JP2005084601A - Photothermographic imaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photothermographic imaging material having high sensitivity and low fog with respect to photographic performances and further having excellent storage stability before development (abbreviated as raw stock preservability) and in storage stability after development (abbreviated as image preservability). <P>SOLUTION: In the photothermographic imaging material obtained by providing on a support a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder, a compound represented by formula (1) is contained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photothermographic image forming material which forms an image by heat development, and particularly to a photothermographic image forming material which can obtain high sensitivity and low fog and is excellent in storage stability.

  In recent years, there has been a strong demand for photothermographic materials that do not generate waste liquids due to wet processing in terms of environmental protection and workability in the medical and printing fields. In particular, high-resolution and clear black images can be formed by thermal development. There is a need for techniques relating to photothermographic materials that can be used for photographic technology. Since these photothermographic materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic image forming materials.

  Conventionally, this type of photothermographic image-forming material absorbs a photosensitive layer containing high-sensitivity silver halide grains spectrally sensitized with a dye, an organic silver salt, and a reducing agent, and light irradiated to the photosensitive layer. From an irradiation prevention layer (AI layer) that prevents the light from being diffusely reflected at the interface, intermediate layer, adhesive layer, etc. of the support, or a backing layer (BC layer) provided on the opposite side of the support as necessary. Further, a protective layer is provided on the photosensitive layer or the BC layer to prevent scratches during handling.

In general, the photothermographic image forming material is easy to process because it produces an image only by heat development after exposure. However, since there is no fixing step, it is important to improve the storage stability of the image after development. In order to improve the storage stability after development, it is preferable to develop the image at a temperature as high as possible so that a clear image can be obtained. However, if the temperature is too high, fog is likely to occur and the sensitivity is lowered. Therefore, development is generally performed at a temperature around 120 ° C. ± 10 ° C. The use of a mercapto compound for lowering fog is disclosed (for example, see Patent Document 1). However, mercapto compounds have little effect of suppressing fogging, and it is difficult to obtain high sensitivity, and there is a limit to improving storage stability. The polyhalomethane compound used for suppression of printout silver due to exposure to Saucusten at the time of interpretation after development processing is disclosed to be effective for fog suppression and raw preservation (for example, see Patent Document 2), but the amount used is disclosed. If the number is too large, the sensitivity is lowered and there is a limit. In order to improve the storage stability, attempts have been made to use a compound known as a crosslinking agent for a binder, but it has not been sufficient. The reducing agent is said to be good for improving fog, sensitivity, storage stability, etc. (see, for example, Patent Document 3), but is not sufficient.
JP 2000-19681 A (pages 1 to 20) JP-A-9-319022 (pages 1 to 22) JP 2003-098618 A (pages 1 to 6)

  An object of the present invention is to provide a photothermographic image-forming material excellent in photographic performance with high sensitivity and low fog. A second object of the present invention is to provide a photothermographic image forming material which is excellent in preservative storage (abbreviated as raw storage) and post-development storage (abbreviated as image storage).

The above object of the present invention can be achieved by the following configuration.
(Claim 1)
A photothermographic image forming material in which a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder is provided on a support, contains a compound represented by the following general formula (1). A photothermographic image forming material characterized by the above.

(In the formula, R _H represents a group containing a hydrogen bond promoting group, R ₁ represents a hydrogen atom or a substituent, X ₁ represents a sulfur atom, an oxygen atom or an NH group, and L ₁ represents a divalent linking group. M represents a hydrogen atom, an alkali metal atom or an NH ₄ group, p represents 1 to 3, m represents an integer of 1 to 8. When p is 2 or 3, each R ₁ is the same. Or different.)
(Claim 2)
2. The photothermographic image forming material according to claim 1, wherein the hydrogen bond promoting group is at least one selected from a urea group, an amide group and a phosphoric acid group.
(Claim 3)
The photothermographic image-forming material according to claim 1 or 2, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a phthalazine compound.
(Claim 4)
The photothermographic image forming material according to any one of claims 1 to 3, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a polyhalomethane compound.
(Claim 5)
The photothermographic image according to any one of claims 1 to 4, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a compound having at least one isocyanate group or vinyl sulfone group. Forming material.

  According to the present invention, a photothermographic image forming material having high photographic performance, excellent sensitivity and low fog, and excellent storage stability before development (abbreviated as raw storage stability) and storage stability after development (abbreviated image storage stability). Could be provided.

  The present invention will be described in more detail. The photothermographic image-forming material of the present invention is usually composed of at least two layers in which at least one photosensitive layer and a layer adjacent to the photosensitive layer are provided on a support. A BC layer provided on the opposite side, a protective layer thereof, and the like are included. The photosensitive layer of the photothermographic image forming material contains photosensitive silver halide grains that may be sensitized with a spectral sensitizing dye, and the photosensitive layer or an adjacent layer thereof is an organic silver serving as a silver source. The reducing agent for developing a salt and a silver salt to form a silver image is contained, and the compound represented by the general formula (1) of the present invention is contained. In the photothermographic image forming material, an AI layer or a BC layer containing a dye for preventing irradiation or preventing halation is provided if necessary.

  Hereinafter, the compound represented by formula (1), the phthalazine compound, the polyhalomethane compound, the reducing agent, and the crosslinking agent contained in the photothermographic image forming material of the present invention will be described in order. In the description of the cross-linking agent, a compound having a vinylsulfonyl group and an isocyanate group, which are effective in suppressing fog and preserving, will be taken up. The photosensitive silver halide grains contained in the photosensitive layer of the photothermographic image forming material, the organic silver salt contained in the photosensitive layer or its adjacent layer, the reducing agent, the high content contained in the photosensitive layer or its adjacent layer. The molecular binder and the like will be further described later.

The compound represented by the general formula (1) has a function as an inhibitor and contributes to suppression of fogging and improvement of storage stability. In the general formula (1), R _H represents a group containing a hydrogen bond promoting group, and R ₁ represents a hydrogen atom or a substituent. The group contained in the R _H group (excluding the amide group, urea group, ester group or ether group serving as the base bonding site) that promotes hydrogen bonding is an intermolecular compound represented by the general formula (1) of the present invention. It is believed that self-organization is carried out by a group that promotes hydrogen bonding, and a plurality of the compounds are aggregated to suppress the action of excessively suppressing silver halide at room temperature. In addition, the self-organization by the hydrogen bond promoting group in _RH prevents the silver halide photosensitivity from being lowered at room temperature, prevents the hydrogen bond from being relaxed during heat development, and prevents fog from being amplified, The mechanism is presumed to have improved the storage stability. As a group that promotes hydrogen bonding, deoxyribonucleic acid (referred to as DNA, the molecular structural unit includes phosphoric acid, ribose, and one of the following four compounds of A, C, G, and T. ) At least one of the constituent bases. It is known that adenine (A) and guanine (G) hydrogen bond with cytosine (C) to form a molecule on the helix, and these combine to form biological DNA. In the present invention, such a group that promotes hydrogen bonding can also be introduced into the general formula (1). In the case of introduction, any combination of the above (A) and (C) and (G) and (C) is necessary. For example, half of the molecule having the group (A), (C) You may introduce the thing which has the group of half as. Other than nucleic acid group bases, urea groups, amide groups, phosphate groups, sugar groups (eg, ribose group, glucose group, mannose group, etc.) as main chain introducing groups and hydroxy groups, carboxy groups, etc. as side chain or terminal introducing groups is there. The entire R _H group is a hydrocarbon group having a carbon number of 6 to 36, and the main part is two groups such as a urea group, an amide group, a phosphate group, or a nucleobase that promote intermolecular hydrogen bonding in the middle of the polymethine group. It is preferable that the above is introduced. The introduced nucleobases may be the same or different. Particularly preferred hydrogen bond promoting groups introduced into the main chain are a urea group, an amide group, and a phosphoric acid group. Arbitrary substituents may be introduced into the hydrogen atom of the polymethine group, and an alkyl group (for example, methyl group, ethyl group, butyl group, hexyl group, etc.), alkenyl group (butenyl group, hexenyl group) which may be substituted. Octenyl group), aromatic group (phenyl group, naphthyl group), heterocyclic group (pyridyl group, imidazolyl group, furyl group, etc.), halogen atom, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), acyl Group (acetoxy group, benzoyl group, etc.). Preferred _RH is shown below.

R ₁ is independently a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 16 carbon atoms (for example, methyl group, ethyl group, butyl group, hexyl group, octyl group, dodecyl group, hydroxymethyl group) , Hydroxyethyl group, trifluoromethyl group, etc.), C1-C16 alkenyl group (butenyl group, hexenyl group, octenyl group, cyclohexenyl group etc.), aromatic group (phenyl group, naphthyl group), alkoxy group ( Examples thereof include a methoxy group, an ethoxy group, a butoxy group, and a hexyloxy group) and a heterocyclic group (for example, a pyridyl group, a thiophenyl group, a furyl group, an imidazolyl group, and a triazolyl group). p is an integer of _{1 to} 3, X ₁ represents a sulfur atom, an oxygen atom, or an NH group, and L ₁ represents a divalent linking group that may be substituted (for example, an alkylene group such as a methine group or an ethylene group) ( In the middle of the group, an amide group, a urea group, an oxygen atom, a sulfur atom, or a nitrogen atom having a substituent may be included), m represents a repeating unit and represents an integer of 1 to 8. M represents a hydrogen atom, an alkali metal atom (for example, sodium, potassium, lithium, etc.) or an NH ₄ group. Preferred specific examples are shown below. However, V ₁ ~V ₉ in the formula represent groups exemplified by Formula 2.

In the synthesis method of the above compound, an R _H group can be introduced with reference to a known heterocyclic synthesis method. The amount of the compound used is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per 1 mol of silver halide. Addition method is dissolved 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.) and added. Alternatively, fine particles may be dispersed and added. In this case, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion is carried out to form fine particles of 1 μm or less, and if necessary, a surfactant or viscosity modifier can be added and dispersed in water or an organic solvent. .

(Phthalazine compound)
The preferred phthalazine compound used in the present invention exhibits a development accelerating action, and its mechanism acts as a carrier for supplying silver ions from an organic silver salt to silver particles of a physical development nucleus by forming a phthalazine silver complex. It can be obtained by introducing various substituents into the phthalazine ring. A preferred phthalazine compound can be represented by the general formula (2).

In the formula, each of the substituents R ^{2 to} R ⁷ is independently a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aromatic group that may have a substituent. Represents a heterocyclic group. The function of the substituent may be a group such as a group that controls diffusibility, an adsorptive group, or an acidic group. As for carbon number of an alkyl group, an alkenyl group, an alkynyl group, and an alkoxy group, 1-60 are preferable, Most preferably, it is 1-40. When the number of carbon atoms is more than 40, good effects on fog suppression, color tone, and storage stability cannot be obtained. These substituents may be the same as the substituents on the ring of the general formula (1). The method for synthesizing phthalazine can be synthesized with reference to WO 96/05176. Specific examples of preferred phthalazine compounds are shown below.

(Polyhalomethane compound)
The polyhalomethane compound used in the present invention is used as an inhibitor of light fog, and its mechanism is considered to generate halo radicals by heat and light and bleach the fog nuclei of silver halide grains. It is preferable to generate a halo radical capable of bleaching fog nuclei when subjected to the action of heat or light without undergoing the cleavage reaction. In order to bring out this property, it is preferable to design a molecular structure incorporating a radical stabilization mechanism in the substituent of the trihalomethane group. In general, a compound having at least one trihalomethane group or dihalomethane group in one molecule is preferable, and in particular, an aliphatic group, an aromatic ring group or a halomethane group via a linking group that controls radical stability. Those bonded to a heterocyclic group are preferred. The aromatic ring or hetero ring may be further connected to the aromatic ring or hetero ring via a divalent linking group. The aromatic group is preferably a phenyl group or a naphthalene group, and a rogen atom such as a chlorine atom, a bromine atom, a fluorine atom or an alkyl group such as a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group or an octadecyl group on these rings. Examples of the heterocyclic group include a pyridine group, a pyrimidine group, a quinoline group, a furan ring group, a thiophene ring group, an imidazole group, a triazole group, an oxazole group, a thiazole group, a thiadiazole group, and an oxadiazole group. On the ring, you may have a substituent similar to an aromatic ring. In addition, a group for imparting diffusion resistance or a group that promotes adsorption to silver halide may be substituted on the aromatic ring or the hetero ring. The group adjacent to the trihalomethane group or dihalomethane group is preferably a sulfonyl group or a carbonyl group, but may be directly bonded to an aromatic ring or a heterocyclic ring, and the bonding method is not limited. The aromatic ring or the hetero ring is particularly preferably a ring group which is completely or partially reduced. The halogen atom of the trihalomethane group or dihalomethane group is preferably a bromine atom, but may be chlorine, fluorine, iodine, or a combination thereof. A preferred structure is shown in the following general formula (3).

In the formula, X ¹ , X ² and X ³ represent a hydrogen atom, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or an aryl group, at least one of which is a halogen atom. L ₁ represents —C (═O) —, —SO— or —SO ₂ —, and q represents 0 or 1.

The ring represented by Z ₂ may be a saturated or unsaturated monocyclic or condensed ring, preferably a monocyclic or bicyclic group having 6 to 30 carbon atoms (for example, an adamantyl group, a cyclobutane group, a cyclopropane group). Group, cyclopentane group, cyclooctane group, cyclobutene group, cyclopentene group, cyclohexene group, phenyl, naphthyl, etc., more preferably adamantyl group, cyclopentane group, cyclohexane group, cyclohexene group, cyclohexanone group, cyclopentene group, phenyl. A naphthyl group, more preferably a phenyl group. The heterocyclic ring represented by Z ₂ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one atom of N, O or S, which may be monocyclic, A condensed ring may be formed with other rings. The heterocyclic group is preferably a 5- or 6-membered saturated or unsaturated heterocyclic group which may have a condensed ring, and more preferably a 5- to 6-membered aromatic group which may have a condensed ring. It is a heterocyclic group. More preferably, it is a 5- or 6-membered saturated or unsaturated heterocyclic group optionally having a condensed ring containing a nitrogen atom, and particularly preferably a condensed ring containing 1 to 4 nitrogen atoms. A good 5- to 6-membered unsaturated heterocyclic group. The heterocyclic ring in such a heterocyclic group includes imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, phospholene, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline Pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, Thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, te Razole, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, Tetrazole, thiazole, benzimidazole, and benzthiazole are preferable, and pyridine, thiadiazole, quinoline, and benzthiazole are particularly preferable. The ring group represented by Z ₂ may have a substituent in addition to —L ₁ —C (X ¹ ) (X ² ) (X ³ ), and the substituent is preferably an alkyl group, an alkenyl group, Aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl Group, sulfonyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, Acyl group, acylamino group, alkoxycarbonylamino group, aryloxy Rubonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryl An oxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group, and a heterocyclic group, particularly preferably an alkyl group, an aryl group, and a halogen atom. X ¹ , X ² and X ³ are preferably a halogen atom, a haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group or a heterocyclic group, more preferably a halogen atom, A haloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a sulfonyl group, more preferably a halogen atom and a trihalomethyl group, and particularly preferably a halogen atom. Of the halogen atoms, preferred are a chlorine atom, a bromine atom and an iodine atom, more preferred are a chlorine atom and a bromine atom, and particularly preferred is a bromine atom. Specific examples of these compounds are listed below.

The phthalazine compound and polyhalomethane compound used in combination with the compound of the general formula (1) of the present invention are added in an amount of 1 × 10 ⁻² to 1 × 10 ³ mol with respect to 1 mol of the compound represented by the general formula (1) of the present invention. It is preferable to do. The addition position is not limited to the photosensitive layer in which silver halide exists, and may be an adjacent layer or an undercoat layer. The addition method can be performed in the same manner as the compound represented by the general formula (1).

  Next, organic silver salts, reducing agents, photosensitive silver halide grains, binders, dyes, matting agents and other supports used in the photothermographic image forming material of the present invention will be described in order.

(Organic silver salt)
The organic silver salt contained in the photothermographic image-forming material of the present invention is a reducible silver source, and organic acids, heteroorganic acids and acid polymer silver salts containing a reducible silver ion source are used. Also useful are organic or inorganic silver salt complexes whose ligands have a total stability constant for silver ions of 4.0-10.0. Examples of silver salts are described in Research Disclosure Nos. 17029 and 29963 and include the following: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid) Salts of acids and the like).

(Photosensitive silver halide grains)
The photosensitive silver halide contained in the photosensitive layer of the photothermographic image-forming material of the present invention can be obtained by any method known in the field of photographic technology such as a single jet or double jet method, for example, an ammonia emulsion or neutral emulsion. It can be prepared in advance by any method such as a method or an acidic method, and then mixed with the other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide and the organic silver salt, for example, U.S. 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 1,362,970, etc., and means using a polymer other than gelatin such as polyvinyl acetals Or means for enzymatic degradation of gelatin in light sensitive silver halide emulsions as described in British Patent 1,354,186, or as described in US Pat. No. 4,076,539. Thus, each means such as a means for omitting the use of the protective polymer can be applied by preparing photosensitive silver halide grains in the presence of a surfactant.

  The photosensitive silver halide preferably has a small grain size in order to keep white turbidity after image formation low and to obtain good image quality. The average particle size is 0.1 μm or less, preferably 0.01 to 0.1 μm, particularly preferably 0.02 to 0.08 μm. Further, the shape of the silver halide is not particularly limited, and examples thereof include cubic and octahedral so-called normal crystals and non-normal crystals such as spherical, rod-like, and tabular grains. The silver halide composition is 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 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 silver halide and the organic silver salt described later. Various conditions such as reaction temperature, reaction time, reaction pressure, etc. in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of preparation. Usually, the reaction temperature is −20 ° C. to 70 ° C., the reaction time is 30 seconds to 15 hours, and the reaction pressure is preferably set to 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. . Regarding the method and procedure of this chemical sensitization, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850 and the like, JP-A-51-22430, JP-A-51-78319. , 51-81124, etc. In order to achieve sensitization, as described in US Pat. No. 3,980,482, when a part of the organic silver salt is converted to photosensitive silver halide by the silver halide forming component. In addition, an amide compound having a low molecular weight may coexist.

  Further, these photosensitive silver halides include illuminance failure and metals belonging to Groups 6 to 10 of the Periodic Table of Elements, such as Rh, Ru, Re, Ir, Os, Fe, etc. for gradation adjustment. Ions, their complexes or complex ions can be included. In particular, it is preferable to contain ions or complex ions of metals belonging to Groups 6 to 10 of the Periodic Table of Elements. As the above metal, W, Fe, Co, Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, and Au are preferable. Among them, when used for a photosensitive material for printing plate making, Rh, Re, It is preferably selected from Ru, Ir, and Os. These metals can be introduced into the silver halide in the form of a complex.

The content of metal ions or complex ions is generally 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, preferably 1 × 10 ⁻⁸ to 1 × 10. ^-4 moles. The compounds providing these metal ions or complex ions are preferably added at the time of silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening , May be added at any stage before or after chemical sensitization, but is preferably added at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, most preferably Preferably, it is added at the stage of nucleation. In addition, it may be divided and added several times, or it can be uniformly contained in the silver halide grains. JP-A-63-29603, JP-A-2-306236, 3 As described in publications such as 167545, 4-76534, 6-110146, and 5-273683, the particles can be contained with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving in water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation, or the silver salt solution and the halide solution are mixed simultaneously. When adding a third aqueous solution, a method of preparing silver halide grains by a method of three-liquid simultaneous mixing, a method of adding a required amount of an aqueous solution of a metal compound to the reaction vessel during grain formation, or a silver halide preparation There is a method of adding and dissolving another silver halide grain that has been previously doped with metal ions or complex ions. In particular, a method of adding an aqueous solution of a metal compound powder or an aqueous solution in which a metal compound and NaCl, KCl are dissolved together is added to the water-soluble halide solution. When added to the particle surface, a necessary amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particle, during or after the physical ripening, or at the chemical ripening.

(Spectral sensitizing dye)
Spectral sensitizing dyes used in the present invention are, for example, disclosed in JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651, 63-304242, 63-15245. No. 4,639,414, US Pat. No. 4,740,455, US Pat. No. 4,741,966, US Pat. No. 4,751,175, US Pat. No. 4,835,096 Sensitizing dyes described in each specification such as No. can be used. Useful sensitizing dyes used in the present invention are described in, for example, the literature described or cited in Research Disclosure Item 17643IV-A (December 1978, p.23), Item 1831X (August 1978, page 437). ing. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, the compounds described in JP-A Nos. 9-34078, 9-54409, and 9-80679 are preferably used.

(Reducing agent)
Preferred for use in the present invention are those contained in a photothermographic image-forming material and exhibiting a reducing action in heat development. US Pat. Nos. 3,770,448, 3,773,512, 3,593, The thing described in each specification, such as 863 number, can be mentioned.

  Particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (4).

In the formula, R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, —C ₄ H ₉ , 2,4,4-trimethylpentyl), an aromatic ring group (for example, a phenyl group, a naphthyl group, A cyclopentadienyl group, a cyclohexenyl group, or the like, or a heterocyclic group (furyl group, thiophenyl group, pyridyl group, oxazolyl group, thiazolyl group, etc.), and R ′ and R ″ are straight-chain groups having 1 to 5 carbon atoms. Represents a chain or branched alkyl group (for example, methyl, ethyl, t-butyl) In particular, in the formula, R is preferably a cyclic group, more preferably an unsaturated ring group, and the most preferable ring group is A cyclohexenyl group, and a 2,4-dimethylcyclohexenyl group, a cyclohexenyl group, a pentadienyl group, a furyl group, a thiophenyl group and the like are subsequently preferable.

  Specific examples of the compound represented by the general formula (4) are shown below. However, the present invention is not limited to the following compounds.

The amount of the compound represented by the general formula (4) is preferably 1 × 10 ⁻² to 10 mol, particularly 1 × 10 ^{−2 to} 3 mol, per mol of silver. As the addition method, a method similar to the method of adding the compound of the general formula (1) can be employed.

(Binder)
As the polymer binder used in the photosensitive layer or the non-photosensitive layer of the photothermographic image forming material of the present invention, a material preferable as a place where silver halide, an organic silver salt and a reducing agent react, a thermochromic dye is 80 to A material that is preferable for a reaction that can be erased by heat of 200 ° C. or less, or a material that allows the base generating precursor to quickly generate a base by heat is selected. Examples of the polymer binder include alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, polymers used by dissolving in polar solvents including dimethyl sulfoxide and dimethylformamide, and water-dispersed polymers. The polymer binder of the photothermographic image forming material of the present invention may be any. Further, regarding the preferred polymer composition, the glass transition point is preferably from -20 ° C to 80 ° C, particularly preferably from -5 ° C to 60 ° C. This is because when the glass transition point is high, the temperature at which heat development is performed becomes high, and when the glass transition point is low, fogging is likely to occur, resulting in a decrease in sensitivity and softness.

  Examples of the polymer used by dissolving in the above polar solvent include cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, and ethyl cellulose, starch and derivatives thereof, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, poly Ethylene oxide, acrylic acid amide-acrylic acid ester copolymer, styrene-maleic anhydride copolymer, polyacrylamide, sodium alginate, gelatin, casein, polystyrene, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic acid ester, styrene -Butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-a Such as Lil copolymer. Further, after drying, a film is formed, and then the coating film having a low equilibrium water content is preferable. Examples of particularly low water content include poly ((methacrylic acid) such as cellulose acetate, cellulose acetate butyrate, and poly (methyl methacrylic acid). Acrylic esters), poly (acrylic acid), poly (methacrylic acid), poly (vinyl chloride), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl) Acetals) (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates) Poly (vinyl acetate), cellulose esters, poly (amino ) S can be mentioned.

(Crosslinking agent)
By forming the binder alone, it is possible to maintain adhesion to the lower layer and upper layer and to obtain a film strength that is difficult to get scratched. However, the use of a crosslinking agent further increases film adhesion and film strength. be able to. In addition, the crosslinking agent can not only improve the film physical properties but also improve fog suppression and storage stability. The mechanism is considered as follows. Amine compounds produced by corona discharge treatment on the surface of the support or the undercoat layer migrate to the coated photosensitive layer and increase fogging. However, the presence of a crosslinking agent that captures or inactivates the amine compound suppresses the generation of fog. The generation of the amine compound is due to the fact that nitrogen in the air, hydrogen atoms in the film, and in some cases, oxygen atoms, etc., enter a plasma state during corona discharge, and the rearrangement of atoms proceeds. Ammonia water used as a pH regulator is also considered to be left in the reaction as a causative substance for fogging. In addition, it is estimated that some of the trace amounts of impurities in the materials used as photographic additives increase fog. In using the crosslinking agent, there are a method of adding it to the undercoat layer, AI layer, photosensitive layer, protective layer, BC layer or protective layer of the BC layer. From the viewpoint of the stability of the coating solution, it is preferably added using a static mixer immediately before coating, but may be added at the time of preparing the coating solution. A preferred crosslinking agent is a crosslinking agent having an isocyanate group or a vinylsulfonyl group. Particularly preferred crosslinking agents include polyfunctional crosslinking agents having at least 2, more preferably 3, isocyanate groups or vinylsulfonyl groups. JP, 2003-002874, A can refer to the synthesis method of a vinyl sulfonyl compound. H1-H13 are shown below as preferable crosslinking agents.

(H1) Hexamethylene diisocyanate (H2) Trimer of hexamethylene diisocyanate (H3) Tolylene diisocyanate (H4) Phenylene diisocyanate (H5) Xylylene diisocyanate

The compound having an isocyanate group or vinylsulfonyl group used in combination with the compound of the general formula (1) of the present invention is 1 × 10 ⁻² to 1 × 1 mol of the compound represented by the general formula (1) of the present invention. It is preferable to add × 10 ³ mol. The addition position is not limited to the photosensitive layer in which silver halide exists, and may be an adjacent layer or an undercoat layer. The addition method can be performed in the same manner as the compound represented by the general formula (1).

(Dye used for AI layer or BC layer if necessary)
The photothermographic image-forming material of the present invention is provided with an AI layer or BC layer for preventing irradiation or preventing halation of the photothermographic image-forming material, if necessary, and the dye used for the AI layer or BC layer is an image. Any dye can be used as long as it absorbs exposure light. Preferably, the thermodecolorable dye described in US Pat. No. 5,384,237 described above is used. If the dye used is not thermodecolorable, the amount used is limited to a range that does not affect the photothermographic image-forming material, but if it is a thermodecolorable dye, a sufficient amount of dye is necessary if necessary. Can be added.

(Matting agent)
The matting agent may be either organic or inorganic. Examples of the inorganic matting agent include silica described in Swiss Patent No. 330,158 and polystyrene or polymeta described in Swiss Patent No. 330,158. Acrylate, polyacrylonitrile described in US Pat. No. 3,079,257, polycarbonate described in US Pat. No. 3,022,169, and the like can be used.

  The shape of the matting agent may be either a regular shape or an irregular shape, but is preferably a regular shape, and a spherical shape is preferably used. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle size of the matting agent indicates the diameter converted into a spherical shape. The matting agent used in the present invention preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. The monodispersity of the particles is preferably 50 or less, more preferably 40 or less, and particularly preferably 20 or less. Here, the monodispersity of the particles is represented by a number obtained by dividing the standard deviation of the particle size by the average value of the particle size and multiplying by 100. The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed and applied in advance in the coating solution, or a method in which the matting agent is sprayed after the coating solution is applied and before drying is completed. May be.

(Support)
As the support, a support such as paper, synthetic paper, non-woven fabric, metal foil, and plastic film can be used, and a composite sheet combining these may be arbitrarily used.

<Image exposure>
As an exposure method, laser exposure can be performed by the methods described in JP-A-9-304869, JP-A-9-311403 and JP-A-2000-10230.

<Heat development device>
As an apparatus for developing the photothermographic image forming material, apparatuses described in JP-A Nos. 11-65067, 11-72897 and 84619 can be used.

  Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1
<Preparation of underdrawn support>
The both sides of a 175 μm thick polyethylene terephthalate support were subjected to a corona discharge treatment of 600 W / m ² · min, and the following undercoat coating solution a-1 was applied on one surface to a dry film thickness of 0.8 μm. The undercoat layer A-1 is provided by drying, and the following undercoat coating solution b-1 is applied on the opposite surface so as to have a dry film thickness of 0.8 μm and dried to form the undercoat layer B-1. Provided.

<< Undercoat coating liquid a-1 >>
Copolymer latex liquid of butyl acrylate (30% by mass), t-butyl acrylate (20% by mass), styrene (25% by mass), 2-hydroxyethyl acrylate (25% by mass) (solid content 30%) 270 g
Hexamethylene-1,6-bis (ethylene urea) 0.8g
Finish to 1 liter with water.

<< Undercoating liquid b-1 >>
270 g of copolymer latex liquid (solid content 30%) of butyl acrylate (40 mass%), styrene (20 mass%), glycidyl acrylate (40 mass%)
Hexamethylene-1,6-bis (ethylene urea) 0.8g
Finish to 1 liter with water.

Subsequently, a corona discharge of 600 W / m ² · min is applied to the upper surfaces of the undercoat layer A-1 and the undercoat layer B-1, and the following undercoat upper layer A-2 is formed on the undercoat layer A-1. The following undercoating upper layer B-2 was provided on the undercoating layer B-1.

<< Undercoating Upper Layer A-2 >>
Gelatin 0.43 g / m ²
Silica particles (average particle size 3 μm) 0.01 g / m ²
<< Undercoating Upper Layer Coating Liquid B-2 >>
Styrene butadiene copolymer latex liquid (solid content 20%) 0.08 g / m ²
Polyethylene glycol (mass average molecular weight 600) 0.06 g / m ²
<Preparation of silver halide grain emulsion A>
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 900 ml of water and adjusting the temperature to 28 ° C. and pH to 3.0, bromide with a molar ratio of (98/2) to 370 ml of an aqueous solution containing 74 g of silver nitrate An aqueous solution containing potassium and potassium iodide (equivalent mole of silver halide to silver nitrate) was added over 10 minutes by the controlled double jet method while maintaining pAg 7.7. In synchronization with the addition of silver nitrate, 10 ^-6 mol / silver 1 mol of sodium salt of hexachloroiridium was added. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.036 μm, and the variation coefficient of the projected diameter area was 8%. Cubic silver iodobromide grains having a [100] face ratio of 87% were obtained. This emulsion was coagulated and precipitated using a gelatin flocculant, desalted and then 0.1 g phenoxyethanol was added to adjust the pH to 5.9 and pAg 7.5 to obtain silver halide grain emulsion A.

<Preparation of water-dispersed organic silver salt>
In 4720 ml of pure water, 111.4 g of behenic acid, 83.8 g of arachidic acid, and 54.9 g of stearic acid were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 molar sodium hydroxide aqueous solution was added while stirring at high speed, and 6.9 ml of concentrated nitric acid was added, followed by cooling to 55 ° C. to obtain an organic acid sodium solution. While maintaining the temperature of the organic acid sodium solution at 55 ° C., the silver halide grain emulsion A (containing 0.038 mol of silver) and 420 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of 1 mol silver nitrate solution was added over 2 minutes, and the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, the filtrate was repeatedly washed with deionized water and filtered until the electric conductivity of the filtrate reached 2 μS / cm, and finally dried to obtain 335 g of a solid content.

<Coating of photosensitive layer and BC layer>
The following layers were sequentially formed on the support provided with the undercoat layer to prepare a sample. The drying was performed at 45 ° C. for 1 minute.

<< BC layer side application >>
On the back surface side, a BC coating layer was formed by applying and drying a coating solution prepared by adding water to an aqueous dispersion or water dispersion of the following thermodecolorable dye composition and adding the following amount.

<< BC layer application >>
Inert gelatin 1.8g / m ²
Dye C 1.2 × 10 ⁻⁵ mol / m ²
Activator: N-propyloctylsulfonamidoacetic acid 0.02 g / m ²
Dihexyl sulfosuccinic acid sodium salt 0.02 g / m ²
Cross-linking agent: 1,2-bis (vinylsulfonamide) ethane 0.02 g / m ²
<< Application of BC protective layer >>
Inert gelatin 1.1 g / m ²
Cross-linking agent: 1,2-bis (vinylsulfonamide) ethane 0.01 g / m ²
Activator: N-propyl perfluorooctylsulfonamidoacetic acid 0.02 g / m ²
Matting agent (PMMA: average particle size 5 μm) 0.12 g / m ²
<< Coating on the photosensitive layer side >>
<Application of AI layer>
Binder: PVB-1 0.4 g / m ²
Dye C 1.2 × 10 ⁻⁵ mol / m ²
A coating solution was prepared by dissolving the following composition in a methyl ethyl ketone solvent for forming a photosensitive layer. This coating solution was kept at around 35 ° C. and dried so as to have the following weight. An amount of the preparation solution that was 0.86 g / m ² as silver amount was mixed with the polymer binder.

Binder: PVB-1 2.6 g / m ²
Compounds of general formula (1): listed in Table 1 3.2 × 10 ⁻⁴ mol / m ²
Incidentally, it was used as shown below as a non-hydrogen bonding promoting groups R _N a (SB-0) as a comparison.

Compound represented by the general formula (2): listed in Table 1 2.2 × 10 ⁻⁴ mol / m ²
Compound represented by the general formula (3): listed in Table 1 1.2 × 10 ⁻⁴ mol / m ²
Compound represented by formula (4): listed in Table 1 3.8 × 10 ⁻³ mol / m ²
Spectral sensitizing dye D 2 × 10 ⁻⁵ mol / m ²
Antifoggant-1: pyridinium hydrobromide perbromide 0.3 mg / m ²
Antifoggant-2: isothiazolone 1.2 mg / m ²
Cross-linking agent: listed in Table 1 2 × 10 ⁻⁵ mol / m ²
Phenylaminoethoxytrimethoxysilane (H-0) was used as a comparative crosslinking agent.

<Surface protective layer>
A coating solution prepared by adding the following composition was applied and dried on the photosensitive layer so as to have the following weight to form a surface protective layer.

Cellulose acetate butyrate 1.2 g / m ²
4-methylphthalic acid 0.7 g / m ²
Tetrachlorophthalic acid 0.2g / m ²
Tetrachlorophthalic anhydride 0.5g / m ²
Silica matting agent (average particle size 5 μm) 0.5 g / m ²
Surfactant E 0.1 g / m ²

<Evaluation of photographic performance>
After preparing 50 samples with the size of 5 cm × 12 cm, the sample was divided into two, and one was exposed to a 810 nm semiconductor laser exposure photometer in an atmosphere of 46% RH at 23 ° C., and 120 after exposure. After heating at 0 ° C. for 10 seconds, the photographic performance of the obtained sample was evaluated (room temperature photographic performance). The other was heat sealed under reduced pressure (10 hPa) in a confidential aluminum foil packaging bag at 23 ° C. RH 46%, stored in a constant temperature room at 48 ° C. for 30 days, and then exposed and developed in the same manner to evaluate the performance (high temperature Photographic performance, ie raw storage). The laser exposure and the development treatment were performed in a room adjusted to a humidity of 25% ± 1 ° C. and a relative humidity of 54% ± 1%.

  The sensitivity and fog were measured with a transmitted light densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the exposure amount giving a density 0.3 higher than the fog density, and expressed by relative evaluation with the sample 101 as a reference (100). The storage stability after image development (image storage stability) is a light fog value after a developed sample is left on a shaucusten having a luminance of 10,000 lux for 10 hours.

  From Table 1, it can be seen that when the compound represented by the general formula (1) of the present invention is used, the photographic performance (sensitivity and fog characteristics), the raw storability and the image storability during development are excellent. When a compound represented by the general formula (1) of the present invention and a phthalazine, polyhalomethane or bisphenol compound are used in combination or further crosslinked with an isocyanate or a vinylsulfonyl crosslinking agent, the room temperature photographic performance and the raw storability and image preservation at the time of heat development It can be seen that the performance is improved.

Claims (5)

A photothermographic image forming material in which a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder is provided on a support, contains a compound represented by the following general formula (1). A photothermographic image forming material characterized by the above.

(In the formula, R _H represents a group containing a hydrogen bond promoting group, R ₁ represents a hydrogen atom or a substituent, X ₁ represents a sulfur atom, an oxygen atom or an NH group, and L ₁ represents a divalent linking group. M represents a hydrogen atom, an alkali metal atom or an NH ₄ group, p represents 1 to 3, m represents an integer of 1 to 8. When p is 2 or 3, each R ₁ is the same. Or different.) 2. The photothermographic image forming material according to claim 1, wherein the hydrogen bond promoting group is at least one selected from a urea group, an amide group and a phosphoric acid group. The photothermographic image-forming material according to claim 1 or 2, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a phthalazine compound. The photothermographic image forming material according to any one of claims 1 to 3, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a polyhalomethane compound. The photothermographic image according to any one of claims 1 to 4, wherein the photosensitive layer or a layer adjacent to the photosensitive layer contains a compound having at least one isocyanate group or vinyl sulfone group. Forming material.