JP2001192365A - Novel phenolic compound and image recording material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image-recording material that comprises a phenol represented by formula (I), wherein R1-R4 are each H or a substituent; L is a divalent bridge group bearing at least one methylene; X is a divalent bridge group; n represents zero or 1; Z is a residual group derived from a photographically useful compound, and a binder; provide a phenol that is represented by the formula (I) and provide a phenol that is represented by the formula (I) to be used as an image-recording material. SOLUTION: The above-described image-recording material can be prepared, for example, to a heat developing image-recording material which is characteristically highly sensitive with the thermal fogging suppressed on the non-image areas, stable to the fluctuations in developing conditions and reveals good color tone and high thermal and/or optical stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel phenol compound and an image recording material containing the compound. More specifically, the present invention provides high sensitivity, low fog, stability to fluctuations in development processing conditions, excellent stability during storage before development and image stability after development, and an image with good color tone. Related to recording materials.

[0002]

2. Description of the Related Art There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technique for forming an image by thermal development is a system that can simplify environmental preservation and image forming means. 2. Description of the Related Art In recent years, in the medical and photoengraving fields, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental conservation and space saving. Therefore, a technology relating to a photosensitive heat developing material for medical and photoengraving applications, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a clear black image having high resolution and sharpness. Is needed. These photosensitive heat-developable materials eliminate the use of solution-based processing chemicals and can provide customers with a simpler heat-development system that does not damage the environment.

A method of forming an image by thermal development is described in, for example, US Pat. Nos. 3,152,904 and 3,4,904.
57,075, and D.C. Morgan
And B. "Thermally Processed Silver Systems" by Shely
A "(Imaging Processes and Materials) Neblette
Eighth Edition, Sturge, V.E. Wallwards (Wa
lworth), A. Edited by Shepp, page 2, 1969
Year). Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

Since the visible image is obtained exclusively from elemental silver (Ag °), the amount of silver in the emulsion cannot be easily reduced without reducing the maximum image density. However, it is often desirable to reduce the amount of silver to reduce the cost of the raw materials used in the emulsion and / or to enhance performance. One way to increase the maximum image density in photographic and photothermographic emulsions without increasing the amount of silver in the emulsion layer is to incorporate a dye-forming substance into the emulsion. Upon image formation, the leuco dye is oxidized and a dye and reduced silver image are simultaneously formed in the exposed areas. It is also known to incorporate a leuco dye to adjust the silver tone.

Fog is a major problem in heat-developable photographic materials. Many studies have been made to reduce fog of heat-developable photographic materials. For example, US Pat. No. 3,589,
No. 903 discloses a mercury salt. In addition, U.S. Pat. No. 4,152,160 discloses carboxylic acids such as benzene and phthalic acid, and U.S. Pat.
U.S. Pat. No. 84,939 discloses a benzoylbenzene compound; U.S. Pat. No. 4,569,906 discloses indane or tetralin carboxylic acid; U.S. Pat.
No. 0,617 describes dicarboxylic acids, U.S. Pat.
626,500 discloses heteroaromatic carboxylic acids. U.S. Pat. No. 4,546,075, U.S. Pat. No. 4,756,999, U.S. Pat. No. 4,452,885, U.S. Pat.
No. 4,946 and US Pat. No. 3,955,98.
No. 2 discloses a halogenated compound. U.S. Pat. No. 5,028,523 discloses halogen molecules or halogen atoms combined with a heteroatom ring. U.S. Pat. Nos. 4,103,312 and 1,502,670 disclose palladium compounds; U.S. Pat. No. 4,128,428 discloses iron-based metals; U.S. Pat. U.S. Pat. No. 4,129,557 and U.S. Pat. No. 4,125,430 disclose substituted triazoles.
U.S. Pat. No. 4,213,784, U.S. Pat. No. 4,245,033 and JP-A-51-260.
No. 19 discloses a sulfur compound, U.S. Pat. No. 4,002,4.
No. 79 describes thiouracils and JP-A-50-123.
No. 331 discloses sulfinic acid, US Pat.
No. 5,403, U.S. Pat. No. 4,152,160 and U.S. Pat. No. 4,307,187 disclose metal salts of thiosulfonic acid, JP-A-53-20923 and JP-A-53-20923. No. 53-19825 discloses a combination use of a metal salt of thiosulfonic acid and sulfinic acid, Japanese Patent Publication No. 62-508.
No. 10, JP-A-7-209797 and JP-A-9-43760 disclose thiosulfonic acid esters.

Further, disulfide compounds are disclosed in JP-A-51-42529 and JP-B-63-37368, and polyhalogen compounds are disclosed in JP-B-54-165. However, these compounds have insufficient antifogging effects, insufficient storage stability of the photosensitive material before development, and image storage stability after heat development (for example, non-image areas due to heat or light). ) Is insufficient, and when an amount that sufficiently suppresses fog is added, sensitivity is reduced and _Dmax is reduced.

Further, compounds known in the art for forming a dye image in photothermographic materials have poor storage stability.
There is a problem that the _min part is colored, and when a small amount of a strong reducing agent or the like is used as a development accelerator, the storage stability is poor and heat fogging often occurs. Further, in the case of a photothermographic material, development conditions (eg, heating time, temperature, humidity)
There was a problem that the sensitivity fluctuated due to the fluctuation of the sensitivity.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems of the prior art. That is, the present invention provides a heat-developable image having high sensitivity, low fog, stable against fluctuations in development processing conditions, good stability during raw storage and storage stability of dark / photothermal images, and good color tone. Providing a recording material was an issue to be solved.

[0009]

The above objects have been achieved by the following means. That is, the present invention provides the following formula (I):

Embedded image (Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, L represents a divalent linking group containing at least one methylene group, X represents a divalent linking group, and n Represents 0 or 1, and Z represents a residue derived from a photographically useful compound), and a binder.

According to a preferred embodiment of the present invention, the image recording material further contains a photocatalyst; the image recording material further contains a reducing agent; the image recording material further contains a reducible silver salt; The above-mentioned image recording material containing an agent is provided.

From another viewpoint, the present invention provides a phenol compound represented by the above formula (I) and a phenol compound represented by the above formula (I) used for an image recording material. Furthermore, there is provided use of the phenol compound represented by the above formula (I) for producing an image recording material. In the formula (I), preferably, (1) Z contains a hetero atom in the molecule, and the hetero atom is bonded to L or X, and the hetero atom is preferably oxygen, sulfur, or nitrogen; 2) X contains a heteroatom, which is bonded to L, said heteroatom is preferably oxygen, sulfur, nitrogen; (3) L has one or more substituents May represent an alkylene group having a carbon chain length of 2 or more, more preferably L is an alkylene group having 2 to 4 carbon atoms; (4) Z is derived from an antifoggant, a reducing agent, or a dye (5) R ¹ and R ⁴ are other than a hydrogen atom.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, “to” is a range including numerical values described before and after. As the substituent represented by R ^{1 to} R ⁴ , any substituent may be used as long as it does not adversely affect photographic properties. For example, a halogen atom (a “halogen atom” in the present specification may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a straight-chain, branched-chain, cyclic, or a combination thereof An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methyl, ethyl, iso-propyl, tert-butyl, tert-octyl, te
rt-amyl, cyclohexyl and the like. Hereinafter, in the present specification, the same applies as above unless otherwise specified in the “alkyl group” or the alkyl part of the substituent containing the alkyl part. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like), aryl Group (preferably having 6 to 30 carbon atoms, more preferably 6 to 2 carbon atoms)
0, particularly preferably 6 to 12, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methoxy, ethoxy, butoxy, etc.), and an aryloxy group (preferably carbon atoms). Number 6-
30, more preferably 6 to 20, particularly preferably 6 to 1
2, for example, phenyloxy, 2-naphthyloxy and the like. ), An acyloxy group (preferably having 1 to 20, more preferably 2 to 16, and particularly preferably 2 to 12; examples thereof include acetoxy and benzoyloxy); and an amino group (preferably having 0 carbon atoms). To 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a dimethylamino group, a diethylamino group, a dibutylamino group and the like, and an acylamino group (preferably having 1 to 20 carbon atoms). Preferably from 2 to 16, particularly preferably from 2 to 12, for example,
Acetylamino, benzoylamino and the like can be mentioned. ), A sulfonamide group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16, particularly preferably 1 to 12
And examples thereof include methanesulfonamide and benzenesulfonamide. ), A ureido group (preferably having 1 to 20, more preferably 1 to 16, and particularly preferably 1 to 12; examples thereof include ureido, methylureide, and phenylureide), and a carbamate group (preferably, 2-20 carbon atoms, more preferably 2-16, particularly preferably 2-12, for example,
Methoxycarbonylamino, phenyloxycarbonylamino and the like can be mentioned. ), A carboxyl group or a salt thereof, and a carbamoyl group (preferably having 1 to 20, more preferably 1 to 16, and particularly preferably 1 to 12, for example, carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl) Etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, etc.), and acyl. Group (preferably having 1 carbon atom)
~ 20, more preferably 2 ~ 16, particularly preferably 2 ~ 2
12, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), A sulfo group or a salt thereof, a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include mesyl and tosyl), and a sulfamoyl group ( It preferably has 0 to 20 carbon atoms, more preferably 0 to 16, and particularly preferably 0 to 12, and includes, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like.), Cyano Group, nitro group, hydroxyl group, mercapto group, alkylthio group (preferably having 1-2 carbon atoms)
0, more preferably 1 to 16, particularly preferably 1 to 12
And examples thereof include methylthio and butylthio. ), A heterocyclic group (preferably having 2 to 20, more preferably 2 to 16, particularly preferably 2 to 12, and examples thereof include pyridyl, imidazoyl, and pyrrolidyl).

R ¹ and R ⁴ are preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a sulfonylamino group, a carbamate group, a carbamoyl group, an alkoxycarbonyl group, and an acyl group. , A sulfonyl group, a sulfamoyl group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an alkylthio group, more preferably a halogen atom, a tertiary alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group, An acyl group or a nitro group, particularly preferably a halogen atom,
Graded alkyl, alkoxy and acyl groups. R ²
And R ³ is particularly preferably a hydrogen atom.

In the formula (I), the substituents represented by R ^{1 to} R ⁴ may be the same or different from each other, and these substituents may further have one or more same or different substituents. And such substituents may be those exemplified above. Also, the formula
In (I), R ¹ and R ² , and R ³ and R ⁴ may combine with each other to form a cyclic structure.

In the formula (I), L represents a divalent linking group containing at least one methylene group, for example, an alkylene group, an alkenylene group, an alkynylene group, a hetero atom (oxygen, nitrogen, sulfur, selenium, etc.), Or a group obtained by combining these. L is preferably 1 or 2
An alkylene group having a carbon chain length of 2 or more which may have at least two substituents (preferably having a carbon chain length of 2 to 12, more preferably 2 to 6, particularly preferably 2 to 4, And, for example, ethylene, triethylene, tetraethylene and the like.)

As the substituent of L, any substituent may be used as long as it does not adversely affect the photographic properties. For example, the same substituents as those represented by R ^{1 to} R ⁴ in the formula (I) may be used. Things. Preferred are an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a cyano group, a hydroxyl group and the like, and particularly preferred is an alkyl group. These substituents may combine with each other to form a ring.

In the formula (I), X represents a divalent linking group. X preferably contains a hetero atom, and the hetero atom is preferably bonded to L. The hetero atom is preferably an oxygen, sulfur, or nitrogen atom, and particularly preferably a sulfur atom.

Specific examples of X are shown below, but the present invention is not limited to these. In the specific examples, * indicates a binding site to L.

[0019]

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Z represents a residue derived from a photographically useful compound, and Z is preferably bonded to L or X via a heteroatom (oxygen, nitrogen, sulfur, etc.) in the molecule. . Photographically useful compounds include known antifoggants and development inhibitors in the field of silver halide photographic materials, and heteromercapto compounds that form stable salts with silver ions, such as mercaptotetrazole and mercaptotriazole , Mercaptoimidazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptopyrimidines, mercaptooxadiazoles, thiouracils, mercaptothiadiazoles and the like, N-containing aromatic compounds such as benzotriazoles, indazoles, salicylic acid Compounds, U.S. Pat. Nos. 4,152,160 and 4,784,9
No. 39, No. 4,569,906, No. 4,820,617, No. 4,626,500
And thiosulfonic acids.

Further, as the photographically useful compound,
Examples include known development accelerators in the field of silver halide photographic light-sensitive materials. Specific examples include hydroxamic acids, polyhydroxybenzenes, aminophenols, and hindered compounds described in US Pat. No. 5,545,507. Examples include phenols, phenidones, sulfonamide phenols, reducing compounds, and the like. Further, as photographically useful compounds, dyes, leuco dyes and the like known in the photographic industry can be mentioned.

Next, specific examples of the compound of the formula (I) of the present invention are shown, but the present invention is not limited to these.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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In one particularly preferred embodiment of the present invention, L
The compound having a carbon chain length of 2 is obtained by coupling a corresponding phenol compound having no substitution at the 4-position with bromoacetic acid ester under basic conditions to introduce an alkoxycarbonylmethylene group at the 4-position, after reduction of parts to alcohol LiAlH ₄ or the like, turned into Br hydroxy groups with PBr ₃ or the like, the Br
At the heteroatom site of X residue or X.

Alternatively, if 4-hydroxyphenethyl alcohol (CAS registration number 501-94-0) is used as a starting material,
After halogenation of the terminal hydroxy group, Z or X can be introduced by a substitution reaction as described above. in this case,
In some cases, the yield is higher when the hydroxy group of phenol is protected with a benzyl group, an acyl group, or the like. The introduction of a substituent into the phenolic nucleus may be carried out by using a known electrophilic aromatic substitution reaction at an appropriate step if a raw material to which the substituent is previously bonded is available if available. You can also.

Further, 3- (4-hydroxyphenyl)-
When 1-propanol (CAS registration number 10210-17-0) is used as a starting material, a compound having a carbon chain length of L of 3 can be synthesized in the same manner as described above. The length of the carbon chain of L is determined one by one by repeating the substitution of sodium cyanide, acid hydrolysis of a cyano group, reduction of a generated carboxyl group to a hydroxy group, and halogenation of the terminal halogen compound. You can increase the coal.

In a particularly preferred embodiment of the present invention, the compound having a carbon atom of L having a length of 3 is formylated by a Vilsmeier reaction or the like with a corresponding phenol compound having no substituent at the 4-position. After reducing the formyl group with NaBH ₄ or the like, then Brifying with form PBr ₃ or the like, replacing Br with malonic acid diester,
A carboxyl group is obtained by acid hydrolysis and decarboxylation, and thereafter, it can be synthesized by introducing X or Z according to the method described above.

The compound of the formula (I) of the present invention may exist as a salt, but the compound in a free form or a salt thereof is included in the scope of the present invention. Hydrates or solvates of the compound or its salt in the free form are also included in the scope of the present invention. Further, the compound represented by the formula (I) may have one or more asymmetric carbons,
Stereoisomers such as optically active or diastereoisomers,
Any mixtures, racemates and the like of the stereoisomers are included in the scope of the present invention. When the compound represented by the general formula (I) of the present invention has a double bond, the geometric isomer based on the double bond may be either Z-configuration or E-configuration, and a mixture thereof may be a compound of the present invention. Included in the range.

The compound represented by the formula (I) of the present invention can be used in an image recording material. In that case, the formula (I)
The compound represented by, for example, water or a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone),
It can be used by dissolving in dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also,
The compound to which the acidic group is bonded may be neutralized with an equivalent amount of alkali and used as a salt.

Further, by an emulsification dispersion method well known in the art, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution and mechanical dissolution. An emulsion dispersion can be prepared and used in an image recording material. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer or an ultrasonic wave by a method known as a solid dispersion method, and used in an image recording material.

The type of the image recording material in which the compound represented by the formula (I) of the present invention can be used is not particularly limited. Either a thermosensitive recording material for forming an image or a photothermographic material for forming an image by heat development after imagewise exposure may be used.

The image recording material provided by the present invention comprises:
An image forming layer containing an organic silver salt and a binder as a reducible silver salt on a support, a layer on the image forming layer side containing a reducing agent, and further containing a photosensitive silver halide as a photocatalyst. The image forming layer is preferably a photosensitive layer containing photosensitive silver halide. For example, European Patent Publication EP0
No. 803764A1 can be referred to.
The photocatalyst refers to a substance that generates a trigger of a reaction for forming an image by light irradiation, and examples thereof include a photoradical generator, a photoacid generator, and photosensitive silver halide.
The preferred photocatalyst in the present invention is photosensitive silver halide.

