JP2003330145A - Heat-developable photographic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-developable photographic material excellent in antistatic performance and conveyability in a developing step and having no adverse effect on photographic performance. <P>SOLUTION: In the heat-developable photographic material comprising photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, a compound having an organic electroconductive polymer chain on a silsesquioxane mother nucleus is contained. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable photographic material which forms an image by post-exposure heat development, and more particularly to a heat-developable photographic material excellent in antistatic performance and transportability in a development processing step.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of environmental protection and workability in the medical field, there has been a strong demand for a photographic material capable of forming an image by light or heat treatment that does not generate waste liquid associated with wet processing, and utilizes both light and heat. A photographic light-sensitive material provided with a technique relating to a photothermographic material capable of forming a clear black image with high resolution by such development has been commercialized and rapidly spread. Since these photothermographic materials are usually subjected to dry heat development at a temperature of 80 ° C. or higher, they are called photothermographic image forming materials in distinction from conventional wet photosensitive materials which are liquid-developed in the range of 25 ° C. to 45 ° C.

Conventionally, this type of photothermographic image-forming material has a problem that it is liable to be charged with static electricity due to friction and peeling, and static marks and dust, which are image defects, are easily attached. As a method for solving these problems, there has been a method in which an ionic organic polymer or conductive inorganic fine particles such as tin oxide and indium oxide are applied between the support and the photosensitive layer.

These techniques are disclosed in Japanese Patent Laid-Open No. 19413/1991.
Nos. 5,216,164, 5,216,165, 5,271,523, 5,271,524, 5-3.
No. 20390 is disclosed.

However, an ionic conductive compound has high hygroscopicity and deteriorates storage stability. The conductive compound contains fine particles to a density at which fine particles in the conductive compound come into contact with each other in order to obtain conductivity. When the photothermographic image-forming material contains a conductive compound having fine particles of this density, the film strength is deteriorated, and the antistatic performance and transportability are adversely affected.

Although a strong binder and a cross-linking hardener have been used to strengthen the film strength, a solution has been attempted.
It was not possible to obtain satisfactory performance.

On the other hand, the use of an organic conductive polymer compound has been studied, but in all cases, there is no suitable solvent for dissolving the polymer compound, and thus it is difficult to apply the coating, and the absorption of π electron Therefore, it is difficult to put into practical use due to the drawbacks such as easy coloring.

As a technique for improving this problem, Japanese Patent Laid-Open No. 8-1
No. 60568, No. 8-202078, No. 8-2019
No. 79, No. 8-212555, No. 8-277338.
No. 8-3339049, the improvement method thereof, and further, JP-A-5-273702, 6-73271, 6-
No. 264024, No. 6-295016, No. 7-900
No. 60, European Patent No. 1031875A1, etc.
The use of water dispersible polythiophene compounds with water soluble dopants is disclosed.

However, if the amount of the doping agent or the doping agent having a weak ionic polarization state is small, the antistatic effect cannot be obtained, and if a large amount of the doping agent or the doping agent having a strong ionic polarization state is used. The required antistatic effect is obtained, but strong coloring, fog,
There is a problem that the photographic performance such as sensitivity, storability, light resistance or color tone is impaired.

[0010]

The object of the present invention is to provide excellent antistatic performance and transportability in the development processing step, and
The object is to provide a heat-developable photographic material that does not adversely affect photographic performance.

[0011]

The above object of the present invention can be achieved by the following constitutions.

1. Photosensitive silver halide grains on a support,
A heat-developable photographic material containing an organic silver salt, a reducing agent and a binder, which contains a compound having an organic conductive polymer chain in the silsesquioxane mother nucleus.

2. 1 wherein the organic conductive polymer chain is polythiophene or polyfuran
The heat-developable photographic material described in 1.

3. 3. The photothermographic material according to 1 or 2 above, wherein the silsesquioxane mother nucleus contains a compound having an organic conductive polymer chain in the outermost layer.

4. 4. The compound having an organic conductive polymer chain in the silsesquioxane mother nucleus has a substituent that hydrogen bonds with the organic conductive polymer chain and the binder, according to any one of 1 to 3 above. Photothermographic material.

