JP2002268177A - Fluorine-containing anionic surfactant, method for preparing the same and photothermographic image forming material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-containing anionic surfactant and a photothermographic image forming material which forms a uniformly coated even silver image without adversely affecting fog, sensitivity and preservability. SOLUTION: The fluorine-containing anionic surfactant is represented by formula (1) (where R<f> is a fluorine substituted chain aliphatic group; Hr is a 5- or 6-membered ring group selected from pyridine, furan and thiophene rings; L1 is a 1-4C divalent linking group; M is H or an alkali metal atom; and (p) is 0 or 1). The photothermographic image forming material has a layer containing the fluorine-containing anionic surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing anionic surfactant, a method for producing the same, and a photothermographic image-forming material containing the fluorine-containing anionic surfactant.
More specifically, the present invention relates to a novel fluorine-containing anionic surfactant capable of obtaining a photothermographic imaging material capable of forming a uniformly coated silver image without adversely affecting fog, sensitivity and storage stability.

[0002]

2. Description of the Related Art Conventionally, a typical fluorine-containing anionic surfactant is a fluorine-containing anionic surfactant in which a sulfonic acid is bonded as an anion to an aliphatic group or an aromatic group containing a fluorine atom. Also known as Further, fluorine-containing anionic surfactants having an aromatic benzene ring group between a group containing fluorine and a group serving as an anion are also widely known. Fluorinated anionic surfactants have strong hydrophobicity of fluorine-containing groups and hydrophilicity of sulfonic acid groups that are easily dissociated as anions. it can. For photographic photosensitive materials such as photothermographic image forming materials, applicability (coating surface is uniform and free of unevenness), charging characteristics (reduction of static electricity due to friction between films and peeling), scratch resistance , Improvement in the resistance to dust (to prevent the films from sticking to each other when the films are stacked and stored at a high temperature) and the like, and a surfactant is used for this purpose. As the agent, a fluorine-containing anionic surfactant capable of obtaining an excellent effect has been used. However, conventional fluorinated anionic surfactants were insufficient to improve the coating properties, charging properties, scratch resistance and dustiness without adversely affecting the photographic properties. Accordingly, the present inventors have studied and found that a novel fluorine-containing compound having a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring between a group containing fluorine and a group serving as an anion. Anionic surfactants are used for photographic materials,
In particular, it has been found that in the photothermographic image forming material, the coating properties, the charging properties, the scratch resistance, and the resistance to dustiness can be sufficiently improved without adversely affecting the photographic properties. A pyridine ring, a furan ring, introduced into a fluorine-containing anionic surfactant,
The thiophene ring is inferior in hydrophobicity to the benzene ring, so the hydrophobicity brought about by the introduction of fluorine atoms is reduced, weakening the function as a surfactant, and it seems that the effect on photographic materials cannot be obtained. On the other hand, on the other hand, the coating properties, the charging properties, the scratch resistance and the tightness were sufficiently improved without adversely affecting the photographic characteristics of the photographic light-sensitive material.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a photothermographic image forming material capable of forming a uniformly coated and uniform silver image without adversely affecting fog, sensitivity and storage stability. An object of the present invention is to provide a novel fluorine-containing anionic surfactant obtained. A second object of the present invention is to provide a photothermographic image-forming material which forms a uniformly coated and uniform silver image without adversely affecting fog, sensitivity and storage stability.

[0004]

The object of the present invention is to provide (1) a fluorine-containing anionic surfactant represented by the general formula (1).

[0005]

Embedded image (In the formula, R ^f represents a chain aliphatic group substituted by a fluorine atom, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, and L ₁ represents the number of carbon atoms. Represents a divalent linking group of 1 to 4, M represents a hydrogen atom, an atom or a group of atoms forming a salt, and p represents 0 or 1.) (2) In the general formula (1), R ^f The fluorine-containing anionic surfactant according to the above (1), wherein the represented chain-like aliphatic group substituted with a fluorine atom is a perfluoroalkenyl group or a (perfluoroalkyl) alkyl group. (3) The compound represented by the above (1) or (2), wherein the compound represented by the general formula (2) is dissolved or dispersed in a non-aqueous polar solvent and reacted with a chain aliphatic compound substituted with a fluorine atom. ).

[0006]

Embedded image (In the formula, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, M represents a hydrogen atom, Represents an atom or a group of atoms forming a salt, M ₁ represents an alkali metal atom, and p represents 0 or 1.) (4) The compound represented by the general formula (3) is dissolved in a non-aqueous polar solvent or The method for producing a fluorine-containing anionic surfactant according to the above (1) or (2), wherein the surfactant is dispersed, reacted with a chain aliphatic compound substituted with a fluorine atom, and then sulfonated.

