyl), R 'and R "1 carbon atoms 5 represents an alkyl group (for example, methyl, ethyl, t-butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0093]

Embedded image

[0094]

Embedded image

The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mole of silver.
It is 10 ^{-2 to} 10 mol, especially 1 × 10 ^{-2 to 1.5} mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (arabic). (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch,
Poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly ( Vinyl acetal) (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resin, poly (vinylidene chloride), poly (epoxide) s, poly ( Carbonates), poly (vinyl acetate), cellulose esters, and poly (amide) s. It may be hydrophilic or non-hydrophilic. In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer may be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, in order to increase the speed of thermal development, the amount of binder in the photosensitive layer is 1.5 to 10 g / m ^2.
It is preferred that More preferably, 1.7 to 8 g
/ M ² . If it is less than 1.5 / m ² , the density of the unexposed portion will increase significantly, and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and in order to prevent damage to the image after thermal development, it is preferable to provide a matting agent on the surface of the photosensitive material. The matting agent is preferably contained in a weight ratio of 0.5 to 30% based on all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starches described in U.S. Pat. No. 2,322,037, Belgian Patent 625,451 and British Patent 981,19.
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,1
An organic matting agent such as polycarbonate described in No. 69 or the like can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. Further, the matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. here,
The variation coefficient of the particle size distribution is a value represented by the following equation. (Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably photosensitive in order to achieve the object of the present invention. It is a constituent layer other than the layer, and is more preferably the outermost layer as viewed from the support.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. It is preferable that the photothermographic material contains a color toning agent which suppresses the color tone of the present invention in a state of being usually dispersed in an (organic) binder matrix.

The photothermographic material of the present invention is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or a pigment may be included in the active layer. The dye to be used may be any compound as long as it has a desired absorption in a desired wavelength range. For example, JP-A-59-6481 and JP-A-59-182436 may be used.
No. 4,271,263, U.S. Pat.
No. 4,312, European Patent Publication Nos. 533,008, 65
2,473, JP-A-2-216140, 4-34
No. 8339, No. 7-191432, No. 7-30189
The compounds described in No. 0 and the like are preferably used.

These non-photosensitive layers preferably contain the binder and the matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax and liquid paraffin.

The light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation.

It is preferable to add a toning agent to the photothermographic material of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are Research Discl
No. 17029, which includes the following: Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-
5-one, 1-phenylurazole, quinazoline, and 2,4-thiozolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt) , Mercaptans (for example, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) eardicarboximides (for example, N
-(Dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isothi
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H,
-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole,
Benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotetrazole, imidazole, oxazole, pyrazole, triazole, thiandiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine,
Pyridine, purine, quinoline or quinazolinone.
The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy (eg, For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. As the mercapto-substituted heteroaromatic compound, 2
-Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2
-Mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole, 2-mercaptoquinoline, 8-mercaptopurine, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-hydroxy -2
-Mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like, but the present invention is not limited to these.

The photothermographic material of the present invention may contain an antifoggant. What is known as the most effective antifoggant is mercury ion. Regarding the use of mercury compounds as antifoggants in photosensitive materials,
For example, it is disclosed in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Non-mercury antifoggants include, for example, US Pat.
No. 075 and 4,452,885 and JP-A-59
Antifoggants as disclosed in US Pat. No. 5,572,234 are preferred.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,999.
-C (X ₁ ) as disclosed in US Pat.
(X ₂ ) (X ₃ ) (where X ₁ and X ₂ are halogen and X
₃ is a heterocyclic compound having one or more substituents represented by hydrogen or halogen). Examples of suitable antifoggants include paragraphs [003] of JP-A-9-288328.
0] to [0036] are preferably used. As another example of the preferred antifoggant, JP-A-9-90550, paragraph [006]
2] to [0063]. Still other suitable antifoggants are described in U.S. Pat.
8,523 and UK Patent Application No. 9221383.4.
No. 9300147.7 and No. 9311790.
No. 1.