5. The compound having an organic conductive polymer chain in the silsesquioxane mother nucleus and the crosslinking agent with which the binder reacts have an isocyanate group, a vinylsulfonyl group, an epoxy group or an alkoxysilane group, 1 to 4 above The photothermographic material according to any one of 1.

6. 6. The photothermographic material according to any one of 1 to 5 above, wherein the compound having an organic conductive polymer chain in the silsesquioxane mother nucleus has a polymerizable group.

7. 7. The photothermographic material according to any one of 1 to 6 above, wherein the protective layer contains a compound having an organic conductive polymer chain in the silsesquioxane mother nucleus.

The present invention will be described in more detail below. The heat-developable photographic material of the present invention has a layer structure of at least two layers in which a photosensitive layer and a protective layer are provided on one side of a support, and the protective layer and the support are provided on the side opposite to the photosensitive layer side. A back coat (BC) layer and a protective layer for the BC layer may be provided. The photosensitive layer contains photosensitive silver halide grains that may be sensitized, an organic silver salt serving as a silver source, and a reducing agent for developing a silver salt to form a silver image.

The compound having an organic conductive polymer chain in the silsesquioxane mother nucleus of the present invention (hereinafter, also referred to as the compound of the present invention) may be used in the above-mentioned protective layer, but it is adjacent to the photosensitive layer. You may add it to an intermediate | middle layer, an undercoat layer, etc. In terms of not adversely affecting the photographic performance, the protective layer except the photosensitive layer,
An undercoat layer or a backing layer is preferred, but the invention does not adversely affect photographic performance when added directly to the photosensitive layer.

In the present invention, the compound of the present invention is preferably contained in the outermost layer (eg BC layer) of the photothermographic material, and more preferably added to the protective layers on both sides of the photothermographic material.

The compound of the present invention comprises a method in which organotrichlorosilane is added to a saturated aqueous solution of hydrogen chloride, and hydrolysis and condensation are carried out (JP-A-6-179751), and organotrialkoxysilane is contained in an ionic surfactant. A method of adding to an acidic or alkaline aqueous solution to cause a hydrolysis and condensation reaction (Japanese Patent Publication No. 52-12219), an organotrialkoxysilane and / or a partially hydrolyzed condensate thereof, a nonionic surfactant and a cationic surfactant. A method of emulsifying and dispersing in water in the presence of water, adding an alkali to carry out hydrolysis and condensation reaction (Japanese Patent Publication No. 1-14250).
Japanese Patent Application Laid-Open Publication No. 4-311), a method of neutralizing an organosilanol alkali metal salt with an acid in an aqueous solution and conducting a condensation reaction (JP-A-4-3).
(59022 publication) and the like.

A particularly preferred compound having a silsequioxane unit of the present invention has a three-dimensional structure represented by the following general formula (1), eight R ^{1 to} R ⁸ represent a substituent, and R ^{1 to} R ⁸
At least one of the substituents has an organic-organic conductive polymer unit described later.

However, SL-1 to SL-6 in Table 1 described later
Is not a compound of the invention.

[0025]

[Chemical 1]

In the general formula (1), R ^{1 to} R ⁸ represent a substituent of the silsesquioxane mother nucleus, and specifically, for example, hydrogen atom, halogen atom (eg chlorine atom, fluorine atom, etc.). ), A chain or branched alkyl group (eg, methyl group, ethyl group, n-propyl group, i-propyl group,
n-butyl group, i-butyl group, cyclohexyl group, etc.),
Alkenyl group (propenyl group, butenyl group, octenyl group, etc.), alkoxy group (methoxy group, ethoxy group, butoxy group, etc., hydroxyl group, amino group, aromatic (phenyl group, naphthyl group, etc.), heterocyclic group (pyridyl group, Furyl group, thiophenyl group, etc.) and the like.

At least one of the substituents R ^{1 to} R ⁸ is a substituent having a conductive polymer unit, and as the substituent having a conductive polymer unit, each residue such as polyaniline, polyphenylene, polythiophene, or polyfuran is used. Examples thereof include groups, and among them, residues such as polythiophene and polyfuran are particularly preferable in terms of color tone. The structure of the conductive polythiophene or polyfuran unit, which is a substituent of the silsesquioxane mother nucleus of the present invention, is shown by the following general formula (2).