[0007]

Embedded image (Wherein, Hr denotes the pyridine ring, a 5- or 6-membered ring group selected from a furan ring and thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, M ₁ is an alkali metal (5) The chain aliphatic compound substituted by a fluorine atom is a trimer of hexafluoropropene, wherein (3) or (4) The method for producing a fluorinated anionic surfactant according to (1). (6) The non-aqueous polar solvent described above, wherein the non-aqueous polar solvent is a non-aqueous polar solvent selected from N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylimidazoline. (3)-
The method for producing a fluorine-containing anionic surfactant according to any one of (5). (7) The compound represented by the general formula (2) or (3) described in the above (3 or 4) and hexafluoropropene
The method for producing a fluorine-containing anionic surfactant according to the above (5), wherein the reaction temperature with the monomer is 30 ° C to 160 ° C. (8) The production of a fluorine-containing anionic surfactant according to any one of the above (3) to (7), wherein the anionic group is a sodium salt, a lithium salt or a potassium salt of a sulfonic acid group. Method. (9) In the photothermographic image-forming material provided with a layer containing a silver halide, an organic silver salt, a reducing agent and a binder on a support, the fluorine-containing anion interface as described in the above (1) or (2), A photothermographic image-forming material having a layer containing an activator. (10) a layer containing a fluorine-containing anionic surfactant,
The photothermographic image forming material according to the above (9), which is the uppermost layer of the photothermographic image forming material. (11) In a layer containing a fluorine-containing anionic surfactant,
The photothermographic image-forming material as described in the above item (9) or (10), further comprising a fluorine-containing nonionic surfactant. Is achieved by

Hereinafter, the present invention will be described in detail. First, the fluorine-containing anionic surfactant of the present invention will be described.
The fluorine-containing anionic surfactant of the present invention is represented by the following general formula (1).

[0009]

Embedded image (In the formula, R ^f represents a chain aliphatic group substituted by a fluorine atom, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, and L ₁ represents the number of carbon atoms. Represents a divalent linking group of 1 to 4, M represents a hydrogen atom, a salt-forming atom or a group of atoms, and p represents 0 or 1.) In the general formula (1), R ^f is a fluorine atom Although it is a substituted chain aliphatic group, it preferably has 4 to 12 carbon atoms, and particularly preferably 6 to 9 carbon atoms. As the chain aliphatic group substituted with a fluorine atom, a chain aliphatic group in which a fluorine atom is bonded to all of the carbon atoms that can be substituted with a fluorine atom is preferable. A chain aliphatic group having two unsaturated groups, for example, a perfluoroalkenyl group in which all of the carbon atoms that can be substituted with a fluorine atom are substituted with a fluorine atom is a particularly preferred chain aliphatic group in which a fluorine atom is substituted. One of the groups. Further, a conjugate of an alkyl group in which all of the carbon atoms that can be substituted with a fluorine atom is substituted with a fluorine atom and an alkyl group that is not substituted with a fluorine atom is also a particularly preferred chain aliphatic group substituted with a fluorine atom. One. The alkenyl group referred to herein includes those having two or more unsaturated groups. When the chain aliphatic group substituted with a fluorine atom is a conjugate of an alkyl group substituted with a fluorine atom and an alkyl group not substituted with a fluorine atom, all of the carbon atoms that can be substituted with a fluorine atom are fluorine. The carbon of the alkyl group not substituted with an atom is 1 to 1
0 is preferred, and particularly preferably 1 to 3 carbon atoms. The 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring represented by Hr may have a substituent. Hr includes -SO represented by the general formula (1).
₃ M is a (sulfonate) one or more sulfonate in addition can be introduced as a substituent, a pyridine ring, a 5- or 6-membered ring group selected from furan and thiophene rings represented by Hr Has 2 total sulfonate groups
It is preferably 1 or less, and more preferably 1. Examples of the divalent linking group having 1 to 4 carbon atoms represented by L ₁ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, and a butylene group. Examples of atoms or atoms forming a salt represented by M include an alkali metal atom, —NH ₄ , and an amine.
Potassium and lithium are preferred. Hereinafter, preferred specific examples of the compound represented by the general formula (1) are shown below.

[0010]

Embedded image

[0011]

Embedded image The fluorine-containing anionic surfactant represented by the general formula (1) includes: (A) a chain obtained by dissolving or dispersing a compound represented by the following general formula (2) in a non-aqueous polar solvent, and Reaction with linear aliphatic compound (first synthesis method)

[0012]

Embedded image (In the formula, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, M represents a hydrogen atom, Represents an atom or a group of atoms forming a salt, M ₁ represents an alkali metal atom, and p represents 0 or 1.) (B) A compound represented by the following general formula (3) is dissolved in a non-aqueous polar solvent Or disperse, react with a chain aliphatic compound substituted by a fluorine atom, and then sulfonate (second synthesis method)

[0013]

Embedded image (In the formula, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, and M ₁ represents an alkali metal. Represents an atom, and p represents 0 or 1.) In the general formula (2) and _{(3), L 1, Hr} , M is, L _1, Hr, respectively and M is as defined in formula (1). Examples of the alkali metal atom represented by M ₁ include sodium, potassium, and lithium. The reaction scheme of the first synthesis method is shown below.

[0014]

Embedded image In the reaction scheme of the first synthesis method, R ^f , L ₁ , H
r, M, M ₁ is R ^f, L _1, synonymous Hr, M, and M ₁ in the general formula (1) or (2). p represents 0 or 1. R ^f1 is a chain aliphatic compounds substituted with fluorine atom, a compound for introducing the R ^f, R ^f X
(X represents a hydrogen atom or a fluorine atom.) As the chain aliphatic compound substituted with a fluorine atom represented by R ^f1 , an alkyl group having a perfluoroalkyl group as a substituent and hexafluoropropene trimer are particularly preferable. Hexafluoropropene trimer is a mixture of perfluoro compounds having one unsaturated bond. In the first synthesis method, a hydroxy group or a hydroxyalkyl group (for example, an alkali metal salt)
In this method, a heterocyclic group having a hydroxymethyl or hydroxyethyl group is bonded to a compound represented by R ^f1 . As the alkali metal represented by M in the alkali metal salt of a sulfonic acid group and M ₁ in the alkali metal salt of a hydroxy group or a hydroxyalkyl group, potassium, sodium or lithium is preferable.
The reaction between R ^f1 and the compound represented by the general formula (2) is preferably performed using an organic solvent in which these compounds are soluble, and a non-aqueous polar solvent, particularly, N, N-dimethylformamide, N, N It is preferable to use a non-aqueous polar solvent selected from N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylimidazoline. Reaction temperature is 30
C. to 160 C. are preferred. The reaction time is closely related to the reaction temperature, and the reaction time can be shortened at a high temperature. Preferred reaction times are from 1 hour to 24 hours,
The reaction is preferably completed within 8 hours from the viewpoint of productivity. Preferred specific examples represented by the general formula (2) are shown below.