The photothermographic materials of the present invention include, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455,
Nos. 4,741,966 and 4,751,175
No. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
Section 17643 IV-A (p. 23, December 1978),
Item 1831X (August 1978, p. 437)
Or cited in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-80
No. 679 is preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and the other forming layers. The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. These additives and the other additives mentioned above are Research Disclosure Items.
17029 (pp. 9-15, June 1978) can be preferably used.

[0115]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. -Preparation of Polyester (Resin)-(PET-A) 0.05 parts by weight of magnesium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl terephthalate and 65 parts by weight of ethylene glycol, and transesterification was performed according to a conventional method. went. 0.05 parts by weight of antimony trioxide and 0.03 parts by weight of trimethyl phosphate were added to the obtained product. Next, gradually raise the temperature,
The pressure was reduced and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a polyethylene terephthalate A (PE) having an intrinsic viscosity of 0.50.
TA) was obtained.

(PET-B) In the same manner as PET-A, polyethylene terephthalate B (P
ET-B) was obtained.

(PEN-A) 122 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, ethylene glycol 69
To the parts by weight, 0.05 parts by weight of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was performed according to a conventional method. Antimony trioxide 0.0
4 parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then, gradually raise the temperature and reduce the pressure, 290 ° C,
Polymerization was performed at 0.5 mmHg to obtain polyethylene-2,6-naphthalate A (PEN-A) having an intrinsic viscosity of 0.58.

(PEN-B) Polyethylene-2,6-naphthalate B (PEN-B) having an intrinsic viscosity of 0.30 was obtained in the same manner as in PEN-A.

(PEN-C) PEN-A was heated at 130 ° C. for 2 hours.
After preliminarily crystallizing for hours, solid-state polymerization was performed at 215 ° C. under a nitrogen stream to obtain polyethylene-
2,6-Naphthalate C (PEN-C) was obtained.

(PEN-D) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, ethylene glycol 56
4.1 parts by weight (5 mol%) of 1,4-butanediol were added, and 0.1 part by weight of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was performed according to a conventional method. . 0.04 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually raised and reduced to 285.
C., polymerization at 0.5 mmHg, polyethylene-2,6-naphthalate D (PEN-D) having an intrinsic viscosity of 0.40
Was obtained as a main component.

Using the respective polyester resins obtained as described above, biaxially stretched polyester film supports 1 to 14 were prepared as follows. -Preparation of support-(Support-1) PET-A pelletized 15
After vacuum drying at 0 ° C. for 8 hours, the mixture was melt-extruded from a T-die at 285 ° C. in a layered form, adhered on a cooling drum at 30 ° C. while applying static electricity, and cooled and solidified to obtain an unstretched film. This unstretched sheet is rolled into 8 rolls using a roll-type vertical stretching machine.
The film was stretched 3.3 times in the machine direction at 0 ° C. The obtained uniaxially stretched film is stretched by a tenter-type transverse stretching machine in a first stretching zone at 90 ° C. to 50% of the total transverse stretching ratio, and further at a second stretching zone at 100 ° C. to a total transverse stretching ratio of 3.3 times. Stretched so that Next, a pre-heat treatment was performed at 70 ° C. for 2 seconds, followed by heat setting at 150 ° C. in the first fixing zone for 5 seconds and heat setting at 220 ° C. in the second fixing zone for 15 seconds. Then 5% in the horizontal direction
The film was cooled to room temperature over 60 seconds while relaxing, and the film was released from the clip and wound up to obtain a biaxially stretched film having a thickness of 90 μm.

(Support 2) PEN-A was used in place of PET-A of support 1, and the melt extrusion temperature was 300
° C, cooling drum temperature 50 ° C, longitudinal stretching temperature 135 ° C, first transverse stretching zone 145 ° C, second transverse stretching zone temperature 155
℃, pre-heat treatment temperature 100 ℃, first fixed zone temperature 200
A biaxially stretched film having a thickness of 90 μm was obtained in the same manner as in the support 1 except that the temperature was changed while setting the second fixing zone temperature to 230 ° C.