[0028]

[Chemical 2]

In the formula, R ¹ and R ² represent an optionally substituted alkyl group or alkoxy group, X represents a sulfur atom or an oxygen atom, and n represents an integer of 2 to 300. The polythiophene monomer unit preferably has the same substituents at the 3- and 4-positions of the thiophene ring and has a symmetrical structure centered on the sulfur atom, but may be asymmetrical. When the 3- and 4-position substituents are different, it becomes difficult to polymerize a large polymer unit.

The substituents R ¹ and R ² include a ring-forming alkylene group and an alkylenedioxy group. The polythiophene compound doping agent is preferably an inorganic or organic anionic compound. In particular, the doping agent may also serve as an activator used as a coating aid without adding ions.

The addition amount of the compound of the present invention is preferably in the range of 1 microgram to 10 grams per unit area of the photothermographic material. The hydrazine compound, polyhalomethane compound, disulfide compound used in the present invention, When used in combination with a phthalazine compound or a phthalic acid compound, 1 × 10 ⁻⁸ to 1 mol of the compound is used.
It is preferable to add 1 × 10 ³ mol.

The method of addition is to dissolve in water, alcohol (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.), aromatic organic solvent (eg, toluene, xylene, etc.). Alternatively, fine particles may be dispersed and added.

When the compound of the present invention is finely dispersed, the average particle size is preferably 0.7 to 300 nm, and the particle size is such that primary particles can be bound to the compound to form larger particles. it can.

In this case, the substituents R ^{1 to} R ⁸ form a three-dimensional structure in which Si atoms are bonded via oxygen atoms. The layer to be added can be added to any layer, but an antihalation layer (AH layer) under the protective layer or the photosensitive layer,
A subbing layer is preferred. When the protective layer is composed of two layers, it may be added below the protective layer.

A compound having an organic conductive polymer chain in the silsesquioxane mother nucleus is synthesized by synthesizing a silsesquioxane compound as a mother nucleus of a three-dimensional structure and conducting in the side chain of the silsesquioxane mother nucleus. method of binding sex polymer, previously synthesized conductive polymer chains, there is a method of introducing a silsesquioxane compound as a nucleus of a three-dimensional structure in a side chain of the conductive polymer from the later, advance R ¹ ~ Lay easily substituent convert a substituent R ⁸ in the conductive polymer, synthetic methods for converting a substituent of R ¹ to R ⁸ in the conductive polymer units are preferred. The conductive polymer can be easily synthesized with reference to JP-A-7-90060 which uses a redox polymerization method.

Preferred specific examples of the organic electroconductive polymer bonded to the side chain of the silsesquioxane mother nucleus of the present invention are shown below.

[0037]

[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

Specific examples of the side chain having a hydrogen bonding group when the side chain group of the silsesquioxane mother nucleus is not conductive are shown below.

[0041]

[Chemical 6]

Table 1 shows combinations of the substituents R ^{1 to} R ⁸ of the silsequioxane compound.

[0043]

[Table 1]

When the substituents in Table 1 are M8 and M9,
It can be polymerized and can be synthesized using a usual radical polymerization initiator within a molecular weight range of 2,000 to 1,000,000.

When it has a substituent such as M1 to M7, it can be bonded to the binder with a crosslinking agent having an isocyanate group, a vinylsulfonyl group or an epoxy group. The binder is preferably one having an amino group, a hydroxyl group, a carboxyl group, an epoxy group or the like which reacts with these groups, which will be described later.

The compound of the present invention is soluble in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, aromatic solvents such as toluene and xylene, and non-aromatic solvents such as normal hexane and decane. Alternatively, fine particles may be dispersed and added. It is preferable that the total amount of the one side of the support is 1 to 100 g / m < ² > in both the undercoating upper layer or the protective layer of the photosensitive layer, the backing layer and the protective layer of the backing layer. 1
If it is less than mg / m ² , the effect of improving the transportability by the silsesquioxane compound is small, and if it exceeds 100 g / m ² , haze and color tone are impaired, which is not preferable.

(Photosensitive Silver Halide Grain) The photosensitive silver halide contained in the photosensitive layer of the heat-developable photographic material of the present invention can be any of those known in the photographic art such as a single jet method or a double jet method. It can be prepared in advance by any method, for example, an ammonia method emulsion, a neutral method, an acidic method, etc., and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently bring the photosensitive silver halide into contact with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 are used as protective polymers when preparing the photosensitive silver halide. , 565, 3,713,833, 3,748,143, British Patent 1,362,97.
No. 0, a means of using a polymer other than gelatin such as polyvinyl acetals, or a gelatin of a photosensitive silver halide emulsion as described in British Patent 1,354,186. Means of enzymatic degradation,
Alternatively, each means such as by omitting the use of a protective polymer by preparing the photosensitive silver halide grains in the presence of a surfactant as described in U.S. Pat. No. 4,076,539. Can be applied.

The photosensitive silver halide is preferably one having a small particle size in order to suppress white turbidity after image formation and to obtain a good image quality. The average particle size is usually 0.1 μm or less, preferably 0.01 to 0.1 μm, and particularly preferably 0.02 to 0.08 μm.

The shape of the silver halide is not particularly limited, and it may be cubic or octahedral so-called normal crystal or non-normal crystal spherical, rod-like, tabular, etc. grains. The silver halide composition is also not particularly limited and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide.

The amount of the above silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 0.1% by mass based on the total amount of the silver halide and the organic silver salt described below. .

Various conditions such as reaction temperature, reaction time and reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-described silver halide-forming component should be appropriately set according to the purpose of preparation. However, the reaction temperature is usually -2.
It is preferable that the reaction time is 3 to 74 ° C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is atmospheric pressure.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compound, palladium compound, silver compound, tin compound,
It can be chemically sensitized with a chromium compound or a combination thereof. The chemical sensitization method and procedure are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850 and the like, and JP-A-51-1850.
No. 22430, No. 51-78319, No. 51-811
No. 24 and other publications.

The silver halide used in the present invention can be sensitized with a spectral sensitizing dye as required. For example, JP-A-63-159841, JP-A-60-140335 and JP-A-60-140335 can be used.
3-231437, 63-259651, 63
-304242, 63-15245, etc.,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
The sensitizing dyes described in each specification such as No. 175 and No. 4,835,096 can be used. Useful sensitizing dyes used in the present invention are described in, for example, JP-A-9-3407.
Compounds described in No. 8, No. 9-54409 and No. 9-80679 can be preferably used.

(Organic Silver Salt) The organic silver salt contained in the heat-developable photographic material of the present invention is a reducible silver source, and includes organic acids, heteroorganic acids and acid polymers containing a reducible silver ion source. A silver salt or the like is used. Also, the ligand is 4.0
Organic or inorganic silver salt complexes having a total stability constant for silver ions of ˜10.0 are also useful. Examples of silver salts include salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.).

(Reducing Agent) Examples of preferable reducing agents contained in the photothermographic material of the present invention are described in US Pat. No. 3,770,
No. 448, No. 3,773,512, No. 3,59
Although those described in each specification such as 3,863 can be applied, specific examples of preferable reducing agents are shown below.

(K1) 1,1-bis (2-hydroxy-)
3,5-Dimethylphenyl) -3,5,5-trimethylhexane (K2) bis (2-hydroxy-3-t-butyl-5-
Methylphenyl) methane (K3) 2,2-bis (4-hydroxy-3-methylphenyl) propane (K4) 4,4-ethylidene-bis (2-t-butyl-)
6-Methylphenol) (K5) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane The compound shown above is used by being dispersed in water or dissolved in an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatic compounds such as toluene and xylene can be arbitrarily selected. The reducing agent is used in an amount of 1 × 10 ⁻² to 10 mol, preferably 1 × 10 ⁻² to 1.
It is 5 mol.

(Binder) As the polymer binder used in the light-sensitive layer or the non-light-sensitive layer of the heat-developable photographic material of the present invention, polyvinyl butyral, polyacrylamide, polystyrene, polyvinyl acetate, polyurethane, polyacrylic acid ester, Examples thereof include a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, a vinyl chloride-vinyl acetate copolymer, and a styrene-butadiene-acrylic copolymer.

After further drying, after forming a film, it is preferable that the coating film has a low equilibrium water content, and particularly, those having a low water content include, for example, organic solvent-based cellulose acetate, cellulose acetate butyrate and polyacetal. Can be mentioned.

The polyacetal means a polymer obtained by producing polyvinyl alcohol by saponifying polyvinyl acetate and reacting the polyvinyl alcohol with an aldehyde compound. The polyacetal preferable in the present invention is acetalized with butyraldehyde. Preferred are polybutyral and polyacetal acetalized with acetaldehyde (polyacetal in a narrow sense).
The acetalization theoretically exists up to 1 to 100%, but practically 20 to 95% is preferable.

When the degree of acetalization is less than 20%, the number of hydroxyl groups is large, and the photographic performance shows a property of being weak against humidity. When the degree of acetalization exceeds 95%, the reaction temperature and time become harsh, resulting in cost and productivity. Is reduced.

For water-based coating, copolymers of styrene and butadiene which are water-dispersible polymers, copolymers of styrene and alkyl acrylates or alkyl methacrylates, and alkyl acrylates and alkyl methacrylates. A copolymer can be mentioned. Further, the water-dispersed polymer is preferably a fine particle having an average particle diameter in the range of 1 nm to several μm and dispersed in an aqueous dispersion medium. The water-dispersed polymer is particularly preferably hydrophobic because it can improve water resistance among the widely used binders for water-based coating. The degree of polymerization of the polymer can be freely selected from 10 to 10,000, but 100 to 6000 is preferable from the viewpoint of coating properties and productivity during synthesis.

(Crosslinking Agent) The binder can maintain the adhesion to the lower layer and the upper layer by forming a film alone, and can obtain a film strength that is not easily scratched. The film adhesion and film strength can be increased.

Further, the cross-linking agent for cross-linking between the binders also reacts with the organic or inorganic fine particles having a reactive group used in the present invention to chemically bond to the binder and to be immobilized.

The crosslinking agent preferred in the present invention is preferably a crosslinking agent having an isocyanate group, a vinylsulfonyl group, an epoxy group or an alkoxysilane group. Particularly preferred cross-linking agents include polyfunctional cross-linking agents having at least two isocyanate groups, vinyl sulfonyl groups and epoxy groups in one molecule. The preferred crosslinking agent is (H
-1) to (H-5) and (H-6) to (H-22) are represented by structural formulas.

[0065] (H-1) hexamethylene diisocyanate (H-2) hexamethylene diisocyanate trimer (H-3) Tolylene diisocyanate (H-4) Phenylene diisocyanate (H-5) xylylene diisocyanate

[0066]

[Chemical 7]

[0067]

[Chemical 8]

The above-mentioned cross-linking agent may be dissolved in water, alcohols, ketones or non-polar organic solvents and added,
It may be added as a solid to the coating solution. The addition amount is preferably equivalent to the crosslinkable group, but may be increased up to 10 times or may be decreased up to 1/10 or less. If it is less than 0.1, the crosslinking reaction proceeds, and if it exceeds 10 times, the unreacted crosslinking agent deteriorates the photographic properties, which is not preferable.

(Dye Used in AH Layer or BC Layer) The photothermographic material of the present invention is optionally provided with an AH layer or a BC layer for preventing halation of the photothermographic material or for preventing halation. The dye used in the AH layer or the BC layer may be any dye that absorbs image exposure light, and preferable examples thereof are JP-A-2-216140 and JP-A-7-216140.
-13295, 7-11432, U.S. Pat.
Examples thereof include dyes described in the specification of 380,635.

(Support) As the support, a support such as polyethylene terephthalate, polyethylene naphthalate or syndiotactic polystyrene is preferable.
It is preferably axially stretched or heat-fixed and has a thickness of 50 μm to 400 μm, which has high optical isotropy and good dimensional stability.

<Image exposure> An exposure method is disclosed in Japanese Patent Laid-Open No.
No. 304869, No. 9-311403 and JP 20
Laser exposure can be carried out by the method described in 00-10230.

For exposure of the heat-developable photographic material of the present invention, it is desirable to use a light source suitable for the color sensitivity imparted to the heat-developable photographic material. For example, when the heat-developable photographic material is made to be sensitive to infrared light, it can be applied to any light source in the infrared light range, but the laser power is high and the heat-developable photograph An infrared semiconductor laser (780 nm, 820 nm) is more preferably used from the viewpoint that the material can be made transparent.