When the compound represented by the formula (I) of the present invention is used for an image recording material, it is preferred that the compound represented by the formula (I) is contained in a layer on the image forming layer side with respect to the support. For example, the compound represented by the formula (I) may be included in the image forming layer, or may be included in another layer on the image forming layer side, or may be included in two or more layers. Particularly preferred is a case where the compound represented by the formula (I) is contained in the image forming layer or a layer adjacent thereto. Compared with the case where a photographically useful compound other than the compound represented by the formula (I) of the present invention is used, the heat-developable image recording material using the compound represented by the formula (I) has a high sensitivity. In addition, thermal fogging in the non-image area is suppressed, the image is stable against fluctuations in development processing conditions, the color tone is good, and the heat / light storage stability of the image can be improved.

When the compound represented by the formula (I) of the present invention is used in an image recording material, the amount of addition is preferably 1 × 10 ^-6 to 1 mol per mol of silver used in the image recording material. Is 1 × 10 ^{-5 to} 5 × 10 ^-1 mol, more preferably 2 × 10 ^-5 to 2 × 10 ^-1 mol. Further, two or more compounds represented by the formula (I) of the present invention may be used in combination in an image recording material. Hereinafter, a heat-developable image recording material will be described as a preferred embodiment of the image recording material of the present invention, but the image recording material of the present invention is not limited to the embodiments described below.

The organic silver salt that can be used in the present invention includes:
Relatively stable to light, but in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent,
A silver salt that forms a silver image when heated to 80 ° C. or higher. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially silver salts of long-chain fatty carboxylic acids (with 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms) are preferred. The ligand is 4.0-1
Complexes of organic or inorganic silver salts having a complex stability constant in the range of 0.0 are also preferred. The silver donor material can preferably comprise about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of the aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and silver maleate. Silver salt, silver tartrate, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

In the present invention, it is preferable to use silver behenate having a silver behenate content of 75 mol% or more, more preferably 85 mol% or more, of the above-mentioned organic acid silver or the mixture of organic acid silver. . Here, the content of silver behenate indicates the mole fraction of silver behenate with respect to the organic acid silver used. As the organic acid silver other than silver behenate contained in the organic acid silver used in the present invention, those mentioned above can be preferably used.

The organic acid silver which is preferably used in the present invention is
The alkali metal salts of the organic acids shown above (sodium salts,
A potassium salt, a lithium salt, etc.) and a solution or suspension are reacted with silver nitrate. Regarding these preparation methods, the methods described in Paragraph Nos. 0019 to 0021 of Japanese Patent Application No. 11-104187 can be used.

In the present invention, a method of preparing an organic silver salt by adding a silver nitrate aqueous solution and an organic acid alkali metal salt solution to a means for mixing a sealed liquid can be preferably used. Regarding these preparation methods, the method described in Japanese Patent Application No. 11-203413 can be used. In the present invention, a water-soluble dispersing agent can be added to the silver nitrate aqueous solution and the organic acid alkali metal salt solution or the reaction solution when preparing the organic acid silver. Specific examples of the type and amount of the dispersant used are described in paragraph No. 0052 of Japanese Patent Application No. 11-115457.

The organic silver salt used in the present invention is preferably prepared in the presence of a tertiary alcohol. Preferably, the tertiary alcohol is one having a total carbon number of 15 or less,
Particularly preferred is 10 or less. Preferred examples of the tertiary alcohol include tert-butanol, but the present invention is not limited to this. The tertiary alcohol used in the present invention may be added at any time during the preparation of the silver salt of an organic acid, but is preferably added during the preparation of the alkali metal salt of an organic acid to dissolve and use the alkali metal salt of the organic acid. . Further, 0 in the third use of the alcohol weight ratio with respect of H ₂ O as a solvent at the time of organic acid silver preparation of the present invention.
It can be used arbitrarily in the range of 01 to 10,
The range of 0.03 to 1 is preferred.

The shape and size of the organic silver salt which can be used in the present invention are not particularly limited, but are disclosed in Japanese Patent Application No. 11-1041.
No. 87, paragraph 0024 can be used. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. Another method for measuring monodispersity is to determine the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) divided by the volume-weighted average diameter is preferably 80% or less. It is preferably at most 50%, more preferably at most 30%. As a measuring method, for example, the organic silver salt dispersed in a liquid is irradiated with laser light, and the particle size (volume weighted average diameter) obtained by obtaining an autocorrelation function with respect to a time change of the fluctuation of the scattered light is obtained. Can be. A dispersion of solid fine particles having an average particle size of 0.05 μm to 10.0 μm in this measurement method is preferred. More preferably, the average particle size is from 0.1 μm to 5.
0 μm, more preferably 0.1 μm or more in average particle size
2.0 μm.

The organic silver salt which can be used in the present invention is
Preferably, desalting can be performed. The desalting method is not particularly limited, and a known method can be used. A known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used. For the ultrafiltration method, see Japanese Patent Application No. 11-1.
No. 15,457, can be used. In the present invention, in order to obtain an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, the organic silver salt which is an image forming medium is contained and the photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which an aqueous dispersion is converted into a high-speed stream and then the pressure is reduced. These dispersing methods are described in Japanese Patent Application No. 11-104187, paragraph No. 00.
The methods described in 27 to 0038 can be used.

The particle size (volume weight average diameter) of the organic silver salt solid fine particle dispersion of the present invention is determined, for example, by irradiating the solid fine particle dispersion dispersed in a liquid with a laser beam and changing the fluctuation of the scattered light with time. The particle size (volume under load average diameter) obtained by obtaining the autocorrelation function or a transmission electron microscope image can be obtained. A solid fine particle dispersion having an average particle size of 0.05 μm to 10.0 μm is preferred. More preferably, the average particle size is from 0.1 μm to 5.
0 μm, more preferably 0.1 μm or more in average particle size
2.0 μm. The organic silver salt solid fine particle dispersion of the present invention preferably has a monodispersed particle size distribution. Specifically, the percentage (coefficient of variation) of the value obtained by dividing the standard deviation of the volume load average diameter by the volume load average diameter is 80% or less, more preferably 50% or less, and still more preferably 30% or less.

The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio between the organic silver salt and water is not particularly limited, but the ratio of the organic silver salt to the whole is preferably 5 to 50% by weight, and more preferably 10 to 30% by weight.
It is preferable to use the above-mentioned dispersing aid, but it is preferable to use the dispersing aid in a minimum amount within a range suitable for minimizing the particle size.
A range of 15% by weight is preferred. Organic silver salts can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably from 1 to 3 g / m ^2.

In the image recording material of the present invention, Ca, Mg,
It is preferable to add a metal ion selected from Zn and Ag to the non-photosensitive organic silver salt. Ca, Mg, Zn and A
The addition of the metal ion selected from g to the non-photosensitive organic silver salt is preferably performed in the form of a water-soluble metal salt other than a halide, specifically, in the form of a nitrate or a sulfate. Is preferred. Addition with halide is the light of the processed image recording material (room light, sunlight, etc.)
May deteriorate the image storability, that is, the so-called printout property.

Ca, Mg, Zn preferably used in the present invention
And the addition time of the metal ion selected from Ag,
After the particles of the non-photosensitive organic silver salt are formed, immediately after the particles are formed, before the dispersion, after the dispersion and immediately before the coating, such as before and after the preparation of the coating solution, it may be at any time, preferably after the dispersion and before and after the preparation of the coating solution. . The addition amount of the metal ion selected from Ca, Mg, Zn and Ag in the present invention is preferably 10 ^-3 to 10 ^-1 mol per 1 mol of non-photosensitive organic silver,
Particularly, 5 × 10 ^{−3 to} 5 × 10 ⁻² mol is preferable.

The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide can be used. . The grain formation of the photosensitive silver halide emulsion is described in JP-A-11-119374, paragraph 021.
The particles can be formed by the method described in Nos. 7 to 0224, but the method is not particularly limited to this method.
Examples of the shape of silver halide grains include cubic, octahedral, tetradecahedral, tabular, spherical, rod-like, potato-like and the like. In the present invention, cubic grains or tabular grains are particularly preferred. The characteristics of the particle shape such as the particle aspect ratio and surface index are described in JP-A-11-119.
This is the same as that described in paragraph No. 0225 of JP-A-374. The distribution of the halogen composition may be uniform inside and on the surface of the silver halide grains, and the halogen composition may be changed stepwise or may be changed continuously. Further, silver halide grains having a core / shell structure can be preferably used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used. Further, a technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.

The particle size distribution of the silver halide grains used in the present invention is, for example, a value of monodispersity of 30% or less, preferably 1 to 20% or less, and more preferably 5 to 15%.
Here, the monodispersity is defined as a percentage (%) (coefficient of variation) of a value obtained by dividing the standard deviation of the particle size by the average particle size. For convenience, the grain size of the silver halide grains is represented by a ridge length in the case of a cubic grain, and the other grains (octahedral, tetradecahedral, tabular, etc.) are calculated by the projected area circle equivalent diameter.

The photosensitive silver halide grains can contain a metal or metal complex of Group VII or VIII of the periodic table. Rhodium, rhenium, ruthenium, osnium and iridium can be preferably mentioned as the metal of Group VII or VIII of the periodic table or the central metal of the metal complex. Particularly preferred metal complexes are (NH ₄ ) ₃ Rh (H ₂ O) Cl ₅ , K ₂ R
u (NO) Cl ₅ , K ₃ IrCl ₆ and K ₄ Fe (CN) ₆ . One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol, per mol of silver. Specific examples of the structure of the metal complex include a metal complex having a structure described in JP-A-7-225449. The types and addition methods of these heavy metals are described in paragraphs 0227 to 0240 of JP-A-11-119374.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method. Good. It is preferable that the photosensitive silver halide emulsion is chemically sensitized. Regarding chemical sensitization, paragraphs 0242 to 02 of JP-A-11-119374 are used.
50 can be used. A thiosulfonic acid compound may be added to the silver halide emulsion according to the method described in EP 293,917.

Gelatin can be contained in the photosensitive silver halide, and low molecular weight gelatin is used in order to maintain a good dispersion state of the photosensitive silver halide emulsion in an organic silver salt-containing coating solution. Is preferred. The low molecular weight gelatin has a molecular weight of 500 to 60,000, preferably 1,000 to 40,000. These low molecular weight gelatins may be used at the time of particle formation or at the time of dispersion after desalting treatment, but are preferably used at the time of dispersion after desalting treatment. Ordinary gelatin (molecular weight of about 100,000) may be used at the time of particle formation, and low molecular weight gelatin may be used at the time of dispersion after desalting. The concentration of the dispersion medium is about 0.05 to 20% by weight, and a concentration range of 5 to 15% by weight is preferable from the viewpoint of handling. As the kind of gelatin, alkali-treated gelatin is usually used, but modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

The silver halide emulsion used in the production of the image recording material of the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits). And those having different conditions of chemical sensitization). The amount of the photosensitive silver halide to be used is preferably 0.01 mol to 0.5 mol, more preferably 0.02 mol to 1 mol of the organic silver salt.
0.3 mol is more preferable, and 0.03 mol to 0.25 mol is particularly preferable. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt were mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. And the like, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt. There is no particular limitation as long as it appears in. In addition, mixing two or more aqueous dispersions of organic silver salts and two or more aqueous dispersions of photosensitive silver salts during mixing is a method preferably used for adjusting photographic characteristics.

As a sensitizing dye, a sensitizing dye capable of spectrally sensitizing a silver halide particle in a desired wavelength region when adsorbed on the silver halide particle has a spectral sensitivity suitable for the spectral characteristics of an exposure light source. Can be advantageously selected. For example, as the dye that spectrally sensitizes the wavelength region of 550 nm to 750 nm, a dye represented by the general formula (II) in JP-A-10-186572 can be mentioned.
-6, II-7, II-14, II-15, II-1
8, II-23 and II-25. Also, 75
Examples of the dye that spectrally sensitizes the wavelength region of 0 to 1400 nm include a dye represented by the general formula (I) in JP-A-11-119374, and specific examples thereof include (25) and (2).
6), (30), (32), (36), (37), (4)
1), (49) and (54). Furthermore, J-
US Pat. No. 5,51,955 as a band-forming dye
And the dyes described in Example 5 of JP-A Nos. 0,236 and 3,871,887 and the dyes disclosed in JP-A-2-96131 and JP-A-59-48753. Can be These sensitizing dyes may be used alone or in combination of two or more.

These sensitizing dyes can be added by the method described in paragraph 0106 of JP-A-11-119374, but the method is not particularly limited. The addition amount of the sensitizing dye in the present invention may be a desired amount in accordance with the sensitivity and the performance of fog.
^-6 to 1 mol, more preferably 10 ^-4 to 10
^-1 mole.

According to the present invention, in order to improve the spectral sensitization efficiency,
Supersensitizers can be used. The supersensitizer used in the present invention is disclosed in European Patent Publication EP587,338, US Pat. No. 3,877,943, and US Pat.
873, 184, compounds selected from heteroaromatic or aliphatic mercapto compounds, heteroaromatic disulfide compounds, stilbene, hydrazine, and triazine.

Particularly preferred supersensitizers are disclosed in JP-A-5-3.
Heteroaromatic mercap disclosed in Japanese Patent No. 41432
Compound, heteroaromatic disulfide compound,
No. 182639, which is represented by the general formula (I) or (II)
Compound represented by the general formula of JP-A-10-111543
Stilbene compound represented by (I)
No. 9547, which is a compound represented by the general formula (I)
You. Specifically, M-1 disclosed in JP-A-5-341432
To M-24, described in JP-A-4-18239.
Compounds of d-1) to d-14), JP-A-10-1115
No. 43, compounds of SS-01 to SS-07,
31, 32, 37, 38 of JP-A-11-109547,
41 to 45 and 51 to 53. These strong colors
The amount of the sensitizer to be added is 1 mol of silver halide in the emulsion layer.
10 per ^-FourPreferably in the range of ~ 1 mol, more preferably
Or 0.001 to 0.3 moles per mole of silver halide.
Is the amount of le.

The nucleating agent used in the present invention will be described. Although the type of the nucleating agent used in the present invention is not particularly limited, examples of preferred nucleating agents are shown below. A plurality of these nucleating agents may be used in combination. Hydrazine derivatives represented by formula (H) described in Japanese Patent Application No. 11-87297, specifically, hydrazine derivatives described in Tables 1 to 4 of the same specification. JP-A-10-10672, JP-A-10-16
1270, JP-A-10-62898, JP-A-9-304870, JP-A-9-304872, JP-A-9-304871, JP-A-10-3
All hydrazine derivatives described in No. 1282, U.S. Pat. No. 5,496,695, and EP 741,320A. A substituted alkene derivative, a substituted isoxazole derivative and a specific acetal compound represented by formulas (I) to (3) described in Japanese Patent Application No. 11-87297, more preferably a compound represented by the formula (A) described in the same specification. Or a cyclic compound represented by formula (B), specifically, compounds 1 to 72 described in Chemical Formulas 8 to 12 of the same specification.

The nucleating agent may be water or a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used. In addition, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is dissolved by a well-known emulsification dispersion method. Then, an emulsified dispersion can be prepared and used mechanically. Alternatively, a nucleating agent powder can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used. The nucleating agent may be added to the image forming layer or any other layer on the image forming layer side with respect to the support, but is preferably added to the image forming layer or a layer adjacent thereto. The addition amount of the nucleating agent is preferably 1 × 10 ^-6 to 1 mol per mol of silver,
× 10 ^{-5 to} 5 × 10 ^-1 mol is more preferred, and 2 × 10 ^-5 is preferred.
~ 2 x 10 ^-1 mole is most preferred.

In addition to the above compounds, US Pat.
545,515, 5,635,339 and 5,654,130, International Publication WO
97/34196, US Pat. No. 5,686,22.
No. 8 or the compound described in JP-A-11-1
19372, Japanese Patent Application No. 9-309813,
JP-A-11-119373, Japanese Patent Application No. 9-2825
The compounds described in JP-A-64-64, JP-A-11-95365, JP-A-11-95366, and Japanese Patent Application No. 9-332388 may be used.

For forming a super-high contrast image, a high contrast accelerator can be used in combination with the nucleating agent. For example,
Amine compounds described in U.S. Pat. No. 5,545,505, specifically AM-1 to AM-5, hydroxamic acids described in U.S. Pat. No. 5,545,507, specifically, HA-1 to HA-11, U.S. Pat.
Acrylonitriles described in 545,507,
Specifically, CN-1 to CN-13, US Pat.
No. 8,983, specifically, hydrazine compounds, specifically CA-1 to CA-6, and onium salts described in JP-A-9-297368, specifically, A-1 to A-4.
2, B-1 to B-27, C-1 to C-14 and the like can be used.

In a heat-developable image recording material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, formic acid or formate is a strong fogging substance. The content of formic acid or formate on the side of the heat-developable image recording material having the image forming layer containing the photosensitive silver halide is preferably 5 mmol or less, more preferably 1 mmol or less per mole of silver.

In the image recording material of the present invention, an acid or a salt thereof formed by hydration of diphosphorus pentoxide is preferably used in combination with a nucleating agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaline Acids (salts); Particularly preferred acids or salts thereof formed by hydration of diphosphorus pentoxide are orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, Examples include sodium hexametaphosphate and ammonium hexametaphosphate. The acid or salt thereof formed by hydration of diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or the binder layer adjacent thereto in that a desired effect is exhibited in a small amount. The amount of acid or salt thereof formed by hydration of diphosphorus pentoxide (1m
The per ² coating weight) may be desired amount depending on the performance such as sensitivity and fog, but preferably is 0.1 to 500 mg / m ^2, 0.5 to 100 mg / m ² is more preferable.

The image recording material of the present invention preferably contains a reducing agent for an organic silver salt. The reducing agent for the organic silver salt is any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, per 1 mol of silver on the surface having the image forming layer. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50 mol% with respect to 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable image recording material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, and JP-A-49-46427. 49-115540
JP-A-50-34334, JP-A-50-14361
Nos. 0, 50-147711 and 51-32
632, 51-1023721, 51
JP-A-32324, JP-A-51-51933, JP-A-5-51933
JP-A-2-84727, JP-A-55-108654,
JP-A-56-146133, JP-A-57-82828, JP-A-57-82829, JP-A-6-3793, U.S. Pat. Nos. 3,679,426 and 3,751,252 No. 3,751,255
No. 3,761,270, No. 3,
Nos. 782,949, 3,839,048, 3,928,686, and 5,46
No. 4,738, German Patent No. 2,321,328, European Patent Publication EP 692,732 and the like.

For example, amide oximes such as phenylamide oxime, 2-thienyl amide oxime and p-phenoxyphenyl amide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2′-bis (hydroxy A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of methyl) propionyl-β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg, hydroquinone, Bis (ethoxyethyl) hydroxylamine, a combination of piperidinohexose reductone or formyl-4-methylphenylhydrazine); phenylhydroxamic acid, p
Hydroxamic acids such as -hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano Α-cyanophenylacetic acid derivatives such as -2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-
Bis-β as exemplified by dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane -Naphthol; bis-β-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2 ′,
4′-dihydroxyacetophenone); 3
5-methyl-1-phenyl-5-pyrazolone and the like;
Pyrazolones; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4-benzenesulfonamidophenol and p- Sulfonamidophenol reducing agents such as benzenesulfonamidophenol; 2-phenylindane-1,3-dione; and chromanes such as 2,2-dimethyl-7-tert-butyl-6-hydroxychroman; 2,6-dimethoxy- 3,
1,4-dihydropyridines such as 5-dicarbethoxy-1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4- Hydroxy-
3-methylphenyl) propane, 4,4-ethylidene-
Bis (2-t-butyl-6-methylphenol), 1,
1, -bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-
Bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.); ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain Species indane-1,3-dione; chromanol (such as tocopherol). Particularly preferred reducing agents are bisphenol, chromanol.

When a reducing agent is used in the image recording material of the present invention, it may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion, and an emulsified dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

Examples of the development accelerator include Japanese Patent Application No. 11-739.
Phenol derivatives represented by the formula (A) described in JP-A-51-51 are preferably used. The phenol derivative represented by the formula (A) exhibits a strong development promoting effect when used in combination with the above reducing agent. Specifically, A- described in the same specification
1 to A-54 are preferably used. The phenol derivative represented by the formula (A) is used in an amount of 0.01 mol% to 1% based on the reducing agent.
It is preferably used in the range of 00 mol%, more preferably in the range of 0.1 mol% to 20 mol%.

The phenol derivative represented by the formula (A) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on the layer side. It is preferably added to the containing layer. The phenol derivative represented by the formula (A) may be added by any method such as an aqueous solution, an organic solvent solution, powder, solid fine particle dispersion, and emulsified dispersion. Dispersion of solid fine particles can be performed by a known means for making fine (for example, a ball mill, a vibrating ball mill, a sand mill,
Colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

When an additive known as a “toning agent” for improving an image is contained, the optical density may be increased. The toning agent may also be advantageous in forming a black silver image. The toning agent is preferably contained in an amount of 0.1 to 50% mol, more preferably 0.5 to 20% mol, per mol of silver on the side having the image forming layer. Further, the color tone agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a heat-developable image recording material utilizing an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, and JP-A-49-5020. No. 49-91215, No. 49-91215, No. 50-2524, No. 50-32927, No. 50-67132, No. 50-67641, No. 50-11421.
No. 7, No. 51-3223, No. 51-2792
No. 3, No. 52-14788, No. 52-998
No. 13, No. 53-1020, No. 53-760
No. 20, No. 54-156524, No. 54-1
Nos. 56525, 61-183642, JP-A-4-56848, JP-B-49-10727, JP-A-54-20333, U.S. Pat.
0,254, 3,446,648, 3,782,941, 4,12
No. 3,282, 4,510,236, British Patent No. 1,380,795, Belgian Patent No. 841,910, and the like.

Examples of toning agents include phthalimide and N-hydroxyphthalimide; succinimide, pyrazoline-
5-one, and quinazolinone, 3-phenyl-2-
Cyclic imides such as pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (e.g. N-hydroxy-
1,8-naphthalimide); cobalt complex (for example, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl- Mercaptans exemplified by 1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides (for example, (N, N-dimethylaminomethyl) Phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents such as N, N'-hexamethylenebis (1 -Carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6 -Diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole));
And 3-ethyl-5-[(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or a metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,
7-dimethoxyphthalazinone and 2,3-dihydro-
Derivatives such as 1,4-phthalazinedione; combinations of phthalazinone and phthalic acid derivatives (such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); phthalazine, phthalazine derivatives (for example, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-
iso-butylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, and 2,3-
Derivatives such as dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); quinazolinedione, benzoxazine or naphthoxazine derivatives; for silver halide formation in situ as well as color tone regulators Rhodium complexes that also function as sources of halide ions of, for example, hexachlororhodium (II)
I) Ammonium acid, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2 Benzoxazine-2,4-dione, such as 1,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidine And asymmetric-triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil,
And tetraazapentalene derivatives (for example, 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,
3a, 5,6a-tetraazapentalene, and 1,4
-Di (o-chlorophenyl) -3,6-dimercapto-
1H, 4H-2, 3a, 5, 6a-tetraazapentalene) and the like.

As toning agents, Japanese Patent Application No. Hei 10-213487
The phthalazine derivative represented by the general formula (F) described in the specification is preferably used. Specifically, in the case where a color tone agent preferably used in A-1 to A-10 described in the same specification is used, it may be added by any method such as a solution, a powder, and a solid fine particle dispersion. The dispersion of the solid fine particles is carried out by a known fine means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The pH of the film surface of the heat-developable image recording material before the heat-development treatment is preferably 6.0 or less, more preferably 5.5 or less. The lower limit is not particularly limited, but is about 3. The adjustment of the film surface pH is preferably performed using an organic acid such as a phthalic acid derivative, a nonvolatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is preferable in achieving a low film surface pH since ammonia is easily volatilized and can be removed before the application step and the heat development. In addition, membrane surface pH
Is described in paragraph No. 0123 of Japanese Patent Application No. 11-87297.

In the heat-developable image recording material, the silver halide emulsion or / and organic silver salt are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and are stored in stock. Can be stabilized against a decrease in sensitivity in the medium. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination include US Pat. No. 2,131,03.
No. 8, No. 2,694,716, azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605, U.S. Pat. No. 2,728,663, mercury salts described in U.S. Pat. No. 3,287,135, urazole described in U.S. Pat. No. 3,287,135, U.S. Pat. No. 3,235,652.
Patent No. 62, UK Patent No. 62
Oxime, nitrone, nitroindazole described in US Pat. No. 3,448, polyvalent metal salt described in US Pat. No. 2,839,405, US Pat. No. 3,220,839.
No. 2,566,263 and U.S. Pat. No. 2,597,9.
15, palladium, platinum and gold salts described in US Pat. No. 4,108,665 and US Pat.
No. 4,128,557 and U.S. Pat. No. 4,137,079, U.S. Pat. No. 4,138,365 and U.S. Pat. And the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog.
The benzoic acids may be any benzoic acid derivative, but examples of preferred structures include those described in US Pat. No. 4,784,939.
No. 4,152,160, Japanese Unexamined Patent Application Publication No.
Compounds described in JP-A-3298663, JP-A-9-329864, and JP-A-9-281637 are exemplified. The benzoic acid may be added to any layer of the image recording material, but is preferably added to the layer having the image forming layer, more preferably to the organic silver salt-containing layer. The benzoic acid may be added in any step of the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed. To just before application. The benzoic acid may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent, and a color tone agent. The benzoic acid may be added in any amount, but is preferably 1 × 10 ^-6 mol to 2 mol, more preferably 1 × 10 ^-3 mol to 0.5 mol, per 1 mol of silver.

Mercury (I) was used as an antifoggant in the image forming layer.
I) It may be advantageous to add a salt. Good for this purpose
Preferred mercury (II) salts are mercury acetate and mercury bromide.
You. The amount of mercury used in the present invention is
1 × 10 per mole of silver^-9Mol ~ 1 x 10
^-3Mol, more preferably 1 × 10^-8Mol ~ 1 x 10 ^-Four
Range of moles.

The antifoggants particularly preferably used in the present invention are organic halides, for example, US Pat.
No. 874,946, U.S. Pat. No. 4,756,999.
No. 5,340,712, US Pat. No. 5,369,000, US Pat.
64,737, JP-A-50-137126, JP-A-50-89020, and 50-196624.
JP, JP-A-59-57234, JP-A-50-1203
No. 28, No. 51-121332, No. 54-5
Nos. 8022, 56-70543, 56-
Nos. 99335, 59-90842 and 61
129,642, 62,129,845,
JP-A-7-2781, JP-A-7-5621, JP-A-9-160164, JP-A-10-197988, JP-A-9-244177, JP-A-9-244178, JP-A-9-160167, 9-319022
JP-A-9-258367, JP-A-9-265515
Nos. 0, 9-319022 and 10-197
Nos. 989, 11-242304, 6-2
08191, 8-15809, Japanese Patent Application No. 1
Nos. 0-181449, 10-292864, 11-90095, and 11-8977.
Compounds described in JP-A Nos. 3 and 11-205330 are exemplified.

[0082] Japanese Patent Application No. 11-87297 describes
The hydrophilic organic halide represented by the formula (P) prevents fog
It is preferably used as a stopping agent. Specifically, the same specification
(P-1) to (P-118) described in are preferably used.
It is. The addition amount of the organic halide is based on 1 mol of silver.
In terms of mol (mol / mol Ag)
Is 1 × 10^-Five~ 2 mol / mol Ag, more preferably
5 × 10^-Five~ 1 mol / mol Ag, more preferably
1 × 10^-Four~ 5 × 10 ^-1mol / mol Ag. This
These may be used alone or in combination of two or more.

A salicylic acid derivative represented by the formula (Z) described in Japanese Patent Application No. 11-87297 is preferably used as an antifoggant. Specifically, (A-1) to (A-60) described in the same specification are preferably used. The amount of the salicylic acid derivative represented by the formula (Z) is:
It is preferably 1 × 10 ^{−5 to} 5 × 10 ⁻¹ mol / m, expressed as a mol amount per mol of silver (mol / mol Ag).
olAg, more preferably 5 × 10 ^-5 to 1 × 10 ^-1 mo
1 / mol Ag, more preferably 1 × 10 ^{−4 to} 5 × 1
0 ^-2 mol / mol Ag. These may be used alone or in combination of two or more.

As the antifoggants preferably used,
Formalin scavengers are effective, for example, the compounds represented by the formula (S) described in Japanese Patent Application No. 11-23995 and the exemplified compounds (S-1) to (S-2).
4).

The antifoggant is dissolved in water or a suitable organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Can be used. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder can be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a Manton-Gaulin, a microfluidizer, or an ultrasonic wave by a method known as a solid dispersion method.

The antifoggant may be added to the layer on the image forming layer side with respect to the support, ie, to the image forming layer or any other layer on the layer side. It is preferred to add. The image forming layer is a layer containing a reducible silver salt (organic silver salt), and is preferably an image forming layer further containing a photosensitive silver halide.

The image-recording material of the present invention may contain a mercapto compound, a disulfide compound or a thione compound in order to suppress or accelerate the development and control the development, and to improve the storage stability before and after the development. When a mercapto compound is used in the present invention, it may have any structure, but is preferably a compound represented by Ar-SM or Ar-SS-Ar. Wherein M is a hydrogen atom or an alkali metal atom, and Ar is one or more nitrogen, sulfur,
An aromatic ring or a condensed aromatic ring having an oxygen, selenium or tellurium atom. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine,
Pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, a halogen atom (eg, Br and C
l), a hydroxy group, an amino group, a carboxy group, an alkyl group (for example, one or more carbon atoms, preferably
), An alkoxy group (for example,
It may have one selected from a substituent group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and an aryl group (which may have a substituent). .

Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2′-dithiobis- (benzothiazole), 3
-Mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto -4 (3H) -quinazolinone, 7
-Trifluoromethyl-4-quinolinethiol, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,
3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydrokilocy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,
6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1
-Phenyl-5-mercaptotetrazole, 3- (5-
Mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N '-{3- (5-mercaptotetrazolyl) phenyl} urea, 2-mercapto-4-
Examples include, but are not limited to, phenyloxazole. The addition amount of these mercapto compounds is 0.0001 to 1.0 per mol of silver in the image forming layer.
A molar range is preferred, more preferably an amount of 0.001 to 0.3 mole per mole of silver.

As the binder, it is preferable to use the polymer latex described below. In the image recording material of the present invention, at least one of the image forming layers containing the photosensitive silver halide is preferably an image forming layer using the polymer latex described below as 50% by weight or more of the total binder. Further, the polymer latex may be used not only for the image forming layer, but also for the protective layer and the back layer.In particular, when the heat-developable image recording material of the present invention is used for printing in which dimensional change is problematic, It is preferable to use a polymer latex also for the back layer.
However, the "polymer latex" referred to here is a polymer in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and the molecular chains themselves are molecularly dispersed. Any of them may be used. The polymer latex of the present invention is described in "Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Polymer Publishing Association (1978))", "Application of Synthetic Latex (Edited by Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Published by The Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, Published by the Society of Polymer Publishing (19)
70))). The average particle size of the dispersed particles is 1 to 50000 nm, more preferably 5 to 1000 n.
A range of about m is preferable. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

As the polymer latex, a so-called core / shell type latex may be used in addition to the usual polymer latex having a uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell. The glass transition temperature (Tg) of the polymer latex preferably used for the binder generally differs between the protective layer, the back layer and the image forming layer. The temperature of the image forming layer is preferably from -30 to 40 ° C. in order to promote the diffusion of useful photographic materials during thermal development. When used for the protective layer or the back layer, a glass transition temperature of 25 to 70 ° C. is preferable for contacting various devices.

The minimum film forming temperature of polymer latex (MF
T) is −30 ° C. to 90 ° C., more preferably 0 ° C. to 70 ° C.
The degree is preferred. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film-forming aid is an organic compound (usually an organic solvent) which is also called a plasticizer and lowers the minimum film-forming temperature of the polymer latex.
0)) ".

Examples of the polymer used for the polymer latex include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized.
In the case of a copolymer, it may be a random copolymer or a block copolymer. The polymer has a number average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 1, as a number average molecular weight.
About 00000 is preferable. If the molecular weight is too small, the mechanical strength of the image forming layer may be insufficient, and if it is too large, the film forming property may be poor.

Specific examples of the polymer latex used as a binder in the image forming layer of the image recording material of the present invention include the following. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, methyl methacrylate / butadiene /
Latex of itaconic acid copolymer, latex of ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, styrene /
Butadiene / acrylic acid copolymer latex, styrene / butadiene / divinylbenzene / methacrylic acid copolymer latex, methyl methacrylate / vinyl chloride / acrylic acid copolymer latex, vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer latex. More specifically, a copolymer latex of methyl methacrylate / ethyl acrylate / methacrylic acid = 33.5 / 50 / 16.5 (wt%), methyl methacrylate / butadiene / itaconic acid = 47.5 / 47.5 / 5 ( % By weight) and a copolymer latex of ethyl acrylate / methacrylic acid = 95/5 (% by weight).

Further, such polymers are commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635,4658
3, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Ni
pol LX811, 814, 821, 820, 857
(Nippon Zeon Co., Ltd.), VONCORT-R33
As polyester resins such as 40, R3360, R3370, 4280 (all manufactured by Dainippon Ink and Chemicals, Inc.), FINETEX ES650, 611, 675, 8
50 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-siz
e, polyurethane resins such as WMS (all manufactured by Eastman Chemical) include HYDRAN AP10, 20,
Rubber-based resins such as 30, 40 (all manufactured by Dainippon Ink and Chemicals, Inc.) include LACSTAR 7310K, 330
7B, 4700H, 7132C (all manufactured by Dainippon Ink and Chemicals, Inc.), Nipol LX410, 430, 43
5, 438C (manufactured by Nippon Zeon Co., Ltd.); vinyl chloride resins such as G351 and G576 (manufactured by Nippon Zeon Co., Ltd.); and vinylidene chloride resin, L50.
2, L513 (all made by Asahi Kasei Corporation), Aron D7
020, D504, D5071 (Mitsui Toatsu Co., Ltd.
Chemical Pearl S12 as an olefin resin
And SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.). These polymers may be used alone or as a mixture of two or more as necessary.

In the image forming layer, the above-mentioned polymer latex is preferably used as 50% by weight or more of the total binder, and more preferably 70% by weight or more of the above-mentioned polymer latex. If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, or hydroxypropylmethylcellulose may be added to the image forming layer in an amount of 50% by weight or less of the whole binder. The amount of the hydrophilic polymer to be added is preferably 30% by weight or less, more preferably 15% by weight or less of the total binder in the image forming layer.

The image forming layer is preferably prepared by applying an aqueous coating solution and then drying. Here, "aqueous" means that 60% by weight or more of the solvent (dispersion medium) of the coating liquid is water. As components other than water of the coating solution, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used.
Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 7
0/30, water / ethanol = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 9
5/5, water / methanol / dimethylformamide = 80
/ 15/5, water / methanol / dimethylformamide =
90/5/5. (However, numbers represent weight%.)

The total amount of the binder in the image forming layer is 0.2 to 3
0 g / m ^2, more preferably in the range of 1 to 15 g / m ^2. A crosslinking agent for crosslinking and a surfactant for improving coating properties may be added to the image forming layer. further,
As a binder for the protective layer, a combination of polymer latexes having different I / O values obtained by dividing an inorganic value by an organic value based on an organic conceptual diagram described in paragraphs 0025 to 0029 of Japanese Patent Application No. 11-6872. Can be preferably used.

In the present invention, if necessary, Japanese Patent Application No.
Paragraph Nos. 0021 to 002 of the specification of 1-114358
5 plasticizer (eg, benzyl alcohol, 2,2,
4-trimethylpentanediol-1,3-monoisobutyrate) can be added to control the film formation temperature. Further, as described in paragraphs 0027 to 0028 of Japanese Patent Application No. 11-6872, a hydrophilic polymer may be added to a polymer binder, and a water-miscible organic solvent may be added to a coating solution.

Each of the layers is described in Japanese Patent Application No. 10-1996.
No. 26, using a first polymer latex having a functional group introduced therein and a crosslinking agent having a functional group capable of reacting with the first polymer latex and / or a second polymer latex. Can also be formed. Specific examples of the functional group include a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, and an oxazolinyl group. Examples of the crosslinking agent include an epoxy compound, an isocyanate compound, a blocked isocyanate compound, and methylo. And carboxylic acid compounds, hydroxy compounds, carboxyl compounds, amino compounds, ethyleneimine compounds, aldehyde compounds, and halogen compounds. As specific examples of the crosslinking agent, isocyanate compounds: hexamethylene isocyanate, duranate WB40-80
D, WX-1741 (manufactured by Asahi Kasei Kogyo Co., Ltd.), Baihijur 3100 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate WD725 (manufactured by Takeda Pharmaceutical Co., Ltd.), Aquanate 100, 200 (manufactured by Nippon Polyurethane Co., Ltd.) ),
Water-dispersed polyisocyanates and amino compounds described in JP-A-9-160172: Sumitex Resin M-3
(Manufactured by Sumitomo Chemical Co., Ltd.), epoxy compound: Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.), halogen compound: 2,4 dichloro-6-hydroxy-1,3,3
And sodium 5-triazine.

The total amount of the binder for the image forming layer is from 0.2 to
30 g / m ^2, more preferably in the range of 1.0~15g / m ^2. The total amount of the binder for the protective layer is 0.2 to 10.
0 g / m ^2, more preferably in the range of 0.5 to 6.0 g / m ^2. The total binder amount for the back layer is 0.01 to 1
0.0 g / m ² , more preferably 0.05 to 5.0 g /
m ² .

Each of these layers may be provided in two or more layers. When the image forming layer has two or more layers, it is preferable to use a polymer latex as a binder for all the layers. Further, the protective layer is a layer provided on the image forming layer, and may have two or more layers.
Preferably, a polymer latex is used for the layer, especially the outermost protective layer. The back layer is a layer provided on the undercoat layer on the back surface of the support, and there may be two or more layers. However, it is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.

The slip agent is not particularly limited, and any compound may be used as long as it reduces the coefficient of friction on the surface of the object when it is present on the surface of the object, as compared to when it is not present. Examples of the slipping agent include paragraphs 0061 to 0064 of JP-A-11-84573, and Japanese Patent Application No. 11-10688.
The compounds described in Paragraph Nos. 0049 to 0062 of the specification 1 can be used. Specific examples of preferable slip agents include Cellolsol 524 (main component carnauba wax), Polylon A, 393, H-481 (main component polyethylene). Wax), High Micron G-110 (main component ethylene bisstearic acid amide), High Micron G-270
(Main component stearic acid amide) (all from Chukyo Yushi (Co.)), W-1: C 16 H 33 -O-SO 3 Na, W-
2: and the like _{C 18 H 37 -O-SO 3} Na. The amount of the slipping agent used is 0.1 to 50% by weight, preferably 0.5 to 30% by weight of the binder amount of the added layer.

As described in Japanese Patent Application No. 10-346561 and Japanese Patent Application No. 11-106881, the preheating section is conveyed by a facing roller, and the heat development processing section uses a roller on the side having the image forming layer. In the case of using a heat development processing apparatus which conveys the opposite back surface by sliding it to a smooth surface by driving, the outermost surface layer on the side having the image forming layer of the heat development image recording material at the development processing temperature and the back surface The ratio of the coefficient of friction with the outermost layer is 1.5 or more, and there is no particular upper limit, but it is about 30. Further, μb is 1.0 or less, preferably 0.8 to 0.05. This value is obtained by the following equation. Ratio of friction coefficient = dynamic friction coefficient (μe) between the roller member of the heat developing machine and the surface having the image forming layer / dynamic friction coefficient (μb) between the smooth surface member of the heat developing machine and the back surface (heat) at the heat development processing temperature The slipperiness of the outermost surface layer on the surface having the developing machine member and the image forming layer and / or the opposite surface can be adjusted by adding a slipping agent to the outermost surface layer and changing the amount of addition.

On both sides of the support, JP-A-64-2054
No. 4, JP-A-1-180537, JP-A-1-18037
No. 209443, JP-A-1-285939,
JP-A-1-296243, JP-A-2-24649
JP, JP-A-2-24648, JP-A-2-18
4844, JP-A-3-109545, JP-A-3-137637, JP-A-3-141346, JP-A-3-141347, JP-A-4-96
No. 055, U.S. Pat. No. 4,645,731, JP-A-4-68344, and Japanese Patent No. 2,557,
No. 641, P2 right column, line 20 to P3 right column, line 30, paragraph Nos. 0020-00 of Japanese Patent Application No. 10-221039.
37, paragraph number 0 of Japanese Patent Application No. 11-106881
It is preferable to provide an undercoat layer containing a vinylidene chloride copolymer containing 70% by weight or more of the repeating units of the vinylidene chloride monomer described in No. 063 to 0080.

When the amount of the vinylidene chloride monomer is less than 70% by weight, sufficient moisture-proof properties cannot be obtained, and the dimensional change over time after thermal development becomes large. Further, the vinylidene chloride copolymer preferably contains a repeating unit of a carboxyl group-containing vinyl monomer as another constituent repeating unit of the vinylidene chloride monomer. The inclusion of such a constitutional repeating unit is because the polymer (polymer) is crystallized by using only the vinyl chloride monomer, so that it is difficult to form a uniform film when the moisture-proof layer is applied, and This is because a carboxyl group-containing vinyl monomer is indispensable for stabilizing (polymer). The molecular weight of the vinylidene chloride copolymer is preferably 45,000 or less, more preferably 10,000 or more and 45,000 or less in terms of weight average molecular weight. When the molecular weight increases, the adhesiveness between the vinylidene chloride copolymer layer and the support layer such as polyester may be deteriorated.

The content of the vinylidene chloride copolymer is at least 0.3 μm as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer, and is preferably at least 0.1 μm.
It is in the range of 3 μm to 4 μm. The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support. Usually, one layer is provided on each side, but in some cases, two layers are provided. The above may be provided. When a multi-layer structure of two or more layers is used, the total amount of the vinylidene chloride copolymer may fall within the range of the present invention. Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer.

The support may be coated with an undercoat layer using SBR, polyester, gelatin or the like as a binder, if necessary, in addition to the vinylidene chloride copolymer layer. These undercoat layers may have a multilayer structure or may be provided on one side or both sides of the support. The general thickness (per layer) of the undercoat layer is 0.01 to 5 µm, more preferably 0.05 to 1 µm.

Various supports can be used for the image recording material of the present invention. Typical supports include polyesters such as polyethylene terephthalate, polyethylene naphthalate, cellulose nitrate, cellulose esters,
Examples include polyvinyl acetal, syndiotactic polystyrene, polycarbonate, paper supports coated on both sides with polyethylene, and the like. Among them, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferable in terms of strength, dimensional stability, chemical resistance and the like. The thickness of the support is 90 to 180 as a base thickness excluding the undercoat layer.
μm is preferred.

The support used in the image recording material of the present invention is
JP-A-10-48772, JP-A-10-1067
No. 6, JP-A-10-10677 and JP-A-11-11
No. 65025, Japanese Patent Application No. 9-308898. Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of ° C is preferably used. The dimensional change rate of the support after heating at 120 ° C. for 30 seconds after the heat treatment is the longitudinal direction (MD).
Is -0.03% to + 0.01%, and the transverse direction (TD) is 0 to
It is preferably 0.04%.

The image recording material of the present invention has a reduced dust adhesion.
Low, prevention of static mark generation, conveyance in automatic conveyance process
Japanese Patent Application Laid-Open No. H11-84573 for preventing defects
Oxidation of conductive metal described in paragraph Nos. 0040 to 0051
Antistatic using substances and / or fluorosurfactants
Can be U.S. patents for conductive metal oxides
5,575,957, Japanese Patent Application No. 10-0413
No. 02, paragraphs 0012 to 0020.
Patent application title: Needle-shaped conductive tin oxide doped with antimony
Doping with antimony described in 4-29134
Fibrous tin oxide is preferably used. Metal oxide
The surface resistivity (surface resistivity) of the containing layer is 25 ° C. and a relative humidity of 2
10% in an atmosphere of 0%¹²Ω or less. Preferably 10¹¹Ω or less
Lower is better. Thereby, good antistatic properties can be obtained. This
The lower limit of the surface resistivity at the time of is not particularly limited, but usually
10 ⁷About Ω.

At least one of the surface having the image forming layer of the image recording material of the present invention and the outermost layer surface opposite to the surface,
Preferably, both Beck smoothness are less than or equal to 2000 seconds, more preferably between 10 seconds and 2000 seconds. The Beck smoothness is determined by the Japanese Industrial Standards (JIS) P8119 “Smoothness test method of paper and paperboard using Beck tester” and T
It can be easily obtained by the APPI standard method T479. The Beck smoothness of the outermost layer on the side having the image forming layer of the image recording material and the outermost layer on the opposite side are described in
As described in paragraphs 0052 to 0059 of JP-A-84573, it can be controlled by appropriately changing the particle size and the amount of the matting agent contained in the layers on both surfaces.

A water-soluble polymer can be preferably used as a thickener for imparting coatability. The water-soluble polymer may be any of a natural polymer, a semi-synthetic polymer and a synthetic polymer, and the type thereof is not particularly limited. Natural products include starches (corn starch, starch, etc.), seaweeds (agar, sodium alginate, etc.), vegetable stickies (eg, gum arabic), animal proteins (such as glue, casein, gelatin, egg white), fermented stickies ( Pullulan,
Dextrin) and the like, such as starches (soluble starch, carboxyl starch, dextran, etc.), and celluloses (viscose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, etc.).
Hydroxypropylcellulose, hydroxypropylmethylcellulose, etc.). Synthetic polymers include polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol,
Maleic acid copolymer such as polypropylene glycol, polyvinyl ether, polyethylene imine, polystyrene sulfonic acid or its copolymer, polyvinyl sulfanic acid or its copolymer, polyacrylic acid or its copolymer, acrylic acid or its copolymer, etc. Coalescing, maleic acid monoester copolymer, acryloylmethylpropanesulfonic acid or a copolymer thereof.

Among these, the water-soluble polymers preferably used include sodium alginate, gelatin, dextran, dextrin, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, Polystyrene sulfonic acid or its copolymer, polyacrylic acid or its copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid or its copolymer, and the like are particularly preferably used as a thickener.

Particularly preferred thickeners are gelatin, dextran, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polystyrenesulfonic acid or a copolymer thereof, polyacrylic acid or a copolymer thereof, and maleic acid. And acid monoester copolymers. These compounds are described in detail in “Applications and Markets of New Water-Soluble Polymers” (published by CMC Corporation, edited by Shinji Nagatomo, issued November 4, 1988).

The amount of the water-soluble polymer used as a thickener can be selected so that the viscosity increases when added to the coating solution, and the amount used is not particularly limited. Generally, the concentration in the liquid is 0.01 to 30% by weight, more preferably 0.1 to 30% by weight.
And preferably from 0.1 to 10% by weight.
% By weight. The viscosity obtained by these methods is preferably 1 to 200 mPa · s, more preferably 5 to 100 mPa · s, as an increase from the initial viscosity. In addition,
In the measurement, a value measured at 25 ° C. with a B-type rotational viscometer is shown. When adding to a coating solution or the like, it is generally desirable to add the thickener in a solution as dilute as possible. In addition, it is preferable to perform sufficient stirring during the addition.

Surfactants are classified into dispersants, coating agents, wetting agents, antistatic agents, photographic control agents and the like depending on the purpose of use. The goal can be achieved. As the surfactant, any of nonionic and ionic (anion, cation, betaine) can be used. Further, a fluorine-based surfactant is also preferably used.

Preferred nonionic surfactants include:
Polyoxyethylene, polyoxypropylene, polyoxybutylene, a surfactant having a nonionic hydrophilic group of polyglycidyl and sorbitan, specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Ethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanolamine fatty acid partial ester can be exemplified. .

The anionic surfactants include carboxylate, sulfate, sulfonate and phosphate ester salts. Representative examples are fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and the like.
Alkyl sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N-oleyltaurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl Ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate,
And naphthalene sulfonate formaldehyde condensate.

As cationic surfactants, amine salts,
Examples thereof include quaternary ammonium salts and pyridium salts, and more specifically, primary to tertiary fatty amine salts and quaternary ammonium salts.
Secondary ammonium salts (eg, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridium salts, and alkylimidazolium salts). Examples of betaine-based surfactants include carboxybetaine and sulfobetaine, and N-trialkyl-N-carboxymethylammonium betaine,
-Trialkyl-N-sulfoalkylene ammonium betaine and the like.

These surfactants are described in “Applications of Surfactants (written by Koshobo and Takao Karimei, published on September 1, 1980)”.
It is described in. The amount of the surfactant to be used is not particularly limited, and can be appropriately selected to obtain desired properties. In addition, the application amount of the fluorine-containing surfactant was 0.1 ml / m ² .
Preferred is between 01 mg and 250 mg.

Specific examples of the surfactant are described below, but are not limited thereto (here, -C ₆ H _4- represents a phenylene group). _{WA-1: C 16 H 33} (OCH 2 CH 2) 10 OH WA-2: C 9 H 19 -C 6 H 4 - (OCH 2 CH 2) 12 O
H WA-3: Sodium dodecylbenzenesulfonate WA-4: Sodium tri (isopropyl) naphthalenesulfonate WA-5: Sodium tri (isobutyl) naphthalenesulfonate WA-6: Sodium dodecyl sulfate WA-7: Di-α-sulfosuccinate (2-ethylhexyl) ester sodium salt _{WA-8: C 8 H 17} -C 6 H 4 - (CH 2 CH 2 O) 3 (C
H ₂ ) ₂ SO ₃ K

[0122] WA-10: cetyltrimethylammonium chloride _{WA-11: C 11 H 23} CONHCH 2 CH 2 N (+)
_{(CH 3) 2 -CH 2 COO} (-) WA-12: C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
O) ₁₆ H WA-13: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COO
_{K WA-14: C 8 F} 17 SO 3 K WA-15: C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
_{O) 4 (CH 2) 4} SO 3 Na WA-16: C 8 F 17 SO 2 N (C 3 H 7) (CH 2) 3 O
_{CH 2 CH 2 N (+)} (CH 3) 3 -CH 3 -C 6 H 4 -SO 3
(−) WA-17: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ C
_{H 2 N (+) (CH} 3) 2 -CH 2 COO (-)

In a preferred embodiment of the image recording material of the present invention, an intermediate layer may be provided, if necessary, in addition to the image forming layer and the protective layer. Can be simultaneously coated in an aqueous system. The coating method includes extrusion coating, slide bead coating, curtain coating, etc.
The slide bead coating method disclosed in FIG. 1 of the specification of Japanese Patent Application No. 10-292849 is particularly preferred.

In the case of a silver halide photographic light-sensitive material using gelatin as a main binder, it is rapidly cooled in a first drying zone provided downstream of a coating die, and as a result, gelatinization of gelatin occurs and the coating film is cooled. Is solidified. The coating film that has been cooled and solidified and has stopped flowing is guided to the subsequent second drying zone, where the solvent in the coating solution is volatilized and formed into a film in the subsequent drying zone. As a drying method after the second drying zone, there are an air loop method in which a jet is blown from a U-shaped duct to a roller-supported support, and a wrapper in which a support is wound around a cylindrical duct in a helical shape and transported and dried. System (air floating system).

In the case of a coating liquid in which the main component of the binder is a polymer latex, the flow of the coating liquid cannot be stopped by rapid cooling, so that the preliminary drying may be insufficient only in the first drying zone. In this case, in a drying method such as a silver halide photographic light-sensitive material, flow unevenness and drying unevenness occur, and serious defects are likely to occur on the coated surface. A preferred drying method is drying in a horizontal drying zone at least until the constant-rate drying is completed, regardless of the first drying zone or the second drying zone as described in Japanese Patent Application No. 10-292849. It is a method to make it. The transport of the support immediately after the application until it is led to the horizontal drying zone may or may not be a horizontal transport, and the rising angle with respect to the horizontal direction of the coating machine may be between 0 and 70 °. . The horizontal drying zone means that the support has only to be conveyed within ± 15 ° vertically with respect to the horizontal direction of the coating machine, and does not mean horizontal conveyance.

The constant-rate drying means a drying process in which the amount of heat flowing in at a constant liquid film temperature is used for evaporating the solvent. At the end of drying, the rate of drying decreases at the end of drying due to various factors (such as the rate of diffusion of moisture inside the material and the evaporation surface receding), and the applied heat is also used to raise the liquid film temperature. Drying process. The critical water content at which the transition from the constant rate process to the rate decreasing process is 200 to 300%. When the constant-rate drying is completed, the drying proceeds sufficiently until the flow stops, so that a drying method such as a silver halide photographic light-sensitive material can be employed. Drying in a drying zone is preferred.

The preferable drying conditions are as follows:
Alternatively, the drying conditions when forming the protective layer are not less than the minimum film forming temperature (MTF; usually 3 to 5 ° C. higher than the glass transition temperature Tg of the polymer) of the polymer latex using the liquid film surface temperature during constant rate drying. , Usually due to manufacturing equipment limitations
The temperature is often 5 ° C to 40 ° C. Further, the dry-bulb temperature during the rate-decreasing drying is preferably a temperature lower than the Tg of the support to be used (usually 80 ° C. or lower in the case of PET). The liquid film surface temperature in the present invention refers to the solvent liquid film surface temperature of the coating liquid film applied to the support, and the dry bulb temperature refers to the temperature of the drying air in the drying zone.

When drying is performed under the condition that the liquid film surface temperature during constant-rate drying is low, the drying tends to be insufficient. For this reason, particularly, the film forming property of the protective layer is significantly reduced, and cracks are easily generated on the film surface. In addition, the film strength is weakened, and serious problems such as susceptibility to damage during transport in an exposure machine or a heat developing machine are likely to occur. On the other hand, when dried under conditions that result in a high liquid film surface temperature, the protective layer mainly composed of polymer latex quickly forms a film, while the lower layer such as the image forming layer does not stop flowing, so that the surface is not stopped. Unevenness is likely to occur. Further, when an excessive heat higher than Tg is applied to the support (base), the dimensional stability of the photosensitive material,
The curl resistance tends to deteriorate.

The same applies to the sequential coating in which the lower layer is coated and dried and then the upper layer is coated. In particular, the coating for performing the simultaneous multi-layer coating in which the upper layer is coated before the lower layer is dried and both layers are dried simultaneously. As the liquid properties, the pH difference between the coating solution for the image forming layer and the coating solution for the protective layer is preferably 2.5 or less, and the smaller the difference in pH, the more preferable. When the pH difference of the coating liquid is large, micro-aggregation is likely to occur at the coating liquid interface, and a serious surface failure such as a coating streak tends to occur during continuous continuous coating.

The coating solution viscosity of the image forming layer is 15 to 25 ° C.
100 mPa · s is preferable, and 30 to 7 is more preferable.
It is 0 mPa · s. On the other hand, the coating liquid viscosity of the protective layer is 25 ° C.
Is preferably 5 to 75 mPa · s, more preferably 20 mPa · s.
５０50 mPa · s. These viscosities are measured by a B-type viscometer. Winding after drying is temperature 20 ~ 30 ℃,
It is preferable to carry out under the condition of 45 ± 20% relative humidity,
The winding shape may be such that the surface on the image forming layer side is outside or inside according to the subsequent processing form. Further, when the processing form is a roll product, it is also preferable to use a roll form wound on the side opposite to the winding form at the time of processing in order to remove the curl generated in the winding form. Preferably, the relative humidity of the envelope of the photosensitive material is controlled in the range of 20 to 55% (measured at 25 ° C.).

The photographic emulsion coating solution, which is a viscous solution containing silver halide and containing gelatin as a substrate, which has been conventionally used, usually dissolves and disappears in the solution simply by sending it under pressure, so that the coating solution is not coated. Even when returned to atmospheric pressure, bubbles hardly precipitate, but in the case of an image forming layer coating solution containing an organic silver salt dispersion and a polymer latex which are preferably used in the present invention, only pressure feeding is performed. Then, defoaming tends to be insufficient. Therefore, it is preferable to remove bubbles by applying ultrasonic vibration while feeding the liquid without causing a gas-liquid interface.

The defoaming of the coating solution is performed before the coating solution is applied.
Degas under reduced pressure and further 1.5kg / cm ^TwoIn the above pressurized state
Keeping the liquid flowing continuously without generating a gas-liquid interface
It is preferable to use a method in which ultrasonic vibration is applied while the ultrasonic vibration is applied. Specifically
Is described in JP-B-55-6405 (page 4, line 20 to page 7).
11) is preferred. like this
Japanese Patent Application No. Hei 10-290003 discloses a defoaming device.
The configuration shown in FIG.
Can be.

The pressure condition can be, for example, 1.5 kg / cm ² or more, preferably 1.8 kg / cm ² or more. There is no particular upper limit, but usually 5 kg / cm
^{About 2} . The sound pressure of the applied ultrasonic wave is 0.2 V or more, preferably 0.5 V to 3.0 V. Generally, it is preferable that the sound pressure is high. It becomes a state and causes fogging. The frequency is not particularly limited, but is usually 10 kHz or more, preferably 20 kHz to 200 kHz. In the decompression and deaeration, the inside of the tank (usually, a liquid adjusting tank or a storage tank) is hermetically sealed and decompressed to increase the diameter of bubbles in the coating solution, thereby increasing buoyancy to perform deaeration. The depressurizing condition at the time of degassing under reduced pressure may be a pressure condition of -200 mmHg or lower, preferably -250 mmHg or lower. The lowest pressure condition is not particularly limited, but is usually about -800 mmHg. is there. The decompression time is 30 minutes or more, preferably 45 minutes or more, and the upper limit is not particularly limited.

The image forming layer, the protective layer of the image forming layer, the undercoat layer, and the back layer are described in JP-A-11-84573, paragraphs 0204 to 0208, and Japanese Patent Application No. 11-106881.
As described in paragraphs 0240 to 0241 of the specification, a dye can be contained for the purpose of preventing halation and the like. Various dyes and pigments can be used in the image forming layer from the viewpoints of color tone improvement and irradiation prevention. The dye and pigment used in the image forming layer of the present invention may be any one, and for example, a compound described in paragraph No. 0297 of JP-A-11-119374 can be used. The method of adding these dyes is solution, emulsion,
Any method may be used, such as a solid fine particle dispersion, a state in which it is mordanted with a polymer mordant. The amount of these compounds to be used is determined depending on the desired absorption amount, but it is generally preferable to use them in the range of 1 × 10 ⁻⁶ g to 1 g per 1 m ² .

When an antihalation dye is used, the dye has a desired absorption in a desired range, has a sufficiently low absorption in the visible region after treatment, and has a desirable absorbance spectrum shape of the back layer. Any compound may be used as long as it is present. For example, the compound described in paragraph No. 0300 of JP-A-11-119374 can be used. Further, as described in Belgian Patent No. 733,706, a method in which the concentration by a dye is reduced by discoloration by heating, and the concentration is reduced by decolorization by light irradiation described in JP-A-54-17833. And the like.

When the image-recording material of the present invention is a heat-developable image-recording material and is used as a mask when preparing a printing plate by PS plate after heat-development, the heat-developable image-recording material after heat-development is The apparatus carries, as image information, information for setting exposure conditions for a PS plate and information for setting plate making conditions such as a condition for transporting a mask original and a PS plate. Therefore, the concentration (use amount) of the above-mentioned irradiation dye, halation dye and filter dye may be limited in order to read them. Since this information is read by LED or laser, D _min (minimum density) in the wavelength range of the sensor
Must be low, and the absorbance must be 0.3 or less. For example, a plate making machine S- manufactured by Fuji Photo Film Co., Ltd.
FNR III uses a light source with a wavelength of 670 nm as a detector and a bar code reader for detecting the registration marks. In addition, a 670 nm light source is used as a bar code reader of a plate making machine APML series manufactured by Shimizu Seisakusho. That is, when D _{mi n} (minimum density) is higher in the vicinity of 670nm is transportation failure can not accurately detect information on the film, working errors exposure failure such as plate making machines occurs. Therefore, in order to read information with a 670 nm light source, 670 nm
It is necessary that D _min around nm is low, and 660 after thermal development.
The absorbance at -680 nm needs to be 0.3 or less.
More preferably, it is 0.25 or less. The lower limit is not particularly limited, but is usually about 0.10.

The exposure apparatus used for the imagewise exposure may be any apparatus capable of performing exposure with an exposure time of less than 10 ^-7 seconds, but generally, Laser Diode (LD),
Light Emitting Diode (LED)
Is preferably used as the light source. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as it can generate light of an electromagnetic wave spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.

Exposure can be performed by overlapping light beams of a light source. The overlap means that the sub-scanning pitch width is smaller than the beam diameter. For example, the overlap is determined by changing the beam diameter to a half-width (FWH) of the beam intensity.
M), it can be quantitatively expressed by FWHM / sub-scanning pitch width (overlap coefficient). Preferably, the overlap coefficient is 0.2 or more. The scanning method of the light source of the exposure apparatus is not particularly limited, and a cylinder outer surface scanning method, a cylinder inner surface scanning method, a plane scanning method, or the like can be used. The channel of the light source may be a single channel or a multi-channel, but in the case of a cylindrical outer surface type, a multi-channel is preferably used.

When the image-recording material of the present invention is used as a heat-developable image-recording material, haze at the time of exposure is low, and interference fringes may easily occur. Techniques for preventing the occurrence of interference fringes include a technique disclosed in Japanese Patent Application Laid-Open No. Hei 5-113548 in which a laser beam is obliquely incident on a photosensitive material, and a technique disclosed in International Publication WO95 / 31754. There are known methods using a multimode laser, and it is preferable to use these techniques.

When the image-recording material of the present invention is used as a heat-developable image-recording material, the heat-development step of the image forming method may be any method. And developed. As a preferred embodiment of the heat developing machine to be used, a type in which the heat-developable image recording material is brought into contact with a heat source such as a heat roller or a heat drum is disclosed in Japanese Patent Publication No. 5-56499, Japanese Patent Application Laid-Open No. 9-292695, and Japanese Patent Application Laid-Open No. 297385
JP-A-7-13 as a non-contact type heat developing machine described in Japanese Patent Application Publication No.
294, International Publication WO 97/28489, 9
There are thermal developing machines described in JP-A-7 / 28488 and JP-A-97 / 28487. A particularly preferred embodiment is a non-contact type thermal developing machine. The preferred development temperature is 8
0 to 250 ° C, more preferably 100 to 140 ° C.
° C. The development time is preferably from 1 to 180 seconds,
10 to 90 seconds is more preferred.

As a method for preventing processing unevenness due to a dimensional change during thermal development, heating is performed at a temperature of 80 ° C. or more and less than 115 ° C. for 5 seconds or more so that an image is not formed, and then 110 ° C. to 1 ° C.
A method of forming an image by thermal development at 40 ° C. (a so-called multi-stage heating method) is effective. When the image recording material of the present invention is used as a heat-developable image-recording material, it is exposed to a high temperature of 110 ° C. or more in the heat-development process. Some evaporate. These volatile components may cause uneven development, corrode the components of the heat developing machine,
It is known that there are various adverse effects such as deposition at a low temperature place, causing deformation of a screen as a foreign substance, and adhering to the screen to become dirty. In order to eliminate these effects, it is known to install a filter in the heat developing machine and to optimally adjust the flow of air in the heat developing machine. These can be effectively used in combination.

International Publication Nos. WO 95/30933, WO 97/21150, and JP-T-Hei 10-500496 disclose first and second openings for binding and absorbing particles and introducing volatile components. International Publication WO96 / 12213 discloses that a filter cartridge having an opening of
Japanese Patent Publication No. Hei 10-507403 describes the use of a filter in which a heat-conductive condensation collector and a gas-absorbing particulate filter are combined. In the present invention, these can be preferably used. U.S. Pat. No. 4,518,845 and Japanese Patent Publication No. 3-54331 disclose a device for removing vapor from a film, a pressurizing device for pressing the film against a heat transfer member, and heating of the heat transfer member. And a device having an apparatus for performing the operation described in
Japanese Patent Application Laid-Open No. 8/27458 describes that a component that increases fog volatilized from a film is removed from the film surface. These can also be preferably used in the present invention.

FIG. 1 shows an example of the configuration of a heat developing machine used for the heat development of a heat-developable image recording material. FIG. 1 is a side view of the heat developing machine. The heat developing machine of FIG. 1 carries in a pair of carry-in rollers 11 for carrying the heat-developable image recording material 10 into a heating section while correcting and preheating the heat-developable image recording material 10 (the upper roller is a silicon rubber roller and the lower roller is an aluminum heat roller). And a carry-out roller pair 12 for carrying out the heat-developed image recording material 10 after the heat development and carrying it out of the heating unit while correcting the heat-developed image recording material 10 into a planar shape. Thermally developed image recording material 10
Is developed while being transported from the carry-in roller pair 11 to the carry-out roller pair 12. In the conveying means for conveying the heat-developable image recording material 10 during the heat development, a plurality of rollers 13 are provided on the side in contact with the surface having the image forming layer, and the non-woven fabric ( For example, a smooth surface 14 to which an aromatic polyamide or Teflon) is attached is provided. The back surface of the heat-developable image recording material 10 is conveyed by driving a plurality of rollers 13 which come into contact with the surface having the image forming layer, on the smooth surface 14. As the heating means, a heater 15 is provided at an upper portion of the roller 13 and a lower portion of the smooth surface 14 so as to be heated from both sides of the heat-developable image recording material 10. As a heating means in this case, a plate heater or the like can be used. Although the clearance between the roller 13 and the smooth surface 14 varies depending on the member of the smooth surface, the clearance is appropriately adjusted to allow the heat-developable image recording material 10 to be transported. Preferably it is 0 to 1 mm.

The material of the surface of the roller 13 and the smooth surface 14
Is a high-temperature durable, heat-developable image recording material 10
Any material may be used as long as it does not hinder the conveyance of the roller. However, the material of the roller surface is preferably silicon rubber, and the member having a smooth surface is preferably a nonwoven fabric made of aromatic polyamide or Teflon (PTFE). It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section is composed of a preheating section A having a carry-in roller pair 11 and a heat development heating section B having a heating heater 15, but a preheating section upstream of the heat development processing section B. A is lower than the heat development temperature (for example, 10 to 3).
It is desirable to set the temperature and time to be sufficient to evaporate the amount of water in the heat-developable image recording material 10, which is lower than the glass transition temperature (Tg) of the support of the heat-developable image recording material 10. It is preferable that the temperature is set so as not to cause uneven development at a high temperature. The temperature distribution between the preheating section and the heat development section is preferably ± 1 ° C. or less, more preferably ± 0.5 ° C. or less.

Further, a guide plate 16 is provided downstream of the thermal development processing section B, and a slow cooling section C having a carry-out roller pair 12 and a guide plate 16 is provided. The guide plate 16 is preferably made of a material having a low thermal conductivity, and is preferably cooled gradually so that the heat-developable image recording material 10 is not deformed. Seconds are preferred. Although the above has been described with reference to the illustrated example, the invention is not limited to this example. For example, the thermal developing machine may have various configurations such as that described in Japanese Patent Application Laid-Open No. Hei 7-13294. Further, in the case of a preferably used multi-stage heating method, in the above-described apparatus, two or more heat sources having different heating temperatures may be provided, and heating may be performed continuously at different temperatures.

[0147]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. The compound numbers correspond to those exemplified above. <Synthesis Example 1: Synthesis of Exemplified Compound P-1> (1) Synthesis of Intermediate B 35 g of Intermediate A synthesized by the method described in Helv. Chim. Acta., 56, 2460 (1973), 40 ml of benzene, Concentrated sulfuric acid 5
The mixture was stirred at 40 ° C. for 5 hours while bubbling isobutylene gas into the mixed solution of ml. Add the reaction solution to ice water,
After extraction with ethyl acetate, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (hexane / ethyl acetate = 10).
As a result of purification by (1/1), 34 g of intermediate B was obtained. (White crystals, yield 62%)

(2) Synthesis of Exemplified Compound P-1 10 g of Intermediate B, 6.3 g of commercially available 1-phenyl-1H-tetrazole-5-thiol, and acetonitrile 100
A mixed solution of 5.2 ml of pyridine and 5.2 ml of pyridine was heated under reflux for 3 hours, and added to 400 ml of ice water. The precipitated crystals were filtered and recrystallized with 120 ml of methanol to obtain 9 g of Exemplified Compound P-1. (White crystals, yield 69%, melting point 132 ° C)

<Synthesis Example 2: Synthesis of Exemplified Compound P-2> (1) Synthesis of Intermediate C 83.6 g of 4-phenyl-3-thiosemicarbazide was added to T
Suspend in 800 ml of HF and add triethylamine 7
After adding 6.7 ml, the mixture was cooled on ice and kept at 10 ° C. or lower. To the mixture under ice-cooling, 39 ml of acetyl chloride was added dropwise, and after stirring for 3 hours, 2.5 l of water was added and the precipitate was filtered. Next, 51.6 g of sodium hydroxide was added to 450 ml of water.
The precipitate obtained above was added to the solution dissolved in
After reacting at 1 ° C. for 1 hour, the mixture was cooled with ice water, concentrated hydrochloric acid (103 ml) was added, and the precipitate was filtered. Recrystallization from 600 ml of ethanol gave 47 g of the desired intermediate C. (White crystals, 50% yield)

(2) Synthesis of Exemplified Compound P-2 A mixed solution of 9.4 g of Intermediate B, 6.3 g of Intermediate C, 4.9 ml of pyridine and 30 ml of DMF was added at 100 ° C. for 5 minutes.
Allowed to react for hours. After returning to room temperature, extraction was performed by adding ethyl acetate and water, and the organic layer was washed with 1M hydrochloric acid, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result of recrystallization with 30 ml of acetonitrile, 9.8 g of Exemplified Compound P-2 was obtained. (White crystals, yield 77%, melting point 162)
℃)

<Synthesis Example 3: Synthesis of Exemplified Compound P-3> (1) Synthesis of Intermediate E Intermediate D synthesized by the method described in J. Chem. Soc. Perkin Trans 1., 1515 (1986) 50 g, benzene 50 ml,
The mixture was stirred at room temperature for 3 hours while bubbling isobutylene gas into a mixed solution of 5 ml of concentrated sulfuric acid. Hexane and water were added to the reaction solution, and after liquid separation, the organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure. Acetone 70 is added to the obtained residue.
0 ml and 62 g of sodium iodide were added, and the mixture was stirred at room temperature for 3 hours. The precipitated salt was filtered, and the filtrate was concentrated under reduced pressure.
The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1),
61 g of intermediate E were obtained. (Oil compound, yield 71
%)

(2) Synthesis of Exemplified Compound P-3 2 g of Intermediate E and 1-phenyl-1H-tetrazole-
0.9 g of 5-thiol, 20 ml of methanol and 2 ml of a 28% methanol solution of sodium methoxide were mixed,
The mixture was heated under reflux for 2 hours. Ethyl acetate, hexane,
Water was added, and after liquid separation, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 1/1) to give 1.4 g of the exemplified compound. (White crystals, yield 62%, melting point 50 ° C)

<Synthesis Example 4: Synthesis of Exemplified Compound P-4> (1) Synthesis of Exemplified Compound P-4 1.1 g of Intermediate E, 0.5 g of Intermediate C, and 1 part of methanol
0 ml and 1.1 ml of a 28% methanol solution of sodium methoxide were mixed, and the mixture was refluxed for 1.5 hours. Water was added to the reaction solution, and the precipitated crystals were filtered. As a result of recrystallizing the obtained crude crystal with acetonitrile, 1.4 g of an exemplary compound was obtained. (White crystals, yield 62%, melting point 13)
5 ℃)

<Synthesis Example 5: Synthesis of Exemplified Compound P-5> (1) Synthesis of Exemplified Compound P-5 A mixed solution of 10 g of Intermediate B, 9.4 g of sodium benzenethiosulfonate and 60 ml of DMF was added at 50 ° C. Stirred for hours. 200 ml of water was added and the precipitate was filtered. As a result of recrystallizing the obtained crude crystals from 30 ml of methanol, 6 g of Exemplified Compound P-5 was obtained. (White crystals, yield 4
6%, melting point 100 ° C)

<Synthesis Example 6: Synthesis of Exemplified Compound P-6> (1) Synthesis of Intermediate G Intermediate F was synthesized by the method described in Tetrahedron., 29, 1931 (1973). A mixture of 5.5 g of Intermediate F, 3.6 g of potassium carbonate, 3.3 ml of methyl iodide and 40 ml of DMAc was stirred at 50 ° C. for 3 hours, and ethyl acetate and water were added thereto for extraction, and the organic layer was extracted with magnesium sulfate. After drying, the solvent was distilled off under reduced pressure. 80 ml of THF was added to the obtained residue,
After cooling to 0 ° C., 0.75 g of LiAlH ₄ was added. After stirring for 2 hours, ethyl acetate and water were added to the reaction solution, followed by extraction. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 1/1) to obtain 1.5 g of an intermediate G. (Oil compound, yield 2
9%)

(Synthesis of Intermediate H) PBr ₃ was added at room temperature to a solution of 1.5 g of Intermediate G and 15 ml of dichloromethane at room temperature.
9 ml was added dropwise. After stirring at room temperature for 1 hour, 30 ml of dichloromethane and 50 ml of water were added and extracted, and the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 1/1), and as a result, 0.44 g of Intermediate H was obtained. (Oil compound, yield 22%)

(Synthesis of Exemplified Compound P-6) 0.44 g of Intermediate H, 1-phenyl-1H-tetrazole-5-
0.36 g of thiol, 0.2 ml of pyridine, DMAc
4 ml of the mixed solution was heated and stirred at 100 ° C. for 30 minutes, ethyl acetate and water were added and extracted. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the selected residue was subjected to silica gel column chromatography. (Hexane / ethyl acetate = 1/1) showed that Exemplified Compound P-6 was 0.3%.
5 g were obtained. (Oil compound, 58% yield)

¹ H—N of the compounds synthesized in Synthesis Examples 1 to 6
The MR data (300 MHz, CDCl ₃ ) is shown below. (P-1) 7.5-7.6 (m, 5H), 7.0 (s, 2H), 5.1 (s, 1H), 3.6 (t,
2H), 3.1 (t, 2H), 1.4 (s, 18H) (P-2) 7.5-7.6 (m, 3H), 7.2-7.3 (m, 2H), 7.0 (s, 2H), 5.
1 (s, 1H), 3.3 (dd, 2H), 2.9 (dd, 2H), 2.3 (s, 3H), 1.4 (s, 18H) (P-3) 7.5-7.6 (m, 5H), 7.0 ( s, 2H), 5.1 (s, 1H), 3.4 (t,
2H), 2.7 (t, 2H), 2.1-2.2 (m, 2H), 1.4 (s, 18H) (P-4) 7.5-7.6 (m, 3H), 7.2-7.3 (m, 2H), 6.9 ( s, 2H), 5.
0 (s, 1H), 3.1-3.2 (t, 2H), 2.6-2.7 (t, 2H), 1.9-2.1 (m, 2H),
1.4 (s, 18H) (P-5) 7.9 (d, 2H), 7.5-7.7 (m, 3H), 6.9 (s, 2H), 5.1 (s,
1H), 3.2 (t, 2H), 2.8 (t, 2H), 1.4 (s, 18H) (P-6) 7.5-7.6 (m, 5H), 6.4 (s, 2H), 5.5 (s, 1H) , 3.9 (s,
6H), 3.6 (t, 2H), 3.1 (t, 2H)

The structures of the intermediate compounds synthesized in Synthesis Examples 1 to 6 are shown below.

[0160]

Embedded image

Example 2 The structure of the compound used in Example 2 is shown below.

[0162]

Embedded image

[0163]

Embedded image

[0164]

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[0165]

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1. Preparation of PET support Using terephthalic acid and ethylene glycol, the intrinsic viscosity IV = 0.66 (phenol / tetrachloroethane = 6/4)
(Measured at 25 ° C. in the weight ratio). This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled to prepare an unstretched film having a thickness of 175 μm after heat fixing. This is longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then a tenter
The film was stretched by a factor of 4.5. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

2. Surface Corona Treatment Both surfaces of the support were treated at room temperature at 20 m / min using a solid state corona treatment machine 6KVA model manufactured by Pillar. From the current and voltage readings at this time, the support
It was found that the treatment was performed at 0.375 kV · A · min / m ² . At this time, the processing frequency was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

[0168] 3. Preparation of Undercoat Support (1) Preparation of Undercoat Layer Coating Solution Coating solutions of the following formulas (1) to (3) were prepared. Formulation (1) (for undercoating layer on the photosensitive layer side) Pesresin A-515GB manufactured by Takamatsu Yushi Co., Ltd. (30% by weight solution) 234 g Polyethylene glycol monononyl phenyl ether (average ethylene oxide number = 8.5) 10% by weight solution 21.5 g Soken Chemical Co., Ltd.MP-1000 (polymer fine particles, average particle size 0.4 μm) 0.91 g distilled water 744 ml

Formulation (2) (for the first layer on the back surface) Butadiene-styrene copolymer latex 158 g (solid content 40% by weight, butadiene / styrene weight ratio = 32/68) 2,4-dichloro-6-hydroxy -S-triazine sodium salt 8% by weight aqueous solution 20 g 1% by weight aqueous solution of sodium laurylbenzenesulfonate 10 ml Distilled water 854 ml

Formulation (3) (for the second layer on the back surface side) SnO ₂ / SbO (9/1 weight ratio, average particle size 0.038 μm, 17% by weight dispersion) 84 g Gelatin (10% aqueous solution) 89 g Shinetsu Chemicals Co., Ltd. Metroose TC-5 (2% aqueous solution) 8.6 g Soken Chemical Co., Ltd. MP-1000 (polymer fine particles) 0.01 g 1% by weight aqueous solution of sodium dodecylbenzenesulfonate 10 ml NaOH (1%) 6 ml Proxel (ICI) 1ml distilled water 805ml

(2) Preparation of Undercoating Support The above-mentioned corona discharge treatment was applied to both surfaces of the biaxially stretched polyethylene terephthalate support having a thickness of 175 μm, and then an undercoating coating solution formulation (1) was formed on one surface (photosensitive layer surface). )
Is applied with a wire bar so that the wet application amount is 6.6 ml / m ² (per side), dried at 180 ° C. for 5 minutes, and then the undercoat coating solution formulation (2) is applied to the back surface (back surface) of the wire bar. in a wet coating amount undercoating liquid prescribe (3) with a wire bar to be applied as a wet coating amount of the 5.7 ml / m ² and dried 5 minutes at 180 ° C., further back surface (back surface) 7.7 ml / m ² and dried at 180 ° C. for 6 minutes to form an undercoat support.

[0172] 4. Preparation of Coating Solution for Back Surface (1) Preparation of Solid Precursor Dispersion (a) of Base Precursor Mix 64 g of base precursor compound 11, 28 g of diphenylsulfone, and 10 g of Kao Corporation surfactant Demol N with 220 ml of distilled water. And mix the mixture with a sand mill (1/4 Gallo
The beads were dispersed using an n-sand grinder mill (manufactured by Imex Co., Ltd.) to obtain a solid precursor dispersion (a) of a base precursor compound having an average particle diameter of 0.2 μm.

(2) Preparation of Dye Solid Fine Particle Dispersion A mixture of 9.6 g of cyanine dye compound 13 and 5.8 g of sodium P-dodecylbenzenesulfonate with 305 ml of distilled water was prepared.
The mixed solution was dispersed in beads using a sand mill (1/4 Gallon sand grinder mill, manufactured by IMEX Co., Ltd.) to obtain a dispersion of solid dye fine particles having an average particle size of 0.2 μm.

(3) Preparation of antihalation layer coating solution 17 g of gelatin, 9.6 g of polyacrylamide, 70 g of solid fine particle dispersion (a) of the above base precursor, 56 g of the above solid fine particle dispersion of dye, and polymethyl methacrylate fine particles (average particle size) (6.5 μm) 1.5 g, Benzoisothiazolinone 0.03
g, sodium polyethylene sulfonate 2.2 g, blue dye compound 14 0.2 g, and water 844 ml were mixed to prepare an antihalation layer coating solution.

[0175] 5. Preparation of Coating Solution for Back Surface Protective Layer Keep the container warm at 40 ° C., gelatin 50 g, polystyrene sodium sulfonate 0.2 g, N, N-ethylenebis (vinylsulfone acetamide) 2.4 g, sodium t-octylphenoxyethoxyethanesulfonate 1 g , Benzoisothiazolinone 30 mg, N-perfluorooctylsulfonyl
-N-propylalanine potassium salt 37mg, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-
Propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide 15] 0.15 g, C ₈ F ₁₇ SO ₃ K 32 mg, C ₈ F ₁₇ SO ₂ N (C ₃ H
₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na 64 mg, acrylic acid / ethyl acrylate copolymer (copolymer weight ratio 5/95) 8.8 g, Aerosol OT (American Cyanamid Co., Ltd.) 0.6g, liquid paraffin emulsion 1.8g as liquid paraffin, water
950 ml was mixed to give a back surface protective layer coating solution.

6. Preparation of silver halide emulsion 1 8.0 ml of a 1% by weight potassium bromide solution was added to 1421 ml of distilled water,
Further, while stirring a liquid containing 8.2 ml of 1N nitric acid and 20 g of phthalated gelatin in a titanium-coated stainless steel reaction bottle, the liquid temperature was maintained at 37 ° C., and distilled water was added to 37.04 g of silver nitrate.
Prepare a solution A diluted to 159 ml and a solution B prepared by diluting potassium bromide 32.6 g to a volume of 200 ml with distilled water, and maintain the pAg at 8.1 by a control double jet method, and adjust the total amount of the solution A to 1 at a constant flow rate. It was added over a minute. Solution B was added by a controlled double jet method. Then 3.5
A 30% by weight aqueous solution of hydrogen peroxide was added, followed by 36 ml of a 3% by weight aqueous solution of benzimidazole. afterwards,
Solution A2 which was again diluted with distilled water to 317.5 ml,
Solution B2 was prepared by dissolving tripotassium hexachloride iridate in a final amount of 1 × 10 ^-4 mol per mol of silver in solution B, and diluting the solution with distilled water to 400 ml twice that of solution B. Using the controlled double jet method, pA
The solution A2 was added at a constant flow rate over 10 minutes while maintaining g at 8.1. Solution B2 was added by a controlled double jet method. Thereafter, 50 ml of a 0.5% by weight methanol solution of 5-methyl-2-mercaptobenzimidazole was added, the pAg was further raised to 7.5 with silver nitrate, the pH was adjusted to 3.8 with 1N sulfuric acid, stirring was stopped, and sedimentation was stopped. A desalting / washing step was performed, 3.5 g of deionized gelatin was added, and 1N sodium hydroxide was added to adjust the pH to 6.0 and a pAg of 8.2 to prepare a silver halide dispersion.

The grains in the completed silver halide emulsion were pure silver bromide grains having an average sphere equivalent diameter of 0.053 μm and a variation coefficient of the sphere equivalent diameter of 18%. The particle size and the like were determined from the average of 1000 particles using an electron microscope. [100] of this particle
The area ratio was determined to be 85% using the Kubelka-Munk method. The emulsion was maintained at 38 ° C. with stirring, and 0.035 g of benzoisothiazolinone (added with a 3.5% by weight methanol solution) was added. After 40 minutes, a solid dispersion of the spectral sensitizing dye A (aqueous gelatin solution) was added to silver 1 5 × 10 ^-3 mol per mol was added and 1 minute later 4
The temperature was raised to 7 ° C., 20 minutes later, 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate was added to 1 mol of silver, and 2 minutes later, tellurium sensitizer B was added at 5 × 10 ⁻⁵ mol per mol of silver. Plus 9
Aged for 0 minutes. Immediately before aging, N, N'-dihydroxy-
5 ml of a 0.5% by weight methanol solution of N "-diethylmelamine
And lower the temperature to 31 ° C.
5 ml of a 5% by weight methanol solution, 5-methyl-2-mercaptobenzimidazole was converted to silver (7 × 10 ^-3 mol per mol of silver) and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole was converted to silver. 6.4 × 10 ^-3 mol was added per 1 mol to prepare a silver halide emulsion 1.

[0178] 7. Preparation of silver halide emulsion 2 In preparing silver halide emulsion 1, the liquid temperature during grain formation was
Except that 37 ° C is changed to 50 ° C, the average equivalent spherical diameter is 0.
A pure silver bromide cubic grain emulsion having a dispersion coefficient of 08 μm and a sphere equivalent diameter of 15% was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1. Further, a spectral sensitizer, a chemical sensitizer and 5-methyl-2-mercaptobenzene were prepared in the same manner as in Emulsion 1, except that the amount of the spectral sensitizing dye A was changed to 4.5 × 10 ^-3 mol per mol of silver. Imidazole, 1-phenyl-2-heptyl-5-
Mercapto-1,3,4-triazole was added to obtain a silver halide emulsion 2.

8. Preparation of silver halide emulsion 3 In preparation of silver halide emulsion 1, the liquid temperature during grain formation was
Except that 37 ° C is changed to 27 ° C, the average equivalent spherical diameter is 0.
A pure silver bromide cubic grain emulsion having a dispersion coefficient of 038 μm and an equivalent sphere diameter of 20% was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1. Further, a spectral sensitizer, a chemical sensitizer, and 5-methyl-2-mercaptobenzene were prepared in the same manner as in Emulsion 1, except that the amount of the spectral sensitizing dye A was changed to 6 × 10 ^-3 mol per mol of silver. Imidazole, 1-phenyl-2-heptyl-5-
Mercapto-1,3,4-triazole was added to obtain a silver halide emulsion 3.

9. Preparation of Mixed Emulsion A for Coating Solution 70% by weight of silver halide emulsion 1 and 1% of silver halide emulsion 2
5% by weight and 15% by weight of silver halide emulsion 3 were dissolved, and benzothiazolium iodide was added as a 1% by weight aqueous solution at 7 × 10 ⁻³ mol per mol of silver.

10. Preparation of scaly fatty acid silver salt Behenic acid (product name Edenor C22-85R) manufactured by Henkel 87.6
g, 423 ml of distilled water, 49.2 ml of 5N-NaOH aqueous solution, and 120 ml of tert-butanol were mixed and reacted at 75 ° C. for 1 hour with stirring to obtain a sodium behenate solution. Separately, 206.2 ml (pH 4.0) of an aqueous solution of 40.4 g of silver nitrate was prepared and kept at 10 ° C. 635m
l of distilled water and 30 ml of tert-butanol were kept at 30 ° C., and while stirring, the total amount of the sodium behenate solution and the total amount of the silver nitrate aqueous solution were each kept at a constant flow rate.
It was added over 62 minutes, 10 seconds and 60 minutes. At this time, only the aqueous silver nitrate solution was added for 7 minutes and 20 seconds after the start of the aqueous silver nitrate solution addition, and then the addition of the sodium behenate solution was started. After the addition of the aqueous silver nitrate solution was completed, only the sodium behenate solution was added for 9 minutes and 30 seconds. Was added. At this time, the temperature in the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. Further, the piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the steam opening was adjusted so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution.

After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water became 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying. When the morphology of the obtained silver behenate particles was evaluated by electron micrographing, a = 0.
14 μm, b = 0.4 μm, c = 0.6 μm, average aspect ratio 5.2, average sphere equivalent diameter 0.52 μm, flake-like crystal with a sphere equivalent diameter variation coefficient of 15% (the shape of silver behenate particles was , And the sides of the rectangular parallelepiped were designated as a, b and c from the shortest one). To a wet cake having a dry solid content of 100 g, 7.4 g of polyvinyl alcohol (trade name: PVA-217) and water were added to adjust the total amount to 385 g, and the mixture was preliminarily dispersed with a homomixer. Next, the pre-dispersed stock solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110SE-E).
H, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber) at a pressure of 1750 kg / cm ^2, and processed three times to obtain a silver behenate dispersion. For cooling operation, install a coiled heat exchanger before and after the interaction chamber, respectively.
The dispersion temperature was set at 18 ° C. by adjusting the temperature of the refrigerant.

11. Preparation of 25% by weight dispersion of reducing agent 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-
10 kg of a 20% by weight aqueous solution of 10 kg of trimethylhexane and a modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval MP203)
Then, 16 kg of water was added thereto and mixed well to form a slurry.
This slurry is fed by a diaphragm pump and the average diameter
Horizontal sand mill filled with 0.5 mm zirconia beads (UV
M-2: manufactured by IMEX Co., Ltd.) for 3 hours and 30 minutes, and then 0.2 g of benzoisothiazolinone sodium salt and water were added to adjust the concentration of the reducing agent to 25% by weight. A dispersion was obtained. The reducing agent particles contained in the reducing agent dispersion thus obtained have a median diameter of 0.42 μm and a maximum particle size of 2.0 μm
It was below. The resulting reducing agent dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored.

12. Preparation of a 10% by weight dispersion of a mercapto compound 5 kg of 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole and 5 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.) Then, 8.3 kg of water was added thereto and mixed well to form a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 6 hours, and then water was added to reduce the concentration of the mercapto compound. Prepared to be 10% by weight,
A mercapto dispersion was obtained. The mercapto compound particles contained in the mercapto compound dispersion thus obtained have a median diameter.
It was 0.40 μm and the maximum particle size was 2.0 μm or less. The obtained mercapto compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored. Immediately before use, the mixture was again filtered through a polypropylene filter having a pore size of 10 μm.

13. Compound of formula (I) of the present invention (solid)
Preparation of solid fine particle dispersion of 4 g of MP-203, an MP polymer manufactured by Kuraray Co., Ltd., per 30 g of the compound of the formula (I) shown in Table 1,
0.25 g and 66 g of water were added and stirred well, and then 200 g of 0.5 mm zirconia silicate beads were prepared and put together with the slurry in a vessel, and the dispersion machine (1/1) was used.
16G sand grinder mill: IMEX Co., Ltd.
For 5 hours to prepare a solid fine particle dispersion.
The particle size is 80% by weight of the particles is 0.3 μm to 1.0 μm
Met. Comparative compounds R-1 to R-3 were similarly dispersed.

14. Preparation of 10% by weight methanol solution of phthalazine compound 10 g of 6-isopropylphthalazine was dissolved in 90 g of methanol and used.

15. Preparation of 20% by weight dispersion of pigment 64 g of CI Pigment Blue 60 and 6.4 mol of Demol N manufactured by Kao Corporation
To 250 g of water, 250 g of water was added and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm were prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours to obtain a pigment dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

16. Preparation of SBR latex 40% by weight Ultrafiltration (UF) purified SBR latex was obtained as follows. The following SBR latex diluted 10 times with distilled water is used for UF-purification module FS03-FC-FUY03A1 (Daisen
Ion conductivity of 1.5 using Membrane System Co., Ltd.
After diluting and purifying to mS / cm, Sandet-BL manufactured by Sanyo Chemical Co., Ltd. was added to a concentration of 0.22% by weight. NaOH and NH
Na ⁺ ion: NH ₄ ⁺ ion = 1: 2.3 (molar ratio) using ₄ OH
And adjusted to pH 8.4. The latex concentration at this time was 40% by weight. (SBR latex: -St (68) -Bu (29) -AA (3)-latex)
Numerical values in parentheses are% by weight. St indicates styrene, Bu indicates butadiene, and AA indicates acrylic acid. Average particle size 0.1μ
m, concentration 45%, equilibrium water content at 25 ° C and relative humidity 60% 0.6% by weight, ionic conductivity 4.2mS / cm (Ion conductivity is measured using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd. Stock solution (4
0%) at 25 ° C), pH 8.2

17. Preparation of Emulsion Layer (Photosensitive Layer) Coating Solution 1.1 g of a 20% by weight aqueous dispersion of the pigment obtained above, 103 g of an organic acid silver dispersion, polyvinyl alcohol PVA-205 (Kuraray Co., Ltd.)
2 g of a 20% by weight aqueous solution, 25 g of the above 25% by weight reducing agent dispersion,
The compound of the formula (I) (type and amount are described in Table 1), 6.2 g of a 10% dispersion of a mercapto compound, 130 g of 40% by weight of SBR latex purified and pH-adjusted by ultrafiltration (UF), and 10% by weight of a phthalazine compound 16 ml of a methanol solution was added thereto, and 10 g of the silver halide mixed emulsion A was mixed well to prepare an emulsion layer coating solution, which was directly fed to a coating die at 70 ml / m ² and coated. The viscosity of the above emulsion layer coating solution was measured with a B-type viscometer of Tokyo Keiki, and was 40 ° C (No. 1 rotor, 60 rpm).
Was 85 [mPa · s]. The viscosity of the coating solution at 25 ° C. using an RFS Fluid Spectrometer manufactured by Rheometrics Far East Co., Ltd. was determined at a shear rate of 0.1, 1, 10, 10
1500, 220, 70, 40, 20 at 0, 1000 [1 / sec]
[mPa · s].

18. Preparation of emulsion surface intermediate layer coating solution 10% by weight of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.)
Aqueous solution 772 g, pigment 20 wt% dispersion 5.3 g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio)
64/9/20/5/2) 2 m of a 5 wt% aqueous solution of aerosol OT (manufactured by American Cyanamid Co.) in 226 g of a latex 27.5 wt% liquid
l, 10.5m of a 20% by weight aqueous solution of diammonium phthalate
l, Water was added to make the total amount 880 g, and the solution was applied to the intermediate layer. The solution was sent to the coating die so as to be 10 ml / m ² . The viscosity of the coating solution is B type viscometer 40 ° C (No.1 rotor, 60r
pm) was 21 [mPa · s].

19. Preparation of Coating Solution for Emulsion Surface Protective Layer First Layer 64 g of inert gelatin was dissolved in water, and a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio 64 /
9/20/5/2) 80 g of latex 27.5 wt% liquid, 64 ml of 10 wt% methanol solution of phthalic acid, 10 wt% of 4-methylphthalic acid
74 ml of aqueous solution, 28 ml of 1N sulfuric acid, 5 ml of 5% by weight aqueous solution of aerosol OT (manufactured by American Cyanamid), 0.5 g of phenoxyethanol, 0.1 g of benzoisothiazolinone, and water to a total amount of 750 g Immediately before coating, 26 ml of 4% by weight chromium alum was mixed with a static mixer and fed to a coating die at 18.6 ml / m ² . The viscosity of the coating liquid is 40 ° C with a B-type viscometer
(No. 1 rotor, 60 rpm) and 17 [mPa · s].

20. Preparation of Coating Solution for Emulsion Surface Protective Layer Second Layer 80 g of inert gelatin was dissolved in water, and methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio 64 /
9/20/5/2) 102 g of latex 27.5% by weight liquid, 3.2 ml of 5% by weight solution of potassium salt of N-perfluorooctylsulfonyl-N-propylalanine, polyethylene glycol mono
(N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide = 15]
32 ml of a 2% by weight aqueous solution of aerosol OT (American
23 ml of a 5% by weight solution of Ianamid Co., Ltd., 4 g of polymethyl methacrylate fine particles (average particle size 0.7 μm), 21 g of polymethyl methacrylate fine particles (average particle size 6.4 μm), 1.6 g of 4-methylphthalic acid, 8.1 g of phthalic acid, 44 ml of 1N sulfuric acid and 10 mg of benzoisothiazolinone were added with water to a total amount of 650 g, and 445 ml of an aqueous solution containing 4% by weight of chrome alum and 0.67% by weight of phthalic acid were mixed with a static mixer immediately before application. The resulting solution was used as a coating solution for the surface protective layer, and sent to a coating die at 8.3 ml / m ² . The viscosity of the coating solution was 9 mPa · s using a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).

21. On the back surface side of the Create the undercoated support of the heat developable image recording material, an antihalation layer coating solution so that the solid content coating amount of the solid particulate dye is 0.04 g / m ^2, also the back surface protective layer coating solution Coating was performed simultaneously so that the amount of gelatin applied was 1.7 g / m ² , followed by drying to form an antihalation back layer. From the undercoating side to the emulsion side on the side opposite to the back side (silver halide coated silver amount 0.14 g / m
² ), an intermediate layer, a protective layer first layer, and a protective layer second layer were simultaneously coated in order by a slide bead coating method to prepare a sample of a heat-developable image recording material. The coating is performed at a speed of 160 m / min, and the distance between the tip of the coating die and the support is 0.14 to 0.
The width of the coating was adjusted to be 28 mm, and the width of the coating was spread by 0.5 mm on both the left and right sides with respect to the width of the slit for discharging the coating solution. The pressure in the decompression chamber was set 392 Pa lower than the atmospheric pressure. At that time, the handling and the temperature and humidity were controlled so that the support was not charged, and the charge was removed by ion wind immediately before coating. In the subsequent chilling zone, air with a dry-bulb temperature of 18 ° C and a wet-bulb temperature of 12 ° C was blown for 30 seconds to cool the coating liquid, and then the dry-bulb temperature was raised in the hovering-type floating type drying zone. After spraying dry air at 30 ° C and wet bulb temperature of 18 ° C for 200 seconds, pass through the 70 ° C dry zone for 20 seconds, then pass through the 90 ° C dry zone for 10 seconds, then cool to 25 ° C and apply. The solvent in the liquid was volatilized. The average wind speed of the wind blowing on the coating liquid film surface in the chilling zone and the drying zone was 7 m / sec.

22. Evaluation of photographic performance After exposing the heat-developable image recording material with a laser sensitometer (details below), the heat-developable image recording material was exposed at 118 ° C for 5 seconds, and then
Processing (thermal development) was performed at 122 ° C. for 16 seconds. Laser sensitometer: 35 mW output two 660nm diode laser combined single mode Gaussian beam spot 1 / e ² feed in the sub-scanning direction by 100 [mu] m 25 [mu] m pitch, writing 4 times one pixel

Evaluation of the obtained image was performed using Macbeth TD904.
The measurement was performed using a densitometer (visible density). The result of the measurement is D
_min , sensitivity (evaluated by the relative value of the reciprocal of the ratio of the exposure amount giving a density higher than D _min by 1.0, and the heat-developable image recording material of Experiment No. 1 shown in Table 1 was set to 100), D _max , It was evaluated by gradation (contrast) (fresh photographic properties). The gradation was represented by the slope of a straight line connecting points of density 0.5 and 1.5, from which the _Dmin part was subtracted, with the logarithm of the exposure amount as the horizontal axis.
The evaluation of the image storability shows that the heat-developable image recording material after the heat development was subjected to image storability-1 at 60 ° C. and a relative humidity of 50% under a humidity control of 24 hours. In the storage stability-2, 1000% under the condition of 40 ° C. and 50% relative humidity.
The change in photographic properties after storage for 24 hours under irradiation of 1 lux light was shown.

[0196]

[Table 1]

As can be seen from Table 1, when the compound of the present invention was used in a heat-developable image recording material, good photographic performance and good image storability could be obtained.

Example 3 The structure of the compound used in Example 3 is shown below.

[0199]

Embedded image

[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

1. Preparation of silver halide emulsion (emulsion A) In 700 ml of water, 11 g of alkali-treated gelatin (2700 ppm or less as calcium content), 30 mg of potassium bromide, 10 m of sodium benzenethiosulfonate
g, and adjusted to pH 5.0 at a temperature of 40 ° C., 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 mol / l of potassium bromide, and (NH ₄ ) ₂ RhCl
₅ (H ₂ O) at 5 × 10 ^-6 mol / l and K ₃ I
An aqueous solution containing 2 × 10 ⁻⁵ mol / l of rCl ₆ was added to p
While maintaining Ag 7.7, it was added over 6 minutes and 30 seconds by the control double jet method. Then, silver nitrate 55.
476 ml of an aqueous solution containing 5 g and 1 mol /
Liter and an aqueous solution of a halogen salt containing 2 × 10 ^-5 mol / l of K ₃ IrCl ₆ were added by a control double jet method over 28 minutes and 30 seconds while keeping the pAg at 7.7. Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, and 0.17 g of compound A, low molecular weight gelatin having an average molecular weight of 15,000 (calculated as 20 ppm in terms of calcium content)
The pH was adjusted to 5.9 and the pAg to 8.0. The obtained particles have an average particle size of 0.08 μm,
Cubic particles having a projection area variation coefficient of 9% and a (100) plane ratio of 90%. The silver halide grains thus obtained were subjected to 60 ° C.
, And 76 μmol of sodium benzenethiosulfonate per 1 mol of silver was added. After 3 minutes, 71 μmol of triethylthiourea was added, and the mixture was aged for 100 minutes, and 4-hydroxy-6-methyl-1,3,3 was added. After adding 5 × 10 ⁻⁴ mol of 3a, 7-tetrazaindene, the temperature was lowered to 40 ° C.
Thereafter, the temperature was maintained at 40 ° C., and 12.8 × 10 ⁻⁴ mol of sensitizing dye A, 6.4 × 10 ⁴ mol per mol of silver halide.
^-3 mol of compound B are added with stirring, and after 20 minutes 3
The mixture was rapidly cooled to 0 ° C. to complete the preparation of silver halide emulsion A.

2. Preparation of Organic Acid Silver Dispersion (Organic Acid Silver A) Behenic acid manufactured by Henkel (product name: Edenor C22-8)
5R) 87.6 g, distilled water 423 ml, 5N-NaOH
49.2 ml of an aqueous solution, tert-butyl alcohol 12
0 ml were mixed and reacted at 75 ° C. for 1 hour with stirring to obtain a sodium behenate solution. Separately, 40.4g of silver nitrate
206.2 ml of an aqueous solution of was prepared and kept at 10 ° C. A reaction vessel containing 635 ml of distilled water and 30 ml of tert-butyl alcohol was kept at 30 ° C., and while stirring, the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes 10 seconds and 60 minutes, respectively. Added over minutes. At this time, 7 minutes after the start of the addition of the aqueous silver nitrate solution 2
Only the aqueous solution of silver nitrate was added for 0 seconds, and then the addition of the sodium behenate solution was started. After the addition of the aqueous solution of silver nitrate was completed, only the sodium behenate solution was added for 9 minutes and 30 seconds. At this time, the temperature in the reaction vessel was set to 30 ° C., and the temperature was controlled so as not to rise. Further, the piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the amount of steam was controlled so that the liquid temperature at the outlet at the tip of the addition nozzle became 75 ° C. Also, the piping for the addition system of the silver nitrate aqueous solution is 2
The temperature was maintained by circulating cold water outside the heavy pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution.

After the completion of the addition of the sodium behenate solution, the mixture was left to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Then, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid thus obtained was stored as a wet cake without drying. The morphology of the obtained silver behenate particles was evaluated by electron microscopic photographing.
It was a flaky crystal having a size of 52 μm, an average particle thickness of 0.14 μm, and a variation coefficient of the average equivalent sphere diameter of 15%. Next, a dispersion of silver behenate was prepared by the following method. Dry solid content 1
For a wet cake equivalent to 00 g, polyvinyl alcohol (trade name: PVA-217, average degree of polymerization: about 170)
0) 7.4 g and water were added to make the total amount 385 g and then predispersed with a homomixer. Next, the pre-dispersed stock solution is dispersed in a dispersing machine (trade name: Microfluidizer M).
-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber) at a pressure of 1750 kg / cm ²
And treated three times to obtain a silver behenate dispersion. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. The silver behenate particles contained in the silver behenate dispersion thus obtained had a volume-weighted average diameter of 0.52
The particles had a size of μm and a variation coefficient of 15%. Particle size measurements are available from Malvern Instruments Ltd.
d. The measurement was performed with MasterSizerX manufactured by KK. When evaluated by electron microscopy, the ratio of the long side to the short side was 1.
5, the grain thickness was 0.14 μm, and the average aspect ratio (the ratio of the circle equivalent diameter of the projected area of the grain to the grain thickness) was 5.1.

3.1,1-bis (2-hydroxy-3,
5-Dimethylphenyl) -3,5,5-trimethylhexane: Preparation of solid fine particle dispersion of reducing agent 25 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 25 g of a 20% by weight aqueous solution of MP-203, an MP polymer manufactured by Kuraray Co., Ltd., and Safinol 1 manufactured by Nissin Chemical Co., Ltd.
After adding 0.1 g of 04E, 2 g of methanol and 48 ml of water, the mixture was stirred well and left as a slurry for 3 hours.
After that, 360 g of 1 mm zirconia beads were prepared, put in a vessel together with the slurry, and mixed with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.).
The mixture was dispersed for a time to prepare a dispersion of solid fine particles of a reducing agent. As for the particle diameter, 80% by weight of the particles were from 0.3 μm to 1.0 μm.

4. Preparation of Solid Fine Particle Dispersion of Compound (Solid) of Formula (I) of the Present Invention For 30 g of the compound of formula (I) shown in Table 2, 4 g of MP-203 of MP polymer manufactured by Kuraray Co., Ltd.
0.25 g and 66 g of water were added and stirred well, and then 200 g of 0.5 mm zirconia silicate beads were prepared and put together with the slurry in a vessel, and the dispersion machine (1/1) was used.
16G sand grinder mill: IMEX Co., Ltd.
For 5 hours to prepare a solid fine particle dispersion.
The particle size is 80% by weight of the particles is 0.3 μm to 1.0 μm
Met. Comparative compounds R-1 to R-3 were similarly dispersed.

5. Preparation of solid fine particle dispersion of ultra-high contrast agent B To 10 g of ultra-high contrast agent B, 2.5 g of polyvinyl alcohol (PVA-217 manufactured by Kuraray) and 87.5 g of water were added, and the mixture was stirred well and left as a slurry for 3 hours. did. Thereafter, 240 g of 0.5 mm zirconia beads were prepared and placed in a vessel together with the slurry, and the dispersion machine (１ ／ G)
The mixture was dispersed for 10 hours with a sand grinder mill (manufactured by Imex Co., Ltd.) to prepare a solid fine particle dispersion. As for the particle diameter, 80% by weight of the particles was 0.1 μm to 1.0 μm, and the average particle diameter was 0.5 μm.

[0209] 6. Preparation of Solid Fine Particle Dispersion of Compound Z To 30 g of Compound Z, 3 g of MP-203 (manufactured by Kuraray Co., Ltd.) and 87 ml of water were added, stirred well, and left as a slurry for 3 hours. Thereafter, a solid fine particle dispersion of the compound Z was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle diameter, 80% by weight of the particles were from 0.3 μm to 1.0 μm.

[0210] 7. Preparation of Emulsion Layer Coating Solution The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver microcrystal dispersion prepared above, and water was added. Liquid. Binder; Luckstar 3307B 500 g as solid content (manufactured by Dainippon Ink and Chemicals, Incorporated; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5 , 5-Trimethylhexane 149 g as solid content Compound of formula (I) Kind and amount (mol) shown in Table 2 Ultra-high contrast modifier B 15 g as sodium ethyl thiosulfonate 0.15 g 4-methylbenzotriazole 04 g polyvinyl alcohol (PVA-235 manufactured by Kuraray Co., Ltd.) 10.8 g 6-iso-propylphthalazine 15.0 g sodium dihydrogen orthophosphate dihydrate 0.37 g Compound Z 9.7 g as solid content Dye A Coating amount at which the optical density at 783 nm becomes 0.3 (0.37 g as a guide) Halogenation Silver Emulsion A 0.06 mol as Ag amount

8. Preparation of Emulsion Surface Lower Layer Protective Layer Coating Solution Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Weight%) of a polymer latex solution having a particle diameter of 120 nm (a copolymer having a glass transition temperature of 57 ° C., a solid content concentration of 21.5% by weight, and a compound D as a film-forming aid of 15% by weight based on the solid content of the latex) H ₂ O in% content) 956G
And 1.62 g of compound E and 3.15 of compound S were added.
g, matting agent (polystyrene particles, average particle size 7 μm)
1.98 g and polyvinyl alcohol (Kuraray Co., Ltd.)
Ltd., a PVA-235) 23.6 g was added, further H ₂ O
Was added to prepare a coating solution.

[0212] 9. Preparation of coating liquid for emulsion upper protective layer Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate /
Acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2
(Weight%) of a polymer latex solution having a particle diameter of 70 nm (a copolymer having a glass transition temperature of 54 ° C., a solid content concentration of 21.5% by weight, and a compound D as a film-forming aid of 15 weight% based on the solid content of the latex) % content) of H ₂ O was added to 630 g, carnauba wax (Chukyo Yushi Co., Ltd., Cellosol 524) 30 wt% solution 6.30 g, compound E
0.72 g, compound F 7.95 g, compound S 0.9
0 g, matting agent (polystyrene particles, average particle size 7 μm)
1.18 g and polyvinyl alcohol (Kuraray Co., Ltd.)
Ltd., a PVA-235) 8.30 g was added, further H ₂ O
Was added to prepare a coating solution.

10. Preparation of PET support with back / undercoat layer (1) Support Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = 6/4 (weight) Ratio) measured at 25 ° C) P
I got ET. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and quenched to prepare an unstretched film having a thickness of 120 μm after heat setting. This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then horizontally stretched 4.5 times using a tenter. The temperature at this time was 11
0 ° C and 130 ° C. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends, and the film was wound at 4.8 kg / cm ² . Thus, the width 2.4 m, length 3500 m, thickness 12
A roll of 0 μm was obtained.

(2) Undercoat layer (a) Polymer latex- (1) (a core shell type latex having a core portion of 90% by weight and a shell portion of 10% by weight, core portion: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile) / Acrylic acid = 93/3/3 / 0.9 / 0.1 (% by weight), shell part: vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (weight) %) And a solid content of 3.0 g / m ² 2,4-dichloro-6-hydroxy-s-triazine 23 mg / m ² matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ²

(3) Undercoat layer (b) Deionized gelatin (Ca ²⁺ content 0.6 ppm, jelly strength 230 g) 50 mg / m ²

(4) Conductive layer Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² alkali-treated gelatin (molecular weight: about 10,000, Ca ²⁺ content: 30 ppm) 42 mg / m ² deionized gelatin (Ca ^{2 +} Content 0.6 ppm) 8 mg / m ² Compound A 0.2 mg / m ² Polyoxyethylene phenyl ether 10 mg / m ² Sumitex Resin M-3 (water-soluble melamine compound, manufactured by Sumitomo Chemical Co., Ltd.) 18 mg / m ² Dye A Coating amount at which the optical density of 783 nm becomes 1.2 SnO ₂ / Sb (9/1 weight ratio, acicular fine particles, major axis / minor axis = 20 to 30, manufactured by Ishihara Sangyo Co., Ltd.) 160 mg / m ² Matting agent (polymethyl methacrylate, average particle size 5 μm) 7 mg / m ²

(5) Protective Layer Polymer Latex- (2) (Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (weight% copolymer) )) 1000mg / m ² polystyrenesulfonate solid basis (molecular weight 1000~5000) 2.6mg / m ² Cellosol 524 (Chukyo Yushi (Co.)) 25mg / m ² Sumitex resin M-3 (water-soluble melamine compound, 218 mg / m ² manufactured by Sumitomo Chemical Co., Ltd.

(6) Preparation of PET support having back / undercoat layer An undercoat layer (a) and an undercoat layer (b) were sequentially applied to both sides of the support (base), and dried at 180 ° C. for 4 minutes, respectively. . Then, a conductive layer and a protective layer are sequentially applied to one side of the upper surface after the undercoat layer (a) and the undercoat layer (b) are applied, and dried at 180 ° C. for 4 minutes, respectively. A PET support was prepared. The dry thickness of the undercoat layer (a) was 2.0 μm.

(7) Heat treatment for transport (7-1) Heat treatment PE thus provided with a back / undercoat layer
The T support was placed in a heat treatment zone having a total length of 200 m set at 160 ° C. and transported at a tension of 3 kg / cm ² and a transport speed of 20 m / min. (7-2) Post-heat treatment After the above heat treatment, post-heat treatment was performed by passing through a zone at 40 ° C for 15 seconds, and the film was wound. The winding tension at this time was 10 kg / cm ² .

11. Preparation of heat-developable image recording material P on the side where the undercoat layer (a) and the undercoat layer (b) were applied
The above emulsion layer coating solution was coated on the undercoat layer of the ET support so that the coated silver amount was 1.6 g / m ² . Further, the emulsion layer lower layer protective layer coating solution was coated simultaneously with the emulsion coating solution such that the solid content of the polymer latex was 1.31 g / m ² . Thereafter, the above-mentioned coating liquid for the upper protective layer on the emulsion surface was applied thereon so that the coating amount of the solid content of the polymer latex was 3.02 g / m ² to prepare a heat-developable image recording material. The film surface pH on the image forming layer side of the obtained heat-developable image recording material is 4.9, and the Beck smoothness is 6
The film surface pH on the opposite side was 5.9, and the Beck smoothness was 560 seconds.

12. Evaluation of photographic performance (exposure processing) The obtained heat-developable image recording material was used as a single-channel cylinder equipped with a semiconductor laser having a beam diameter (FWHM of ビ ー ム of beam intensity) of 12.56 μm, laser output of 50 mW, and output wavelength of 783 nm. Using an inner surface type laser exposure device, the exposure time was adjusted by changing the number of rotations of the mirror, and the exposure amount was adjusted by changing the output value, and exposure was performed at 2 × 10 ⁻⁸ seconds. At this time, the overlap coefficient was set to 0.449.

(Heat Development Processing) The exposed heat-developable image-recording material was heated using the heat-development machine shown in FIG. 1, the roller surface material of the heat-development processing section was made of silicone rubber, and the smooth surface was made of Teflon nonwoven fabric. Preheating unit 90 at a speed of 20 mm / sec.
15 seconds at 110 ° C. (The drive systems of the preheating unit and the heat development unit are independent, and the speed difference between the heat development unit and the heat development unit is −0.5% to −0.5%.)
(Set to 1%), and a heat development treatment was performed at 120 ° C. for 20 seconds and a slow cooling unit for 15 seconds. The temperature accuracy in the width direction was ± 1 ° C.

(Evaluation of Photographic Performance) The obtained images were evaluated using a Macbeth TD904 densitometer (visible density).
The results of the measurement were evaluated by _Dmin and sensitivity (relative value of the reciprocal of the ratio of the exposure amount giving a density higher than _Dmin by 1.0). ), D _max , and gradation (contrast) (fresh photographic properties). The gradation is expressed by D
_It was expressed by the slope of a straight line connecting the points of density 0.3 and 3.0 from which the _min part was subtracted. The evaluation of the image storability shows that the heat-developable image recording material after the heat development was subjected to image storability-1 at 60 ° C. and a relative humidity of 50% under a humidity control of 24 hours. The storage stability-2 showed a change in photographic properties after storage for 24 hours under irradiation of 10,000 lux light at a humidity of 40 ° C. and a relative humidity of 50%.

[0224]

[Table 2]

As can be seen from Table 2, when the compound of the present invention was used in a heat-developable image recording material, good photographic performance and good image storability could be obtained.

[0226]

The image recording material using the compound represented by the formula (I) can be prepared, for example, as a heat-developable image recording material. It is useful as a heat-developable image recording material that is stable to changes in conditions, has good color tone, and has high heat / light storage stability of images.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration example of a heat developing machine suitably used when the image recording material of the present invention is used as a heat development image recording material.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 heat-developed image recording material 11 carry-in roller pair 12 carry-out roller pair 13 roller 14 smooth surface 15 heating heater 16 guide plate A preheating section B heat development processing section C slow cooling section

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07D 257/04 C07D 257/04 N G03C 1/498 502 G03C 1/498 502 504 504 (72) Inventor Shigeo Hirano Kanagawa Prefecture 210 Nakanakanuma, Minamiashigara Fuji Photo Film Co., Ltd. Ashigara Research Laboratory (72) Inventor Kota Fukui 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. Ashigara Research Laboratory F term (reference) 2H123 AB00 AB03 AB23 AB28 BB00 BB02 BB27 BB28 BB31 CB00 CB03 4H006 AA01 AA03 AB76 AB78

Claims (7)

[Claims] (1) The following formula (I): (Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent, L represents a divalent linking group containing at least one methylene group, X represents a divalent linking group, and n Represents 0 or 1, and Z represents a residue derived from a photographically useful compound), and a binder. 2. The image recording material according to claim 1, further comprising a photocatalyst. 3. The image recording material according to claim 1, further comprising a reducing agent. 4. The image recording material according to claim 1, further comprising a reducible silver salt. 5. The image recording material according to claim 1, further comprising a super-high contrast agent. 6. A phenol compound represented by the formula (I) according to claim 1. 7. A phenol compound represented by the formula (I) according to claim 1, which is used for an image recording material.