(Support-3) The PET-A and the PEN-A were blended by a tumbler type mixer such that the weight ratio was as shown in Table 1. Film forming conditions were as follows: melt extrusion temperature 295 ° C., cooling drum temperature 45 ° C., longitudinal stretching temperature 11
0 ° C., first transverse stretching zone temperature 125 ° C., second transverse stretching zone temperature 135 ° C., pre-heat treatment temperature 85 ° C., first fixed zone temperature 180 ° C., and second fixed zone temperature 225 ° C. In the same manner as for the support 1, a biaxially stretched film having a thickness of 90 μm was obtained.

(Support-4) PET-A, P of support 3
PET-B and PEN-C were used instead of EN-A, and blending was performed in the same manner so that the blend ratios shown in Table 1 were obtained. The film forming conditions were the same as those for the support 3.

(Supports 5 to 14) PET of Support 3
A and PEN-A were blended by the same method except that the blend ratio was changed as shown in Table 1 with two kinds of polyester resins. The film forming conditions were the same as those for the support 2.

-Coating of Undercoat Layer and Heat Treatment- 8 W / (m ² /
min), and the following undercoating coating solutions A-1 and A-2 were applied thereon, respectively.
-1 and A-2 are the dry film thicknesses of 0.8 μm and 0.1, respectively.
It was applied so as to be μm. Further, the other surface is subjected to a corona discharge treatment of 8 W / (m ² / min),
Using the undercoating coating solutions B-1 and B-2 below, the undercoating layers B-1 and B-2 each had a dry film thickness of 0.8 μm.
m, and then heat-treated while being transported in a heat-treating oven having a film transport device (zone length 100 m) composed of a plurality of roll groups. At this time, the inlet temperature, the outlet temperature, and the heat treatment time in the oven were changed as shown in Table 2. The term "heat treatment time" used herein refers to a time required to pass through a heat treatment oven when the line transfer speed is changed.

<Undercoat Coating Solution A-1> A copolymer latex solution (solid content: 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate) 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml

<Undercoating Coating Solution B-1> 270 g of a copolymer latex liquid (solid content 30%) of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight Compound (UL-1) 6g Hexamethylene-1,6-bis (ethylene urea) 0.8g Finish with water 1000ml

<Undercoat Coating Solution A-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1g Finish with water 1000ml

<Undercoat Coating Solution B-2> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL -6) 12 g polyethylene glycol (weight average molecular weight 600) 6 g finish with water 1000 ml

[0131]

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[0132]

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The polyester film support prepared by the above method was coated with an undercoat layer, and then subjected to a heat treatment carried out in a temperature range from Tg + 55 ° C. to Tg while transporting and cooling, which is a feature of the present invention. A support was coated with a silver halide photographic material and a photothermographic material as described below.

-Coating of silver halide photographic emulsion layer and backing layer-On the obtained support, the following (emulsion layer) and (backing layer) were coated on A-2 and B-2, respectively. A sample as a silver halide photographic light-sensitive material was prepared. At this time, the gelatin coating amount was 2.7 g / m ² including the gelatin in the emulsion on the emulsion layer side, and 2.7 g / m ^{2 on} the backing layer side.
² and the total amount of gelatin was adjusted to 5.0 g / m ² .

(Preparation of emulsion) A rhodium hexachloride complex was added to a silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide at a concentration of 8 ×.
A solution added so as to have a concentration of 10 ⁻⁵ mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate. After desalting, a cubic crystal having a particle size of 0.13 μm and containing 1 mol% of silver bromide, monodispersed To obtain a silver chlorobromide emulsion. This emulsion was subjected to sulfur sensitization by a conventional method, and then 4-hydroxy-6 was used as a stabilizer.
After adding -methyl-1,3,3a, 7-tetrazaindene, the following additives were added to prepare an emulsion coating solution.