<Heat Developing Device> The devices for developing the heat developing photographic material are disclosed in JP-A Nos. 11-65067 and 11-7289.
No. 7 and No. 11-84619, etc. can be used.

[0074]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of undercoated support> A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 12 W / m ² · min on both surfaces, and one surface of the undercoat coating solution a-1 was prepared as follows.
Is coated to a dry film thickness of 0.6 μm and dried to form an undercoat layer A-1, and the undercoat coating solution b described below is provided on the opposite surface.
-1 was applied so as to have a dry film thickness of 0.6 μm and dried to form an undercoat layer B-1.

<< Undercoat coating liquid a-1 >> butyl acrylate (30% by mass) t-butyl acrylate (20% by mass)
Styrene (25 mass%) 2-hydroxyethyl acrylate (25 mass%) copolymer latex liquid (solid content 3
0%) is diluted 15 times.

<< Undercoat coating liquid b-1 >> A copolymer latex liquid (solid content 30%) of butyl acrylate (40% by mass) styrene (20% by mass) and glycidyl acrylate (40% by mass) is diluted 15 times.

Subsequently, undercoat layer A-1 and undercoat layer B-1
12 W / m ² · min of corona discharge is applied to the surface of the undercoat layer A-1, and the following undercoat top layer coating solution a-2 is applied and dried on the undercoat layer A-2 (photosensitive layer side). For the undercoat layer B-
The following undercoat upper layer coating liquid b-2 was applied and dried on No. 1 to provide an undercoat upper layer B-2 (for BC layer) having an antistatic function.

[0079]   << Undercoat upper layer coating liquid a-2 >>   1: 2 copolymer of styrene and butadiene 0.4g / m²   Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Tylene (25% by mass) 2-hydroxyethyl acrylate (20% by mass) Methac Copolymer latex solution of phosphoric acid (5% by mass) (solid content 30%)                                                          0.3 g / m²   << Undercoat upper layer coating liquid b-2 >>   1: 2 copolymer of styrene and butadiene 0.4g / m²   Butyl acrylate (30% by mass) t-butyl acrylate (20% by mass) Tylene (25% by mass) 2-hydroxyethyl acrylate (20% by mass) Methac Copolymer latex solution of phosphoric acid (5% by mass) (solid content 30%)                                                          0.3 g / m² <Preparation of silver halide grain emulsion A>
Dissolve 7.5 g of nato gelatin and 10 mg of potassium bromide
After unraveling and adjusting the temperature to 28 ° C and pH to 3.0, silver nitrate
Molar ratio of 370 ml aqueous solution containing 74 g and (98/2)
PAg of an aqueous solution containing potassium bromide and potassium iodide
Controlled double jet method while keeping at 7.7
Added over 10 minutes. In sync with the addition of silver nitrate
1 × 10 sodium salt of sachloroiridium ^-6Mol /
1 mol of silver was added. Then 4-hydroxy-6-methyl
0.3 g of 1,3,3a, 7-tetrazaindene
Add, adjust pH to 5 with NaOH and average particle size
0.036 μm, variation coefficient of projected diameter area 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This milk
After gelatinization and sedimentation using gelatin flocculant as the agent,
Water was added to make 160 ml.

<Preparation of Organic Silver Salt> 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 3980 ml of pure water at 80 ° C. Next, while stirring at high speed, a 1.5 mol / L sodium hydroxide aqueous solution 5
After adding 40.2 ml and adding 6.9 ml of concentrated nitric acid,
It cooled at 5 degreeC and the organic-acid sodium solution was obtained. While maintaining the temperature of the above-mentioned sodium salt of an organic acid at 55 ° C., 420 ml of pure water was added to the silver halide grain emulsion A (containing 0.038 mol of silver) and stirred for 5 minutes. Then 1 mol /
760.6 ml of silver nitrate solution of L was added over 2 minutes,
The mixture was stirred for 20 minutes, and the water-soluble salts were removed by filtration. Thereafter, washing with ion-exchanged water and filtration were repeated until the electric conductivity of the filtrate became 2 μs / cm, and finally, centrifuge dehydration and drying were performed.

<< Coating of Photosensitive Layer and Backcoat (BC) Layer >> The following photosensitive layer side and BC layer side layers were coated on the support provided with the undercoat layer. In addition, drying is performed on the photosensitive layer side and B
It was carried out at 45 ° C. for 1 minute on each of the layers C.

<BC layer side coating> On the back surface side, a coating liquid prepared by preparing the following composition was coated simultaneously on the B-2 layer in the following coating amounts and dried to form a BC layer.

(Coating of BC Layer) Binder: PVB-1 1.8 g / m ² Hexamethylene diisocyanate 1 × 10 ⁻⁴ mol / m ² Dye: C1 2.2 × 10 ⁻⁵ mol / m ² (BC Coating of protective layer) Styrene-ethyl acrylate-acrylic acid amide copolymer 1.2 g / m ² silsesquioxane compound (shown in Table 2) 0.10 g / m ² <coating on photosensitive layer side> (anti Coating of antihalation (AH) layer) Binder: PVB-1 0.4 g / m ² Dye: C1 (same type as BC layer) 1.3 × 10 ⁻⁵ mol / m ² (coating of photosensitive layer) Formation of photosensitive layer Therefore, a coating solution of the following composition was prepared, and the photosensitive layer was formed by coating and drying on the A-2 layer so as to have the following coverage. 1.36g / as silver
An amount of m ² of the organic silver salt preparation was mixed with the polymer binder.

Binder: PVB-1 2.6 g / m ² Spectral sensitizing dye A1 2 × 10 ^-5 mol / m ² Antifoggant-1: Pyridinium hydrobromide perbromide 0.3 mg / m ² Antifoggant- 2: isothiazolone 1.2 mg / m ² reducing agent: K-4 3 × 10 ^-4 mol / m ²

[0085]

[Chemical 9]

<< Surface Protective Layer >> A coating solution prepared by adding the following composition was coated and dried on the photosensitive layer to the following coating amounts to form a surface protective layer.

Styrene-ethyl acrylate-acrylic acid amide copolymer 1.2 g / m ² phthalazine 0.2 g / m ² 4-methylphthalic acid 0.7 g / m ² tetrachlorophthalic acid 0.2 g / m ² silsesqui Oxane compound (described in Table 2) 0.12 g / m ² silica (average particle diameter 3 μm) 0.08 g / m ^{2 When} the compound of the present invention is added to the photosensitive layer, BC layer and undercoat upper layer, The amount was the same as the amount of the silsesquioxane compound added to the protective layer.

(Evaluation of Photographic Performance) Two samples were prepared as above.
After storing at 5 ° C and 48% relative humidity for 3 days,
Exposing with a photometer for semiconductor laser exposure of 810 nm,
After heating at 120 ° C. for 8 seconds after exposure, the fog and relative sensitivity (reference 100) of the obtained sample were determined. The relative sensitivity was expressed by the reciprocal of the exposure amount at a density of 0.3.

(Evaluation of Transportability) Each sample was treated at a treatment length of 20.
m, a transportability tester having 19 mirror-finished stainless steel rollers with a diameter of 10 cm, and a tension of 1 N / cm, 100 m /
While being conveyed at a speed of a minute, it was conveyed for 300 m, and the stains on the roller and the film were evaluated. The stain on the roller was evaluated by visually observing stains at 5 points on the 19th surface of the roller in three grades and expressed as an average value. The best level was 5.0 and the worst level was 1.0. 3.0 is an intermediate level, which is practically no problem. The evaluation results of the above test are shown in Table 2.

The stains on the film were obtained by drying the film surface of the B-2 surface of the undercoat support as it passed through the 19th roller, and measuring the density of the dried film surface and the density of the dried film surface around it. Five points were measured, the difference in density was calculated as an average value, and the stain of the film was evaluated.

The evaluation rank of each sample is that the concentration of each sample is 5: less than 0.03 with respect to the surrounding film surface concentration, 4: 0.03 to less than 0.05 with respect to the surrounding film surface concentration, 3: 0.05 to less than 0. 10 with respect to the surrounding film surface concentration, 2: 0.10 to less than 0.20 with respect to the surrounding film surface concentration, 1: 0.20 or more with respect to the surrounding film surface concentration, The results are shown in Table 2.

(Evaluation of Image Defects After Carrying Test) Image defects after development were measured with a density of 1.0 ± 0.
A uniform solid exposure was performed so as to be 1, and the frequency (number of appearances) of image defects due to peeling of fine particles present therein was examined.

(Evaluation of Antistatic Performance) The above unexposed sample was left in a room with a relative humidity of 20% for 18 hours, and then the sample was treated with a synthetic fiber cloth (60% nylon, 40% polyester).
Rubbing was carried out 5 times for each sample, these were held over 100 styrene beads (average particle diameter 3 mm) (approaching distance 15 mm), and the number of beads adsorbed was determined and evaluated as an average value.

[0094] 5: 0 to less than 3 adsorption, 4: 3 to less than 9 adsorption, 3: 9 to less than 16 adsorptions, 2: 16 to less than 25 adsorbed, 1: Adsorption of 25 or more, The results are shown in Table 2.

[0095]

[Table 2]

From Table 2, the samples of the present invention are superior in transportability, less polluted on the rollers, and less than the comparative samples.
It can be seen that the antistatic effect is good and there are no image defects in the photothermographic material. Regarding the photographic performance, it can be seen that there is no fog or sensitivity fluctuation. Further, the compound of the present invention is used in the photosensitive layer, B
It can be seen that the addition to the protective layer improves the transportability of the photothermographic material of the present invention more than the addition to the C layer.

Example 2 As shown in Table 3, samples 202 to 223 were prepared in the same manner as in Example 1 except that a crosslinking agent was added, and the same evaluation as in Example 1 was performed.

[0098]

[Table 3]

From Table 3, it can be seen that the sample using the compound of the present invention and the cross-linking agent has less contamination of the roller and the sample as compared with the sample 108 of the present invention which does not use the cross-linking agent, and has an antistatic property. It can be seen that the heat-developable photographic material has excellent image defects. Further, it can be seen that there is no fog or sensitivity variation in photographic performance.

Example 3 As shown in Table 4, compounds SL-19 and SL-2 of the present invention were prepared.
0 (a compound having a polymerizable vinyl group as a substituent of the silsesquioxane mother nucleus) was polymerized (described in Table 4 of the degree of polymerization) and cross-linking agents were added to prepare Samples 301 to 308. The same evaluation as in 1 was performed.

[0101]

[Table 4]

From Table 4, compounds SL-19 and SL of the present invention can be obtained.
Sample 30 using compound obtained by polymerizing -20 and crosslinking agent
It can be seen that Nos. 1 to 308 did not stain the rollers and the sample, were excellent in antistatic performance, had better transportability, and had no image defects in the photothermographic material. It can be seen that the photographic performance does not affect the fog or sensitivity fluctuation.

Further, it is understood that the samples added to the emulsion layer protective layer and the BC protective layer as the added layers are more excellent in transportability.

[0104]

The heat-developable photographic material of the present invention has excellent antistatic performance and transportability in the development processing step, and has excellent effects that do not adversely affect photographic performance.

Claims (7)

[Claims] 1. A photothermographic material containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, wherein a compound having an organic conductive polymer chain in the silsesquioxane nucleus is used. A heat-developable photographic material characterized by containing. 2. The organic conductive polymer chain is polythiophene or polyfuran.
The heat-developable photographic material described in 1. 3. The photothermographic material according to claim 1, wherein the silsesquioxane mother nucleus contains a compound having an organic conductive polymer chain in the outermost layer. 4. The compound having an organic conductive polymer chain in the silsesquioxane mother nucleus has a substituent that forms a hydrogen bond with the organic conductive polymer chain and the binder. The heat-developable photographic material as described in 1 above. 5. The compound having an organic conductive polymer chain in the silsesquioxane mother nucleus and the crosslinking agent with which the binder reacts have an isocyanate group, a vinylsulfonyl group, an epoxy group or an alkoxysilane group. The heat-developable photographic material according to claim 1. 6. The photothermographic material according to claim 1, wherein the compound having an organic conductive polymer chain in the mother nucleus of silsesquioxane has a polymerizable group. 7. The photothermographic material according to claim 1, wherein the protective layer contains a compound having an organic conductive polymer chain in the silsesquioxane mother nucleus.