[0015]

Embedded image The reaction scheme of the second synthesis method is shown below.

[0016]

Embedded image In the reaction scheme of the second synthesis method, R ^f , L ₁ , H
r, M, M ₁ is R ^f, L _1, synonymous Hr, M, and M ₁ in the general formula (1) or (3). p represents 0 or 1. R ^f1 is a chain aliphatic compounds substituted with fluorine atom, a compound for introducing the R ^f, R ^f X
(X represents a hydrogen atom or a fluorine atom.) As the chain aliphatic compound substituted with a fluorine atom represented by R ^f1 , an alkyl group having a perfluoroalkyl group as a substituent and hexafluoropropene trimer are particularly preferable. Hexafluoropropene trimer is a mixture of perfluoro compounds having one unsaturated bond. In the second synthesis method, a heterocyclic group having a hydroxy group or a hydroxyalkyl group (for example, a hydroxymethyl or hydroxyethyl group) and not having a sulfonic acid group is converted to an alkali metal salt, and then R ^f1
And then sulfonating the compound. Sulfonation can be performed by a usual sulfonation method, and can be carried out by adding fuming sulfuric acid in an amount of about 2 to 2 equivalents. As the alkali metal atom represented by M in the alkali metal salt of a sulfonate group and M ₁ in the alkali metal salt of a hydroxy group or a hydroxyalkyl group, potassium, sodium or lithium is preferable. The reaction of R ^f1 with the compound represented by the general formula (3)
It is preferably carried out using an organic solvent in which these compounds are soluble, and is selected from non-aqueous polar solvents, especially N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylimidazoline. It is preferable to use a non-aqueous polar solvent. The reaction temperature is preferably from 30C to 160C. The reaction time is closely related to the reaction temperature, and the reaction time can be shortened at a high temperature. The preferred reaction time is 1 hour to 24 hours, but the reaction is preferably completed within 8 hours from the viewpoint of productivity. Preferred specific examples represented by the general formula (3) are shown below.

[0017]

Embedded image

By using the above-mentioned fluorine-containing anionic surfactant of the present invention in a photothermographic image forming material, it forms a uniformly coated and uniform silver image without adversely affecting fog, sensitivity and storage stability. A photothermographic image forming material can be obtained. In the photothermographic image forming material, the layer containing the anionic surfactant of the present invention may be any layer, but is preferably added to a protective layer which is a surface layer of the photothermographic image forming material. The photothermographic image forming material is usually provided with at least a photosensitive layer and a protective layer on one side of a support, and a back coat layer (BC layer) on the side of the support opposite to the side having the photosensitive layer. Is provided with a protective layer of a BC layer. The photosensitive layer contains photosensitive silver halide grains that may be sensitized, and further contains a reducing agent for developing an organic silver salt serving as a silver source and a silver salt to form a silver image. You. An organic silver salt serving as a silver source and a reducing agent for developing a silver salt to form a silver image can be contained in a layer different from the photosensitive layer. The fluorine-containing anionic surfactant of the present invention may be added to any of the above-mentioned layers, but is preferably added to the protective layer or the BC layer serving as the surface layer of the photosensitive layer or the protective layer. Further, it is also preferable to add it to the photosensitive layer and the BC layer below the protective layer. Further, it may be added to an intermediate layer, an undercoat layer or the like adjacent to the photosensitive layer, or may be further added to a layer via an intermediate layer.

The fluorine-containing anionic surfactant of the present invention comprises:
1 microgram to 1 per square meter of photothermographic image material
It is preferred to use in the range of 0 grams. Addition methods include water, alcohol (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.),
It can be added by dissolving it in an aromatic organic solvent (for example, toluene, xylene, etc.) or dispersing it in fine particles. When dispersed in fine particles, the average particle diameter of the particles is preferably 1 nanometer to 300 nanometers. Although the fluorinated anionic surfactant of the present invention can be used alone, it is also preferable to use in combination with a conventionally known fluorinated nonionic surfactant or fluorinated cationic surfactant.
In particular, when the fluorinated nonionic surfactant and the fluorinated anionic surfactant of the present invention are used in combination, the coatability is improved by the synergistic effect, and effects such as abrasion prevention and antistatic can be obtained. The fluorinated nonionic surfactant is preferably added to the same layer as the fluorinated anionic surfactant of the present invention. Examples of the fluorine-containing nonionic surfactant that can be used in combination with the above include compounds represented by the following general formula (4).

[0020]

Embedded image (Wherein, R ^f represents a chain aliphatic group substituted by a fluorine atom, L ₂ represents a divalent linking group, Z represents a polyoxyalkylene group, and q and r represent 0 or 1. , Q and r are not simultaneously 0.) In the general formula (4), R ^f is a chain aliphatic group substituted by a fluorine atom, and preferably has 4 to 13 carbon atoms. . The chain aliphatic group substituted with a fluorine atom includes those in which at least one hydrogen atom of the hydrogen-carbon bond of the chain aliphatic group has been substituted with at least one fluorine atom. Examples of the divalent linking group include an alkylene group having 1 to 4 carbon atoms, a phenylene group, and an oxyphenylene group. Examples of the polyoxyalkylene group represented by Z include oxyethylene having a polymerization degree of 2 to 100. Groups, oxypropylene groups, oxybutylene groups, 2-hydroxypropylene groups, and the like. Preferred specific examples of the fluorinated nonionic surfactant that can be used in the present invention are shown below.

[0021]

Embedded image These compounds are commercially available, and these commercially available products can be obtained and used. Moreover, it is also possible to synthesize by an ordinary synthesis method. These fluorine-containing nonionic surfactants can be added to each layer of the photothermographic image forming material by adding them to the coating solution of each layer. Fluorinated nonionic surfactants are used in water, alcohols (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.), and aromatic organic solvents (eg, toluene, xylene, etc.). It can be dissolved or dispersed in fine particles and added to the coating solution. The fluorine-containing nonionic surfactant of the present invention is preferably used in an amount of 1 microgram to 10 grams per square meter of the photothermographic imaging material. The fluorinated nonionic surfactant can be added to the photosensitive layer, the photosensitive layer protective layer, the BC layer, and the BC protective layer, but is preferably added to the photosensitive layer protective layer and / or the BC protective layer.

Next, the photosensitive silver halide grains used in the photothermographic image forming material of the present invention will be described. The photosensitive silver halide contained in the photosensitive layer, using any method known in the field of photographic technology such as a single jet or double jet method, for example, any of ammonia method, neutral method, acid method and the like Can be prepared in advance. The photosensitive silver halide preferably has a small grain size in order to suppress white turbidity after image formation and obtain good image quality. The average particle size (calculated by the average diameter by the projected area method) is 100 nm or less, preferably 10 nm to 100 nm, particularly preferably 20 nm to 80 nm. The shape of the silver halide is not particularly limited, and cubic or octahedral so-called normal crystals, non-normal crystals such as spherical, rod-like, and tabular grains are used. There is no particular limitation on the silver halide composition,
Any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide may be used. The amount of the photosensitive silver halide in the photothermographic image-forming material of the present invention is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 25% by mass or less, based on the total amount of the photosensitive silver halide and the organic silver salt described below. 1
5 to 0.1% by mass. Further, the photosensitive silver halide of the present invention is disclosed in U.S. Pat. No. 4,009,039,
Nos. 3,457,075 and 4,003,7
No. 49, British Patent No. 1,498,956, JP-A-53-27027, JP-A-53-2542.
One of the organic silver salts described later using silver halide forming components such as inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds described in detail in Japanese Patent Publication No. It can also be prepared by converting some parts into silver halide. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting into silver halide can be appropriately set according to the purpose of production, but usually, the reaction temperature is -23 ° C to 74 ° C, and the reaction time is 10 minutes. It is preferably from millisecond to 72 hours, and the reaction pressure is set to the atmospheric pressure. The photosensitive silver halide prepared by the various methods described above can be chemically sensitized by, for example, a sulfur-containing compound, a gold compound, a platinum compound, a palladium compound, a silver compound, a tin compound, a chromium compound, or a combination thereof. it can. The method and procedure of this chemical sensitization are described, for example, in US Pat.
36,650, British Patent 1,518,850
Specification, JP-A-51-22430, and JP-A-51-7
Nos. 8319 and 51-81124. The silver halide used in the present invention can be spectrally sensitized with a spectral sensitizing dye if necessary. For example, Japanese Patent Application Laid-Open Nos.
JP-A-140335, JP-A-63-231437,
JP-A-63-259551, JP-A-63-304242
No. 63-15245, U.S. Pat.
Nos. 9,414, 4,740,455, 4,741,966 and 4,75.
Sensitizing dyes described in 1,175, 4,835,096 and the like can be used. When the photothermographic image forming material of the present invention is a photothermographic image forming material exposed by various scanners, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of the scanner is used. Examples of these sensitizing dyes include, for example,
JP-A-34078, JP-A-9-54409, and JP-A-9-8
The compounds described in JP-A-0679 are preferably used.

Next, the organic silver salt used in the photothermographic image forming material of the present invention will be described. The organic silver salt used in the photothermographic image forming material of the present invention is a reducible silver source, and organic acids, heteroorganic acids, and silver salts of acid polymers containing a reducible silver ion source are used. An organic or inorganic silver salt complex in which the ligand has a value of 4.0 to 10.0 as a total stability constant for silver ions is also useful as the organic silver salt. Preferred organic silver salts include, for example, silver salts such as gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid and lauric acid. The organic silver salt can be prepared by mixing the alkali metal salt of the organic acid and silver nitrate. For the preparation, a controlled double jet method can be used when mixing the alkali metal salt of the organic acid and silver nitrate. Also, the addition may be carried out at a shifted timing. The alkali metal salt of an organic acid and silver nitrate may be added at once, or may be added in several portions.

As the reducing agent used in the photothermographic image forming material of the present invention, generally known reducing agents can be mentioned.
Examples of preferred reducing agents include US Pat.
No. 448, No. 3,773,512, and No. 3,593,863, etc., include the following. (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 These compounds can be used by dispersing in water or dissolving in an organic solvent. As the organic solvent, for example,
Alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatics such as toluene and xylene can be arbitrarily selected. The reducing agent is used in an amount of 1 mmol to 10 mol, preferably 1 mol, per mol of silver.
It is preferable to use from 00 mmol to 2 mol.

A binder is used for forming the photosensitive layer or the non-photosensitive layer of the photothermographic image forming material of the present invention. As these binders, polymer binders, for example, polyvinyl butyral, polyacrylamide, polystyrene, polyvinyl acetate, polyurethane, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-acetic acid Examples include a vinyl copolymer and a styrene-butadiene-acryl copolymer. These binders preferably form a coating film having a low equilibrium moisture content. Examples of the binder that forms a coating film having a low equilibrium moisture content include organic solvent-based cellulose acetate, cellulose acetate butyrate, and polyacetal. Preferred polyacetals include, for example, polybutyral acetalized with butyraldehyde, and polyacetal acetalized with acetaldehyde (polyacetal in a narrow sense). The degree of acetalization theoretically exists from 1% to 100%, but practically preferably from 20% to 95%. If the degree of acetalization is low, the number of hydroxyl groups will increase, and the photographic performance will be weak against humidity. A compound having a high degree of acetalization will have a severe reaction temperature and time during production, resulting in a reduction in cost and productivity. The degree of polymerization of the polymer can be freely selected from about 10 to about 10,000.
00-6,000 are preferable from the viewpoint of applicability and productivity at the time of synthesis. These binders can maintain the adhesion to the lower layer and the upper layer by forming a single film, and can obtain a film strength that is hardly scratched.However, by using a crosslinking agent, the film adhesion and the film strength can be further improved. Can be enhanced. However, when the crosslinking reaction of the crosslinking agent is slow, the photographic performance is not stable and the storage stability is deteriorated. Preferred quick-acting crosslinking agents for use in the present invention include polyfunctional crosslinking agents having at least two isocyanate groups. Preferred crosslinking agents are shown below. (H1) hexamethylene diisocyanate (H2) trimer of hexamethylene diisocyanate (H3) tolylene diisocyanate (H4) phenylene diisocyanate (H5) xylylene diisocyanate

[0026]

Embedded image The crosslinking agent may be added by dissolving in water, alcohols, ketones, and nonpolar organic solvents, or may be added as a solid in the coating solution. The addition amount is preferably equivalent to the group to be crosslinked of the binder, but may be increased up to 10 times or reduced to 1/10 or less. If the amount is too small, the crosslinking reaction does not proceed. If the amount is too large, the unreacted crosslinking agent deteriorates photographic properties, which is not preferable.

The photothermographic image-forming material of the present invention may be provided with an antihalation or antihalation AH layer or BC layer as required. Dyes are used in the AH layer or the BC layer, and any dye may be used as long as it is a dye that absorbs light used for image exposure. Preferred examples thereof include JP-A-2-216140 and JP-A-7-13295. And the dyes described in U.S. Pat. No. 5,380,380,635 and the like. As the support of the photothermographic image forming material of the present invention, a support such as polyethylene terephthalate, polyethylene naphthalate or syndiotactic polystyrene is preferable, and biaxially stretched or heat-fixed, has high optical isotropy, and has a high size. Those having a thickness of 50 μm to 400 μm with good stability are preferable. The photothermographic image-forming material of the present invention can be subjected to laser exposure according to the methods described in JP-A-9-304869, JP-A-9-31403 and JP-A-2000-10230. For the exposure, it is desirable to use a light source appropriate for the color sensitivity imparted to the image forming material. For example, when the photothermographic image forming material is an infrared light-sensitive photothermographic image forming material, any light source that emits light in the infrared light range may be used. A semiconductor laser (for example, 78
0 nm and 810 nm) are more preferably used. Apparatuses for developing the photothermographic image forming material of the present invention are disclosed in JP-A-11-65067 and JP-A-11-65067.
The devices described in JP-A-72897 and JP-A-84619 can be used.

[0028]

Example 1 Synthesis of Compounds G1 to G9 In a 1-liter SUS316 vessel equipped with a reflux condenser and a stirrer, 43.1 g (0.12 mol) of perfluorononene and 600 g of a polar solvent described in Table 1 were used. And heated to the reaction temperature shown in Table 1 with vigorous stirring, and the sulfonic acid salt shown in Table 1 was continuously added at the added mass (0.1 mol) shown in Table 1 for 1 hour. The nozzle was dropped. Thereafter, the reaction was carried out for the reaction time shown in Table 1 with stirring, and then the stirring was stopped. While maintaining the temperature at 52 ° C., the by-produced fluoride salt was separated by filtration, 1200 ml of toluene was added, and the filtrate was treated with 5 ml of toluene.
Cooled to ° C. After a lapse of 16 hours, the precipitated solids were separated by filtration and dried to obtain compounds G1 to G9 shown in Table 1.
Was obtained. In the synthesis of Compound G6 and Compound G9, the fluoride salt was separated by filtration, precipitated with sulfuric acid, and separated by filtration to obtain sulfonic acid. The non-polar solvents used are as follows. DMF; N, N-dimethylformamide DMA; N, N-dimethylacetamide MPN; N-methylpyrrolidone IMZ; N, N-dimethylimidazoline The same applies to the following tables. With respect to the obtained compound, a mass spectrum, an elemental analysis value, and a chemical shift of a carbon atom on the heterocycle were obtained from a ¹³ C nuclear magnetic resonance apparatus. Mass spectrometry is measured by atmospheric pressure chemical ionization (APCI)
And Electrospray Ionization (ESI) compatible 2
Using a double focusing magnetic field type LC / MS system JMS-Lcmate manufactured by JEOL Ltd., a methanol solvent,
Measurement was performed at an acceleration voltage of 2.5 Kv, and a mass analysis peak was determined. Elemental analysis was performed using Elemental Co., Ltd. fully automatic elemental analyzer Vario EL. ¹³
The magnetic resonance spectrum of C is based on Varian's Gemini 300 superconducting FT employing the pulse Fourier transform method and a superconducting magnet (7.05 Tesla).
A nuclear magnetic resonance apparatus was used. Table 2 shows the results of the analysis and measurement.

[0029]

[Table 1]

[0030]

[Table 2]

Example 2 Synthesis of Compounds G10 to G18 Compounds G10 to G18 were synthesized in the same manner as in Example 1. However, the aprotic polar solvent shown in Table 3 was used as the polar solvent, and the sulfonate shown in Table 3 was used as the sulfonate in the addition mass shown in Table 3. The reaction was performed at the reaction temperature and reaction time shown in Table 3. Further, the obtained compound was analyzed in the same manner as in Example 1. Table 4 shows the obtained analysis results.

[0032]

[Table 3]

[0033]

[Table 4]

Example 3 Synthesis of Compounds G19 to G27 Compounds G19 to G27 were synthesized in the same manner as in Example 1. However, in place of perfluorononene as the fluorine compound, the fluorine compound shown in Table 5 was used in the added mass shown in Table 5, and the aprotic polar solvent shown in Table 5 was used as the polar solvent. Used the sulfonate described in Table 5 with the added mass shown in Table 5. The reaction was performed at the reaction temperature and reaction time shown in Table 5. Further, the obtained compound was analyzed in the same manner as in Example 1. Table 6 shows the obtained analysis results. The fluorine compounds used are as follows. PFOE; (perfluorooctyl) ethylene PFHE; (perfluorohexyl) ethylene PFOP; (perfluorooctyl) propylene

[0035]

[Table 5]

[0036]

[Table 6]

Example 4 A 1-liter SUS316 vessel equipped with a reflux condenser and a stirrer was charged with a fluorine compound (0.1 mol) shown in Table 7 and 600 g of an aprotic polar solvent shown in Table 7, and strongly stirred. The temperature was raised to the reaction temperature shown in Table 7 while stirring, and
The unsulfonate described in Table 7 was added to the addition mass (0.1
(Mol) over 1 hour. Thereafter, the reaction was carried out for a reaction time shown in Table 7 with stirring, the temperature was lowered to 40 ° C., and fuming sulfuric acid (0.01 mol) was added dropwise over 30 minutes. After the dropwise addition, stirring was continued for 3 hours, and 0.01 mol of an alkali hydroxide compound from which the target compound shown in Table 7 was obtained was neutralized. While maintaining the temperature at 48 ° C., the by-produced alkali fluoride salt was filtered off, 1200 ml of toluene was added, and the filtrate was cooled to 5 ° C. 16
After a lapse of time, the precipitated solid was collected by filtration and dried to obtain the target compound shown in Table 7. Further, the obtained compound was analyzed in the same manner as in Example 1. Table 8 shows the obtained analysis results. The fluorine compounds used are as follows. PFOE; (perfluorooctyl) ethylene FH3P; hexafluoropropene trimer

[0038]

[Table 7]

[0039]

[Table 8]

Example 5 <Preparation of Subbed Support> A polyethylene terephthalate support having a thickness of 175 μm was provided with 12 W /
After performing a corona discharge treatment for m ² · min, the undercoating coating solution a-1 shown below was applied on one surface so as to have a dry film thickness of 600 nm, and dried to form an undercoating layer A-1. On the other side, the undercoating coating solution b-1 shown below was applied so as to have a dry film thickness of 600 nm, and dried to form an undercoating layer B-1.
Was provided. (Preparation of Subbing Coating Solution a-1) Butyl Acrylate (30
15% by weight of a copolymer latex liquid (300 g solids per liter) of t-butyl acrylate (20% by weight), styrene (25% by weight) and 2-hydroxyethyl acrylate (25% by weight). Dilute. (Preparation of Subbing Coating Solution b-1) Butyl Acrylate (40
%), A copolymer latex liquid of styrene (20% by weight) and glycidyl acrylate (40% by weight) (300 g of solids per liter) is diluted 15 times. Subsequently, after applying a corona discharge of 12 W / m ² · min on the upper surfaces of the undercoat layer A-1 and the undercoat layer B-1, the following undercoat upper layer is coated on the undercoat layer A-1. The solution a-2 was applied and dried to form an undercoating upper layer A-2 (photosensitive layer side), and an undercoating layer B-1
The lower coating layer B-2 (BC layer side) was formed by applying and drying the lower coating layer b-2 shown below. (Undercoat upper layer coating solution a-2) 1: 2 copolymer of styrene and butadiene 0.4 g / m ² butyl acrylate (30 mass%), t-butyl acrylate (20 mass%), styrene (25 mass%) Latex liquid (solid content: 300 g per liter) of 2-hydroxyethyl acrylate (20% by mass) and methacrylic acid (5% by mass) 0.3 g / m ² crosslinking agent (hexamethylene diisocyanate) 0 .1g / m ² (lower pulling layer coating solution b-2) of styrene and butadiene 1: 2 copolymer 0.4 g / m ² butyl acrylate (30 wt%), t-butyl acrylate (20 wt%), styrene (25% by mass), a copolymer latex liquid of 2-hydroxyethyl acrylate (20% by mass) and methacrylic acid (5% by mass) (solids per liter) 300 g) 0.3 g / m ² crosslinking agent (hexamethylene diisocyanate) 0.1 g / m ²

<Preparation of silver halide grain emulsion A>
In 0 ml, 7.5 g of inert gelatin and 10 mg of potassium bromide are dissolved, the temperature is adjusted to 28 ° C. and the pH is adjusted to 3.0. Potassium (molar ratio 98 /
370 ml of an aqueous solution containing 2) was added over 10 minutes by a controlled double jet method while keeping the pAg at 7.7. Synchronously with the addition of silver nitrate, the sodium salt of hexachloroiridium was added at 100 nmol / mol of silver. Thereafter, 4-hydroxy-6-methyl-1,3,3
0.3 g of a, 7-tetrazaindene was added, and NaOH was added.
The pH was adjusted to 5 by adjusting the average particle size to 36 nm, the variation coefficient of the projected diameter area to 8%, and the (100) plane ratio to 8
7% of cubic silver iodobromide grains were obtained. The particles were desalted using a reverse osmosis membrane, and then dried to 90 g. <Preparation of organic silver salt> In 3980 ml of pure water at 80 ° C,
111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved. Next, 540 ml of 1.5 mol sodium hydroxide was added while stirring at a high speed, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the obtained organic acid sodium acid solution at 55 ° C., 7.1 g (containing 0.038 mol of silver) of the silver halide grain emulsion A was added, and the mixture was stirred for 5 minutes. Next, a 1 molar silver nitrate solution 76
0.6 ml was added over 2 minutes, stirred for another 20 minutes, and the water-soluble salts were removed by filtration. Thereafter, the filtrate was repeatedly washed with deionized water and filtered until the conductivity of the filtrate became 2 μS / cm, centrifugally dehydrated, and dried.

[Coating of photosensitive layer and BC layer] On the surface having the undercoating upper layer B-2 of the undercoated support, the following layers on the back surface side, and then the undercoating upper layer A-2 An AH layer, a photosensitive layer and a surface protective layer having the following compositions were simultaneously coated on the surface having The drying was performed at 45 ° C. for 1 minute on both the BC side and the photosensitive layer side. << Coating on back surface side >> A coating solution having the following composition (shown in the attached amount) is simultaneously and multi-layer coated on the back surface side, dried and BC
A layer and a BC protective layer were formed. (BC layer coating solution) Binder (PVB-1) 1.8 g / m ²

[0043]

Embedded image Glycidyltrimethoxysilane 1 × 10 ⁻⁴ mol / m ² Dye (C1) 2.2 × 10 ⁻⁵ mol / m ²

[0044]

Embedded image (Coating solution for BC protective layer) Binder (cellulose acetate butyrate) 1.1 g / m ² Cross-linking agent (hexamethylene diisocyanate) 1 × 10 ⁻⁴ mol / m ² Fluorine-containing anionic surfactant: described in Table 9 1.3 × 10 ⁻⁴ mol / m ² Fluorine-containing nonionic surfactant: described in Table 9 6 × 10 ⁻⁵ mol / m ² Matting agent: Synthetic silica having an average particle diameter of 3 μm 18 mg / m ²

<< Coating on the photosensitive layer side >> A coating solution having the following composition (shown in the amount added) was simultaneously and multi-layer coated on the photosensitive layer side, and dried to form an AH layer, a photosensitive layer and a surface protective layer. (AH layer coating solution) Binder (PVB-1) 0.4 g / m ² Dye (C1) 1.3 × 10 ⁻⁵ mol / m ² (photosensitive layer coating solution) Binder (PVB-1) 2.6 g / M ² crosslinking agent (hexamethylene diisocyanate) 2 × 10 ⁻³ mol / m ² Spectral sensitizing dye (A1) 2 × 10 ⁻⁵ mol / m ²

[0046]

Embedded image Antifoggant (pyridinium hydrobromide perbromide) 0.3 mg / m ² Antifoggant (isothiazolone) 1.2 mg / m ² Reducing agent (K1) 3 × 10 ^-4 mol / m ² 1.36 g as silver amount / M ² of the organic silver salt was mixed with the binder. (Surface protective layer coating solution) Binder: cellulose acetate butyrate 1.2 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Fluorine-containing anionic surfactant: described in Table 9 1.3 × 10 ^-4 Mol / m ² fluorine-containing nonionic surfactant: described in Table 9 6 × 10 ⁻⁵ mol / m ² matting agent: synthetic silica having an average particle diameter of 3 μm 18 mg / m ² PVB-1 used as a binder in the above
Is polyvinyl butyral, which was used by dissolving in methyl ethyl ketone (MEK). PVB-1 has a degree of polymerization of 5
After 98% saponification of polyvinyl acetate of 98%, 8
6% is butyralized. As a comparative surfactant, sodium perfluorooctylbenzenesulfonate (comparative a) was used.

The obtained samples 501 to 533 were evaluated as follows. Table 9 shows the obtained results. (Evaluation of photographic performance) The obtained unexposed sample was treated at 25 ° C for 48 hours.
Exposure was performed using a sensitometer using a 810 nm semiconductor laser as a light source in an atmosphere of% relative humidity. After exposure, the film was heated at 120 ° C. for 8 seconds, and the fog and sensitivity of the sample were determined. Fog was represented by a density value of an unexposed portion. The sensitivity was determined by the logarithm of the reciprocal of the exposure amount giving a density of 0.2, and was expressed as a relative sensitivity with the reference sample taken as 100. (Evaluation of storage stability) The obtained unexposed sample was 80% at 35 ° C.
After being stored in an atmosphere of relative humidity for 7 days, it was exposed using a sensitometer using a semiconductor laser of 810 nm as a light source, and heated at 120 ° C. for 8 seconds after the exposure to determine fog of the sample. (Evaluation of antistatic effect) After leaving the obtained unexposed sample in a room at a relative humidity of 20% for 18 hours, the sample was rubbed five times with a synthetic fiber cloth (60% nylon, 40% polyester) and styrene beads. 100 (average particle diameter 3m
m) (approx. distance 15 mm), and evaluated by the degree of adsorption of beads. The level at which no suction is performed is 5, the level at which 3 to 8 suctions are performed, the level at which 9 to 15 suctions are performed is 3,
The level at which 16 to 25 pieces were adsorbed was 2, and the level at which 25 or more pieces were adsorbed was 1. (Evaluation of coatability) The optical density of the coated sample was 1.0 ± 1.0%.
The resultant was solid-exposed to 0.1 and heated at 120 ° C. for 8 seconds after the exposure. The optical density deviation of the obtained sample was examined. Optical density deviation: sample application width 2.47m x application length 30cm
Was automatically measured at 5 mm intervals, the deviation of the optical density was divided by the average density and multiplied by 100 was used as a measure of the applicability. The smaller the value, the more uniform the coating without variation in density. The numerical values are in the range of 0 to 10 as rank 5, the level in the range of 10 to 20 as rank 4, and the level in the range of 20 to 30 as rank 3, 30 to 40.
Were evaluated as rank 2, and the level of 40 or more was evaluated as rank 1.

[0048]

[Table 9]

From Table 9, it can be seen that the photothermographic image forming material using the fluorine-containing anionic surfactant of the present invention has an excellent antistatic effect and also has excellent photographic characteristics and storage stability. Also. It can be seen that the combined use of the anionic surfactant of the present invention and the fluorine-containing nonionic surfactant improves the antistatic effect and coatability. It can also be seen that excellent coating performance can be obtained when the fluorine-containing anionic surfactant of the present invention is added to the coating solution for forming the photothermographic image forming material.

[0050]

The fluorinated anionic surfactant of the present invention is novel, and the photothermographic image forming material using the fluorinated anionic surfactant of the present invention adversely affects fog, sensitivity and storage stability. Therefore, a uniform coated silver image without unevenness can be formed. Also, the antistatic effect is excellent.

Claims (11)

[Claims] 1. A fluorine-containing anionic surfactant represented by the general formula (1). Embedded image (In the formula, R ^f represents a chain aliphatic group substituted by a fluorine atom, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, and L ₁ represents the number of carbon atoms. Represents a divalent linking group of 1 to 4, M represents a hydrogen atom, a salt-forming atom or a group of atoms, and p represents 0 or 1.) 2. In the formula (1), the chain aliphatic group substituted by a fluorine atom represented by R ^f is a perfluoroalkenyl group or a (perfluoroalkyl) alkyl group. Item 4. The fluorine-containing anionic surfactant according to Item 1. 3. The method according to claim 1, wherein the compound represented by the general formula (2) is dissolved or dispersed in a non-aqueous polar solvent and reacted with a chain aliphatic compound substituted with a fluorine atom.
Or the method for producing a fluorine-containing anionic surfactant according to 2. Embedded image (In the formula, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, M represents a hydrogen atom, Represents an atom or a group of atoms forming a salt, M ₁ represents an alkali metal atom, and p represents 0 or 1.) 4. The method according to claim 1, wherein the compound represented by the general formula (3) is dissolved or dispersed in a non-aqueous polar solvent, reacted with a chain aliphatic compound substituted with a fluorine atom, and then sulfonated. A method for producing the fluorinated anionic surfactant according to claim 1. Embedded image (In the formula, Hr represents a 5- or 6-membered ring group selected from a pyridine ring, a furan ring and a thiophene ring, L ₁ represents a divalent linking group having 1 to 4 carbon atoms, and M ₁ represents an alkali metal. Represents an atom, and p represents 0 or 1.) 5. The method for producing a fluorine-containing anionic surfactant according to claim 3, wherein the chain aliphatic compound substituted with a fluorine atom is a trimer of hexafluoropropene. . 6. The non-aqueous polar solvent is a non-aqueous polar solvent selected from N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylimidazoline. Claim 3 to
5. The method for producing a fluorine-containing anionic surfactant according to any one of 5. 7. The general formula (2) according to claim 3 or 4.
Or the reaction temperature of the compound represented by (3) with a trimer of hexafluoropropene is 30 ° C to 160 ° C, and the production of the fluorinated anionic surfactant according to claim 5 is performed. Method. 8. The method for producing a fluorine-containing anionic surfactant according to claim 3, wherein the anionic group is a sodium salt, a lithium salt or a potassium salt of a sulfonic acid group. . 9. A photothermographic image forming material comprising a support having thereon a layer containing silver halide, an organic silver salt, a reducing agent and a binder, wherein the fluorine-containing anionic surfactant according to claim 1 or 2. A photothermographic image forming material having a layer containing an agent. 10. The photothermographic image forming material according to claim 9, wherein the layer containing a fluorine-containing anionic surfactant is the uppermost layer of the photothermographic image forming material. 11. The photothermographic image forming material according to claim 9, wherein the layer containing a fluorine-containing anionic surfactant contains a fluorine-containing nonionic surfactant.