<Preparation of Emulsion Coating Solution> Gelatin 1.0 g / m ² Compound (a) 1 mg / m ² NaOH (0.5 N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² saponin (20% aqueous solution) 0.5 ml / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg / m ² compound ( f) 6 mg / m ² latex (m) 1.0 g / m ² Styrene-maleic acid copolymerizable polymer (thickener) 90 mg / m ²

<Emulsion protective layer coating solution> Gelatin 0.5 g / m ² compound (g) (1% aqueous solution) 25 ml / m ² Compound (h) 120 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² spherical Monodispersed silica (3 μm) 10 mg / m ² Compound (i) 100 mg / m ² Latex (m) 0.5 g / m ² Citric acid Adjusted to pH 6.0

(Coating solution for backing layer) Gelatin 0.8 g / m ² Compound (j) 100 mg / m ² Compound (k) 18 mg / m ² Compound (l) 100 mg / m ² Saponin (20% aqueous solution) 0.6 ml / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² Styrene-maleic acid copolymerizable polymer (thickener) 45 mg / m ² Glyoxal 4 mg / m ²

(Coating solution for backing protective layer) Gelatin 0.5 g / m ² Compound (g) (1% aqueous solution) 2 ml / m ² Spherical polymethyl methacrylate (4 μm) 25 mg / m ² Sodium chloride 70 mg / m ² Glyoxal 22 mg / m ² compound (n) 10 mg / ^{m 2} latex (m) 0.5 g / ^{m 2}

[0140]

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[0141]

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[0142]

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-Coating of heat-developable photosensitive layer-After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 900 ml of water, adjusting the temperature to 35 ° C and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (98/2) molar ratio solution and [Ir (NO) Cl _5] salt per mole silver 1 × ^{10 -6} mol and 1 mol of silver per rhodium chloride salt containing potassium bromide and potassium iodide in 1 × 10 ⁻⁴ mol was added by the controlled double jet method while keeping the pAg at 7.7. Then 4
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the variation coefficient of the projected diameter area with an average particle size of 0.06 μm and a monodispersity of 10% was 8 % [100] cubic silver iodobromide grains having a face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion. Further, chemical sensitization was performed with chloroauric acid and inorganic sulfur.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 m of a 1.5 M aqueous sodium hydroxide solution was added.
1 was added. Next, after adding 0.93 ml of concentrated nitric acid, 5
The solution was cooled to 5 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. 147m of 1M silver nitrate solution
was added over 7 minutes, and the mixture was further stirred for 20 minutes, and the water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed six times with water and removed, and then dried.

(Preparation of Photosensitive Emulsion) Polyvinyl butyral (average molecular weight: 300
544 g of 0) methyl ethyl ketone solution (17 wt%)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 psi. The following layers were sequentially formed on the support to prepare a sample. In addition, each drying is 60
C. for 15 minutes. Back side coating: A liquid having the following composition was applied. Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² Dye-B 7 mg / m ² Dye-C 7 mg / m ² Matting agent: monodispersity 15% Monodisperse silica with an average particle size of 10 μm 30 mg / m ² C ₉ H ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0147]

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Photosensitive layer surface side coating Photosensitive layer 1: A solution having the following composition was coated and the silver amount was 2.1 g / m ^2.
It was applied so that Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Antifoggant- 2 (10% methanol solution) 1.2 ml 2- (4-chlorobenzoylbenzoic acid) (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) Solution) 17 ml Developer-1 (20% methanol solution) 29.5 ml

[0149]

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Surface protective layer: A solution having the following composition was applied on the photosensitive layer. Acetone 35 ml / m ² Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² 4-Methylphthalic acid 180 mg / m ² Tetrachlorophthalic acid 150 mg / m ² Tetrachlorophthalic anhydride 170 mg / m ² matting agent: monodispersity 10%, monodisperse silica having an average particle size of 4 μm 70 mg / m ² C ₉ H ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ²

The samples prepared as described above were evaluated as described below, and the results are shown in Tables 1 and 2. (Evaluation method)-Intrinsic viscosity-Pellets or films were mixed with phenol and 1,1,
2,2-tetrachloroethane mixed solvent (weight ratio 60 /
40), dissolved in a concentration of 0.2 g / dl, 0.6 g / d
A solution of 1, 1.0 g / dl is prepared, and a specific viscosity (η _sp ) at each concentration (C) is determined at 20 ° C. using an Ubbelohde viscometer. Then, η _sp / C is plotted against C, and the obtained straight line is extrapolated to zero concentration,

[0152]

(Equation 1) Ask for. The unit is indicated by dl / g. Table 1 shows the intrinsic viscosity values of each pellet and film.

