JP2002031875A - Heat developable sensitive material packaged body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable sensitive material packaged body capable of suppressing pressure fog due to the weight of the sensitive materials in the packaged state. SOLUTION: In the heat developable sensitive material packaged body obtained by stacking and packaging plural sheetlike heat developable sensitive materials each containing an organic silver salt, photosensitive silver halide, a reducing agent for silver ions and a binder on the base in a packaging bag 3, (1) the lowest one of the stacked heat developable sensitive materials 1 receives <=300 Pa surface pressure, (2) a sheet which protects at least the undersurface of the stacked heat developable sensitive materials is disposed and the bending stiffness of the sheet measured by a method stipulated by JIS P 8125 is >=4 mNm or (3) the lowest one of the stacked heat developable sensitive materials receives <=300 Pa surface pressure, a sheet which protects at least the undersurface of the stacked heat developable sensitive materials is disposed and the bending stiffness of the sheet measured by a method stipulated by JIS P 8125 is >=4 mNm. The packaging bag 3 has light shielding and moisture- proof properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material package, and more particularly, to a photothermographic material package capable of suppressing pressure fog due to the weight of the photosensitive material in a packaged state.

[0002]

2. Description of the Related Art In the medical field and the printing plate-making field, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. In recent years, the amount of processing waste liquids has been reduced from the viewpoint of environmental protection and space saving. Is strongly desired. Therefore, laser
There is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with an imager and a laser imagesetter, and can form a high-resolution and clear black image. This technique includes, for example, U.S. Patent Nos. 3,152,904 and 3,487,075 and D.C. Morgan (Dry Silver Photogr)
aphic Materials) "(Handbook
k of Imaging Materials, M
arcelDekker, Inc. 48, 199
The methods described in 1) and the like are well known. Since these photosensitive materials are developed at a high temperature of 80 ° C. or higher, they are called photothermographic materials. Since these photothermographic materials do not use any solution-based processing chemicals, it is possible to provide users with a system that is simpler and does not damage the environment.

[0003] However, such a photothermographic material (sometimes referred to as a film if necessary) is sold in the market with the final product being packaged in a packaging bag.

[0004] In the present specification, a bag for packaging such a photothermographic material is referred to as a packaging bag, and a package in which the photothermographic material is housed and packed therein is referred to as a photothermographic material package.

[0005] In the case of a photothermographic material, the reaction to pressure is sensitive, and there is a problem that pressure fog occurs in the lower layer of the laminated film due to its own weight.

In addition, after the photothermographic material packed in the light-shielding packaging bag is stored in an apparatus or a magazine, only the packaging bag is pulled out and the film is left in a light room. Has reduced the contact area with the package in order to reduce the pulling load of the packaging bag. Therefore, there is a problem that pressure fogging occurs because the film's own weight is concentrated at the contact portion.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material package capable of suppressing pressure fog caused by the weight of the photosensitive material in a packaged state.

[0008]

The object of the present invention is solved by the following invention. 1. A photothermographic material obtained by laminating a plurality of sheet-shaped photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder on a support and packaging the same in a packaging bag The photothermographic material package according to claim 1, wherein a surface pressure applied to a lowermost layer of the stacked photothermographic material is 300 Pa or less, and the packaging bag has a light-shielding property and a moisture-proof property. 2. 2. The photothermographic material package according to the above item 1, wherein the surface pressure received on the lowermost layer of the plurality of laminated photothermographic materials is 270 Pa or less. 3. A photothermographic material obtained by laminating a plurality of sheet-shaped photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder on a support and packaging the same in a packaging bag In the package, a sheet for protecting at least the lower surface of the plurality of laminated photothermographic materials is arranged, and the sheet has a bending stiffness of 4 mNm or more according to JIS P 8125 measurement method, and the packaging bag is A photothermographic material package having a light-shielding property and a moisture-proof property. 4. 4. The photothermographic material package according to the above item 3, wherein the sheet has a bending stiffness of 6 mN · m or more according to JIS P 8125 measurement method. 5. A photothermographic material obtained by laminating a plurality of sheet-shaped photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder on a support and packaging the same in a packaging bag In the package, a surface pressure applied to the lowermost layer of the plurality of stacked photothermographic materials is 300 Pa or less, and a sheet for protecting at least a lower surface of the plurality of stacked photothermographic materials is arranged. , J of the sheet
A photothermographic material package characterized by having a bending stiffness of 4 mN · m or more according to an ISP 8125 measurement method, wherein the packaging bag has a light-shielding property and a moisture-proof property. 6. 6. The photothermographic material package according to the above item 5, wherein the surface pressure received on the lowermost layer of the plurality of laminated photothermographic materials is 270 Pa or less. 7. 7. The photothermographic material package according to the above item 5 or 6, wherein the sheet has a bending stiffness of 6 mN · m or more according to JIS P 8125 measurement method.

[0009]

Embodiments of the present invention will be described below.

FIG. 1 is a view showing a production example of a photothermographic material package of the present invention. In FIG. 1, reference numeral 1 denotes a sheet-like photothermographic material in which a plurality of sheets are laminated, and 2 denotes a plurality of sheets. This is a sheet for protecting at least the lower surface of the laminated photothermographic material 1. The laminated photothermographic material 1 is a sheet 2
And stored in a packaging bag 3 as shown on the right side of the figure to obtain a photothermographic material package (not shown).

In the present invention, the surface pressure applied to the lowermost layer of the laminated photothermographic material 1 inside the packaging bag 3 is 30.
0 Pa or less, preferably 270 Pa or less. 30
If the pressure exceeds 0 Pa, pressure fog occurs due to the weight of the photosensitive material. In the present invention, the surface pressure of the lowermost layer is the pressure received by the film's own weight when it is placed on a flat surface. The film mass is measured (kg), the gravitational acceleration is multiplied, and the force applied to the lowermost layer (N) Was calculated as the force applied per unit area, that is, the pressure.

In the present invention, JIS P 81 of the sheet 2 is used.
25 The bending stiffness according to the measuring method is 4 mN · m or more, more preferably 6 mN · m or more.

In the present invention, the JIS P 8125 measurement method is a stiffness test method for paperboard, and the bending stiffness when a material other than paperboard is used as a sheet is also described.
The value measured according to JIS P8125 measurement method was adopted.

As long as the sheet 2 can protect at least the lower surface of the photothermographic material, a U-shaped sheet is used to protect the side surface and the upper surface in addition to the lower surface as shown in the figure.

The material of the sheet 2 can be selected from the following materials. (A) Natural pulp: Wood, chemical pulp (B) Synthetic pulp: Polyethylene pulp (C) Synthetic fiber: Acrylic nitrile, polyamide, polyacrylonitrile, polypropylene, polyvinyl alcohol, polyester (D) Water-based resin for internal addition or impregnation: SBR latex, N
BR, chloroprene, natural rubber, isoprene, polyurethane, polyacrylate, polyvinyl acetate, ethylene vinyl acetate copolymer latex, polyvinyl chloride latex, polyvinylidene latex, polyacrylamide latex, acrylic ketene dynamer latex,
Starch, PVA, dextrin (E) Solvent resin for impregnation: EVA, SBR, NBR, M
BR, alkyd resin, polyester resin, amino alkyd resin, polyvinyl acetate resin, polyvinyl chloride resin, polyurethane resin, polyacrylate resin

The material of the sheet 2 is preferably selected from one or more of the above (A),
(A), (B) and (C) are used in combination, or base paper obtained by further adding (D) is impregnated with (D) or (E).

When the above materials are mixed and used, a preferable mixing ratio of each material is (A) :( B)-(C) = 100
-30%: 0-70%, the addition of (D) to the pulp is preferably 0-20%, and the preferred impregnation ratio of (E) is 3-70% by weight to pulp.

The packaging bag 3 is a bag having a light-shielding property and a moisture-proof property, and may be formed of any material having a light-shielding property and a moisture-proof property or a material having a light-shielding property and a moisture-proof property. As the moisture-proof material, a laminated sheet in which the inner surface is laminated with a polyolefin film such as polyethylene is preferably used. In order to impart light-shielding properties, carbon black may be contained in any layer of the sheet, an aluminum foil may be provided on the surface layer, or an aluminum vapor-deposited layer may be formed.

According to the present invention, the surface pressure applied to the lowermost layer of the laminated photothermographic material 1 inside the packaging bag 3 is 300.
Pressure fog can be more effectively prevented when the sheet 2 has a bending stiffness of 4 mN · m or more according to JIS P 8125 measurement method.

Hereinafter, the photothermographic material to which the present invention is applied (hereinafter referred to as the photothermographic material of the present invention, if necessary) will be described.

The photothermographic material of the present invention is provided on a support.
It is preferable that a photographic constituent layer containing an organic silver salt, a photosensitive silver halide, and a silver ion reducing agent is formed by applying a solvent, and that at least one protective layer is provided on the photographic constituent layer. A so-called single-sided photosensitive material having a backing layer on the other side of the support is preferred.

The photographic constituent layer of the photothermographic material of the present invention comprises a photosensitive layer and a non-photosensitive layer, wherein the photosensitive layer contains an organic silver salt and photosensitive silver halide particles. An embodiment containing a reducing agent is preferred.

(Photosensitive Silver Halide) Silver halide grains function as an optical sensor. In the present invention, the average particle size is preferably smaller in order to suppress white turbidity after image formation and to obtain good image quality.
0 μm or less, more preferably 0.02 μm or more and 0.15
μm or less, more preferably 0.03 μm or more and 0.11 μm
m or less is good.

When the silver halide grains are cubic or octahedral so-called normal crystals, the average grain size means the length of the edge of the silver halide grains. 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.

The silver halide grains are preferably monodisperse grains. The term “monodisperse particles” as used herein means particles having a degree of monodispersity of 40% or less, more preferably 30% or less, particularly preferably 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Miller index [1
The ratio of the [00] plane is determined by T. Tani, J. Ima using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane.
ging Sci., 29, 165 (1985).

The average particle diameter of the monodisperse particles is 0.1 μm.
The following is preferable, and more preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm.

Another preferred form of silver halide grains is tabular grains. Here, the tabular grains are:
The aspect ratio (= r / h) is 3 or more when the square root of the projected area of the particle is r μm and the thickness in the vertical direction is h μm. Among them, those having an aspect ratio of 3 or more and 50 or less are preferable.

The average particle diameter of the tabular grains is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm.
μm is more preferred. These are disclosed in U.S. Pat.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained.

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. Silver halide, silver iodide or silver iodobromide, more preferably silver bromide or silver iodobromide. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%, more preferably from 0.1 mol% to 10 mol%. The distribution of the halogen composition in the grains may be uniform, the halogen composition may change stepwise, or the grains may change continuously. Preferably, an embodiment using silver halide grains having a core / shell structure having a high silver iodide content inside the grains is preferred.

The photographic emulsion used in the present invention is P. Glafki
Chimie et Physique Photographique by des (Paul Montel
Published by GFDuffin, Photographic Emulsion Ch
emistry (The Focal Press, 1966), VLZelikman et
Making and Coating Photographic Emulsion (The F
ocal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and in order to form a solution by reacting a soluble silver salt and a soluble halide, any one of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like is used. You may.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source.

The silver halide may be prepared by converting a part or all of the silver in the organic acid silver to the silver halide by the reaction between the organic acid silver and the halogen ion,
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

In general, 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 an ion or a complex ion of a metal belonging to VIB, VIIB, VIII or IB belonging to a transition metal of the periodic table. Examples of the above-mentioned metals include Cr and W (the above-mentioned VIB group):
Re (VIIB group): Fe, Co, Ni, Ru, Rh, P
d, Os, Ir, Pt (more than VIII group): Cu and Au (more than IB group) are preferable. Among them, when used for a photosensitive material for printing plate making, it is selected from Rh, Re, Ru, Ir, and Os. preferable.

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.

The general formula [ML ₆ ] ^m

In the formula, M is a group of elements of the periodic table VIB, VIIB, VIII
A transition metal selected from Group I and Group IB elements, L represents a bridging ligand, and m represents 0, -1, -2 or -3.

Specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and alcohols. Each ligand of
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are 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 are rhodium (Rh), ruthenium (Ru), rhenium (Re) or osmium (Os).

The following are specific examples of the transition metal coordination complex.

[0042] ^{_{1: [RhCl 6] 3- 2}} : [RuCl 6] 3- 3: [ReCl 6] 3- 4: [RuBr 6] 3- 5: [OsCl 6] 3- 6: [CrCl 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 (NO) 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-

One of these metal ions or complex ions may be used, or two or more of the same or different metals may be used in combination.

The content of these metal ions or complex ions is generally in the range of 1 to 1 mol of silver halide.
The amount is suitably from ^10-9 to ^1-10-2 mol, preferably 1 mol.
X 10 ^-8 to 1 X 10 ^-4 mol.

It is preferable that the compound providing these metal ions or complex ions is added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening,
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation and placed, or a silver salt solution and a halide solution are used. When mixed simultaneously, a third aqueous solution is added to prepare 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 halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing silver halide 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 particle surface, 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 of the present invention are preferably washed with water to remove soluble salts.

The photosensitive silver halide grains used in the present invention can be subjected to chemical sensitization using various known methods. In particular, chemical sensitization with a chalcogen compound can be performed. Chemical sensitization by a chalcogen compound includes a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method.

The sensitizer used in the present invention may be added at any timing during the formation of the silver halide grains, before the desalting after the formation of the grains, or after the desalting, but preferably during the formation of the grains or after the desalting. Is good.

The photosensitive silver halide grains used in the present invention can be spectrally sensitized to a desired wavelength by a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes,
Holobola cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, pyrazoline- as a nucleus having a ketomethine structure is used.
5-6 nuclei, thiobitantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thioparbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied. Specifically, Research Disclosure Vol. 176, RD17643 (197
(Issued in December 2008) page 2, page 3, US Patent 4,425,425
And No. 4425426 can be used. The sensitizing dye is disclosed in U.S. Pat. No. 3,485,634.
The dissolution may be carried out using ultrasonic vibration described in the above item. Other methods of dissolving or dispersing a sensitizing dye and adding it to an emulsion include, for example, US Pat. No. 3,482,981;
No. 3585195, No. 3469987, No. 3425
Nos. 835 and 3342605, British Patent 127132
Nos. 9, 1038029, 1121174, U.S. Pat. Nos. 3,660,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, particularly for supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in RD17643 (published December 1978), page 23, section J.

(Organic Silver Salt) The organic silver salt that can be used in the present invention is relatively stable to light, but can be used in the presence of an exposed photocatalyst (such as a photographic silver salt) and a reducing agent.
A silver salt that forms a silver image when heated to 80 ° C. or higher.

The organic silver salt may be any organic substance containing a source capable of reducing silver ions. Silver salts of organic acids, especially long-chain fatty carboxylic acids (preferably having 10 to 30 carbon atoms, more preferably having 15 to 28 carbon atoms) are preferred.

Complexes of organic or inorganic silver salts wherein the ligand has a total stability constant in the range of 4.0 to 10.0 are also desirable. The silver source material should preferably make up about 5 to 30% by weight of the photosensitive layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver stearate, silver arachidate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate.
Includes silver fumarate, silver tartrate, silver linoleate, silver butyrate and silver camphorate, mixtures thereof and the like. Silver salts of compounds containing a mercapto or thione group and derivatives thereof can also be used. Preferred examples of these compounds are
Silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, 2- (ethylglycolamide) benzothiazole A silver salt of a thioglycolic acid such as a silver salt, a silver salt of an S-alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, Silver salt of thioamide, silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, U.S. Pat. No. 4,123,274
No. 1,2,4- such as silver salt of 3-amino-5-benzylthio-1,2,4-thiazole.
Silver salts of mercaptothiazole derivatives, US Pat. No. 3,3
3- (3-carboxyethyl) described in 01,678
And a silver salt of a thione compound such as a silver salt of -4-methyl-4-thiazoline-2-thione. Further, a silver salt of a compound containing an imino group can be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole,
As described in U.S. Pat. No. 4,220,709,
Includes silver salts of 2,4-triazole or 1-H-tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, various silver acetylide compounds as described in U.S. Pat. Nos. 4,761,361 and 4,775,613 can be used.

In the present invention, a particularly preferred silver source is silver behenate. More preferred is a mixture with silver stearate and silver arachidate. The content of silver stearate is 0 to 70 mol%, preferably 10 to 30 mol%, based on silver behenate, and silver arachidate is 0 to 70 mol%, preferably, silver silver behenate. 30-6
0 mol%.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used.

In the present invention, the organic silver salt preferably has an average particle size of 1 μm or less and is monodispersed. The average particle size of the organic silver salt means that the particles of the organic silver salt are, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of the organic silver salt grains. 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 grains, and the preferred monodispersity is 1%
３０30%.

In the present invention, the method of mixing the photosensitive silver halide and the organic silver salt and the mixing conditions are not particularly limited as long as the effects of the present invention are sufficiently exhibited. A method of mixing the prepared photosensitive silver halide and the organic silver salt, or a method of mixing the prepared photosensitive silver halide at any timing during the preparation of the organic silver salt, and There is a method of preparing a silver halide by mixing a silver salt and a halogenating agent, and a more preferable mixing method is to mix the prepared photosensitive silver halide with an organic acid, and then to silver chloride the organic acid. There is.

In the present invention, in order to obtain a predetermined optical density, the total amount of silver halide and organic silver salt is preferably from 0.3 g to 1.5 g per m ² in terms of silver amount. . The amount of silver halide relative to the total amount of silver is 50% or less by weight, preferably 25% or less, more preferably 0.1% to 15%.

(Reducing Agent for Silver Ions) The reducing agent for silver ions is a reducing agent for organic silver salts. Examples of the reducing agent that can be used in the present invention include any substance that reduces silver ions to metallic silver. Preferably, it may be an organic substance. Phenidone,
Conventional photographic developers such as hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. Examples of hindered phenols include compounds represented by the following general formula (A).

[0063]

Embedded image

In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, 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.

[0066]

Embedded image

[0067]

Embedded image

The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is 0 ^-2 to 10 mol, particularly preferably 1 × 10 ^{-2 to} 1.5 mol.

The reducing agent is used in one of the photographic constituent layers (image forming layers).
It is preferably present in the range from 10 to 10% by weight. When the light-sensitive material has a multilayer structure, when a reducing agent is added to a layer other than the emulsion layer, a slightly higher ratio of about 2 to 15% by weight tends to be more desirable.

In the photothermographic material, a wide range of reducing agents can be used, for example, phenylamide oxime,
Amide oximes such as 2-thienylamide oxime and p-phenoxyphenylamide oxime;
Azines such as hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2'-bis (hydroxymethyl)
A combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid such as a combination of propionyl-β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg, hydroquinone and bis ( Ethoxyethyl) hydroxylamine, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine, etc.); phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-
Hydroxamic acids such as alinine hydroxamic acid; combinations of azine and sulfonamidophenol (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano-2-methylphenylacetate, ethyl Α-cyanophenylacetic acid derivatives such as -α-cyanophenylacetate;
2'-dihydroxy-1,1'-binaphthyl, 6,6 '
Bis-β-naphthol such as exemplified by dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane;
a combination of β-naphthol and a 1,3-dihydroxybenzene derivative (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxyacetophenone); 5 such as 3-methyl-1-phenyl-5-pyrazolone; Pyrazolones; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-
Sulfonamidophenol reducing agents such as 4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7-t-butyl-6-hydroxychroman and the like 2,6-dimethoxy-
1,4-dihydropyridines such as 3,5-dicarbethoxy-1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol) and bi-2,2-bis (3,5-dimethyl-4-hydroxyphenyl) Ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indane-1,3-diones.

(Binder) 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,
Other film forming media, for example: gelatin, gum arabic, poly (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) s (for example,
Poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate) ), Cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic.

In the present invention, the amount of the binder in the photosensitive layer is preferably 1.5 to 10 for the purpose of preventing dimensional fluctuation after thermal development.
g / m ² .

(Other Additives) In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a matting agent is provided on the surface of the photosensitive material in order to prevent the image after thermal development from being damaged. Preferably, the matting agent is contained in a weight ratio of 0.5 to 10% 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 the organic substance, US Pat. No. 2,322,
037 etc., Belgian Patent No. 625, 45
No. 1 and British Patent Nos. 981, 198, etc., polyvinyl alcohol described in JP-B-44-3643, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic matting agents such as polyacrylonitrile described in 3,079,257 and the like and polycarbonate described in U.S. Pat. No. 3,022,169 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 spherical shape. 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. The variation coefficient of the particle size distribution is 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. However, in order to achieve the object of the present invention, the matting agent is preferably a constituent layer other than the photosensitive layer, and more preferably from the support. The outermost layer to look at.

The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed in a coating solution in advance and applied.
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 is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 220 ° C.) after exposure. Heating produces 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. Silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas,
An image is formed. This reaction process proceeds without supplying a processing liquid such as water from the outside.

To control the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side as or opposite to the photosensitive layer, or a dye or pigment may be contained in the photosensitive layer. May be. As the dye, the compounds described in Japanese Patent Application No. 7-11184 are preferred.

It may be advantageous to include, in addition to the above components, additives known as "toning agents", which enhance the image. For example, the toning material is 0.1% of the total silver holding component.
It may be present in an amount of from 10 to 10% by weight. Toning agents are materials well known in the photographic art, as shown in U.S. Pat. Nos. 3,080,254, 3,847,612 and 4,123,282.

Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazoline-
5-one, and quinazolinone, 3-phenyl-2-
Cyclic imides such as pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (e.g. N-hydroxy-
1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl- Mercaptans exemplified by 1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides (for example, (N, N-dimethylaminomethyl) Phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents such as N, N'-hexamethylenebis (1 -Carbamoyl-3,5-dimethylpyrazole), 1,8- (3, - Jiazaokutan) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl) - (benzothiazole));
And 3-ethyl-5 [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazine; phthalazinone, a phthalazinone derivative or a metal salt, or 4
-(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-
Derivatives such as dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (for example, phthalic acid, 4-
Quinazolinedione, such as methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride;
Benzoxazine or naphthoxazine derivatives; rhodium complexes which function not only as tone modifiers but also in situ as sources of halide ions for silver halide formation, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate And potassium hexachlororhodate (III); inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-1, 3-benzoxazine-2,4-
Dione and 6-nitro-1,3-benzoxazine-
Benzoxazine-2,4-diones such as 2,4-dione; pyrimidines and asymmetric-triazines (e.g. 2,2
4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto-
1,4-diphenyl-1H, 4H-2,3a, 5,6a
-Tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-
2,3a, 5,6a-tetraazapentalene).

In the present invention, a preferable color tone agent is phthalazinone or phthalazine, and a combination with a phthalic acid derivative is more preferable. Among them, a combination of phthalazine and 4-methylphthalic acid, tetrachlorophthalic acid, or tetrachlorophthalic anhydride is preferable.

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 undesirable. Non-mercury antifoggants include, for example, U.S. Pat.
Preferred are antifoggants such as those disclosed in 546,075 and 4,452,885 and JP-A-59-57234.

Particularly preferred non-mercury antifoggants are US Pat. Nos. 3,874,946 and 4,756,993.
Compound as disclosed in No. 9, -C (X1) (X2) (X3)
(Where X1 and X2 are halogen atoms, and X3 is hydrogen or a halogen atom) and is a heterocyclic compound having one or more substituents. Examples of suitable antifoggants include JP-A-9-90550, paragraph number [0062].
To [0063] are preferably used.

Further, more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and British Patent Application No. 92221.
No. 383.4, No. 9300147.7, No. 931
No. 1790.1.

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

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose, etc.) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. Triacetate, polyethylene naphthalate).

Among them, preferred supports include polyethylene terephthalate (hereinafter abbreviated as PET) and plastic (hereinafter abbreviated as SPS) containing a styrene-based polymer having a syndiotactic structure.

The thickness of the support is preferably about 50 to 300 μm, more preferably 70 to 180 μm.

Further, a heat-treated plastic support may be used. The heat treatment of the support means that after forming the support and before the photosensitive layer is applied, the temperature is 30 ° C. or more higher than the glass transition point of the support, preferably 35 ° C.
The heating is carried out at a temperature higher by at least 40 ° C, more preferably at a temperature higher by at least 40 ° C. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

The method for forming a film of a support and the method for producing an undercoat according to the present invention can be carried out by using known methods. Preferably, paragraphs [0030] to [0] of JP-A-9-50094 are used.
070].

In the present invention, it is preferable to provide a backing layer on the photosensitive material in order to improve physical properties or photographic performance. Suitable binders for the backing layer of the present invention are transparent or translucent, generally colorless, natural polymer synthetic resins and polymers and copolymers, and other film forming media such as: gelatin, gum arabic, poly (vinyl alcohol), Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Poly (vinylpyrrolidone), 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) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resins, poly (vinylidene chloride) , Poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

Various auxiliaries can be added to the photothermographic material of the present invention. For example, accelerators, acutance dyes, stabilizers, surfactants, lubricants, coating aids, halogen supply agents, polyhalogen compounds and mercapto compounds, leuco dyes, chelating agents, plasticizers, ultraviolet absorbers and various other Can be usefully added.

Also, in the processing method and the manufacturing method, well-known various techniques, processing, prescriptions, additives and their addition methods can be preferably applied, and the various additives include a photosensitive layer and a non-photosensitive layer. Or any of the other forming layers.

[0099]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 Preparation of heat-developable photosensitive material package sample A heat-developable photosensitive material film having a size of 354 mm × 432 mm (“Konica Medical Film 14 × 17” manufactured by Konica Corp.)
SD-P ") was stored in a packaging bag to prepare a package sample. As the packaging bag, a barrier bag (84 μm in thickness) having a moisture-proof property and a light-shielding property was used. No protective sheet was used.
The photothermographic material package samples 1-1 to 1-6 were prepared by changing the number of the photothermographic materials to be stored. The obtained package sample was placed and stored on a flat table having no irregularities.

Photographic Performance Evaluation Test The packaging bag of the above package sample was broken, the lowermost layer of the developed photosensitive material was taken out, exposed with a laser sensitometer equipped with a 660 nm diode, and then thermally developed at 122 ° C. for 19 seconds. ,
The obtained image was evaluated using a densitometer.

Evaluation Items and Evaluation Methods [Sensitivity] Sensitivity values were measured by storing each sample at 60 ° C. for 120 hours and then measuring the reciprocal of the exposure energy required for a density of 1.0, and before storing each sample. The difference from the sensitivity (sensitivity difference) was evaluated. The average value obtained by measuring 10 random positions on the photothermographic material film having a size of 354 mm × 432 mm was used. The values are shown as relative values when the value of sample 1-2 is taken as 100. Table 1 shows the results.

[Development unevenness] 354 exposed to a density of 1.0
The entire photothermographic material film having a size of mm × 432 mm was visually measured. The values are shown as relative values when the value of sample 1-2 is taken as 100. Table 1 shows the results.

[0104]

[Table 1]

Example 2 Preparation of heat-developable photosensitive material package sample A heat-developable photosensitive material film having a size of 354 mm × 432 mm (“Konica Medical Film 14 × 17” manufactured by Konica Corp.)
SD-P ”) was stored in the packaging bag shown in FIG. 1 to prepare a package sample. As the packaging bag, a barrier bag (84 μm in thickness) having a moisture-proof property and a light-shielding property was used.

As a protection sheet, a natural pulp sheet was used. The bending stiffness of the protective sheet (JIS P 8125 measurement method) was changed as shown in Table 2.

The bending stiffness of the protective sheet, the force applied to the lowermost layer, and the number of laminated sheets were varied as shown in Table 2 to obtain samples 2-1 to 2-
10 was created.

The obtained package sample was placed on an uneven table and stored. For comparison, an experiment was also performed in which the device was placed on a flat table.

Photographic Performance Evaluation Test Same as Example 1.

Evaluation Items and Evaluation Method Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.

[0111]

[Table 2]

[0112]

According to the present invention, it is possible to provide a package of a photothermographic material capable of suppressing pressure fog due to the weight of the photosensitive material in a packaged state.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a photothermographic material, a packaging bag, and a package of a photothermographic material.

[Explanation of symbols]

 1: Photothermographic material 2: Protective sheet 3: Packaging bag

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 81/24 B65D 81/24 F 81/30 81/30 C

Claims (7)

[Claims] 1. A plurality of sheet-form photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder are laminated on a support and packaged in a packaging bag. Wherein the surface pressure applied to the lowermost layer of the plurality of laminated photothermographic materials is 300 Pa
A photothermographic material package, wherein the packaging bag has a light-shielding property and a moisture-proof property. 2. The photothermographic material package according to claim 1, wherein the surface pressure applied to the lowermost layer of the plurality of stacked photothermographic materials is 270 Pa or less. 3. A plurality of sheet-form photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder are laminated on a support and packaged in a packaging bag. In the photothermographic material packaging body, a sheet for protecting at least the lower surface of the plurality of laminated photothermographic materials is arranged, and the bending stiffness of the sheet according to the JISP 8125 measurement method is 4 mNm or more, A package for a photothermographic material, wherein the packaging bag has a light-shielding property and a moisture-proof property. 4. The photothermographic material package according to claim 3, wherein the sheet has a bending stiffness of 6 mN · m or more according to JIS P 8125 measurement method. 5. A plurality of sheet-form photothermographic materials containing an organic silver salt, a photosensitive silver halide, a reducing agent for silver ions, and a binder are laminated on a support and packaged in a packaging bag. Wherein the surface pressure applied to the lowermost layer of the plurality of laminated photothermographic materials is 300 Pa
And a sheet for protecting at least the lower surface of the laminated photothermographic material, wherein the sheet has a bending stiffness of 4 mN according to the JIS P 8125 measurement method.
M, wherein the packaging bag has a light-shielding property and a moisture-proof property. 6. The photothermographic material package according to claim 5, wherein the surface pressure applied to the lowermost layer of the plurality of laminated photothermographic materials is 270 Pa or less. 7. The photothermographic material package according to claim 5, wherein a bending stiffness of the sheet according to JIS P 8125 measurement method is 6 mN · m or more.