-Glass transition temperature Tg-10 mg of the support or pellet is melted at 300 ° C in a nitrogen stream of 300 ml / min, and immediately cooled in liquid nitrogen. This quenched sample was set on a differential scanning calorimeter (DSC8230, manufactured by Rigaku Denki Co., Ltd.), and 100 m / min.
temperature in a nitrogen stream at a rate of 10 ° C./min.
Is detected. Tg was defined as the average value of the temperature at which the baseline began to be skewed and the temperature at which it returned to the new baseline.
Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more. The Tg of each support is shown in Table 1.

-Curl habit- A heat-treated support having a size of 30 mm in width and 160 mm in length and a silver halide photographic light-sensitive material having a photographic emulsion layer coated on the support were subjected to conditions of 23 ° C. and 55% RH. After moisture conditioning for 1 day, fix it so as not to wind it back around the core having a diameter of 8 mm. Next, in this state, it was placed in an aluminum barrier bag and heated at 80 ° C. for 2 hours. Thereafter, the film was released from the winding core, left for 1 hour at 23 ° C. and 55% RH, and measured with a curl gauge. The unit is m
It is ^-1 .

-Rising curl-A heat-developable photosensitive material having a heat-developable photosensitive layer coated on a heat-treated support having a width of 30 mm and a length of 210 mm was prepared by heating 23
After humidity control for 1 day under the conditions of 55 ° C. and 55% RH, the photosensitive layer is fixed inside so that the photosensitive layer side is not wound around the core having a diameter of 50 mm. Next, in this state, it is put in an aluminum barrier bag, heat-treated under the condition of 55 ° C. and 20% RH for 4 hours, and further allowed to cool at 23 ° C. and 55% RH for 1 hour. Thereafter, the film was released from the winding core, the heights of the four corners of the film rising with the protruding portions of the film facing down were measured, and the average value was obtained. The unit is mm.

-Evaluation of flatness of support- The support was heat-treated, cut into a size of 60 cm x 100 cm (width x length), placed on a table having excellent flatness, and visually evaluated for unevenness of the base. ：: Good flatness and tightly adhered to the table △: The base is distorted in some places ×: The base is distorted as a whole

[0157]

[Table 1]

[0158]

[Table 2]

As is clear from Table 2, when the support of the present invention and the heat treatment were applied, the curl was significantly improved and the flatness of the support was also improved.

[0160]

According to the present invention, there is provided a support for a silver halide photographic light-sensitive material and a heat-developable photographic light-sensitive material which are produced or used by being wound into a roll. And a support for a photographic light-sensitive material.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ikuo Kurachi 1 Konica Corporation, Sakura-cho, Hino-shi, Tokyo

Claims (7)

[Claims] 1. A photographic support comprising a biaxially stretched polyester film containing polyethylene naphthalate as a main component, wherein the support is coated with an undercoat layer and dried.
A photographic support obtained by heat-treating a polyester film in a temperature range of Tg to Tg + 55 ° C. for 5 to 60 minutes while transporting and cooling it. 2. The photographic support according to claim 1, wherein said photographic support has an intrinsic viscosity of 0.3 or more and 1.2 or less and a difference of intrinsic viscosity of 0.2 or more and 1.0 or less. The photographic support according to claim 1, comprising a resin mixed with polyester. 3. The photographic support according to claim 2, wherein at least one of the polyester resins is polyethylene-2,6-naphthalate. 4. The polyester resin having a lower intrinsic viscosity is
4. The photographic support according to claim 2, wherein 0 to 80% by weight is mixed. 5. A photographic support according to claim 2, wherein both of said polyester resins are polyethylene-2,6-naphthalate. 6. A silver halide photographic light-sensitive material comprising at least one silver halide photographic emulsion layer provided on the photographic support according to claim 1. 7. A photothermographic material comprising at least one photothermographic layer provided on the photographic support according to claim 1. Description: