JP2001290240A - Heat developable photosensitive material and processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material which ensures very small expansion and contraction of the base before and after heat development, good sharpening of the toe, high Dmax and good adhesion to the base, a heat developable photosensitive material for printing having good image quality and scuffing resistance and free from color smear and a heat developable photosensitive material for printing adaptable to color printing and high definition printing and processed by perfectly dry processing. SOLUTION: Each of the heat developable photosensitive materials contains an organic silver salt, silver halide, a developing agent and a vinyl compound on the base and is imagewise exposed and heat developed. The rate of thermal dimensional change of each of the photosensitive materials is <0.04% under heat development conditions which make the maximum density of the exposed part >=4.0 and the density of the unexposed part <=0.2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic material, and more particularly to a photothermographic material suitable for printing plate making.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method includes a reducible silver source (for example, organic silver salt), a photocatalyst having a catalytic activity (for example, silver halide), and a silver tone. Is usually contained in the binder matrix in a dispersed state. The photothermographic material is stable at room temperature, but is exposed to high temperature (for example, 8
When heated to 0 ° C. or higher, silver is generated by an oxidation-reduction reaction between a reducible silver source (functioning as an oxidizing agent) and a reducing agent. Since 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 organic silver salt in the exposed area provides a black image to form an image.

Such a photothermographic material has been used as a micro-sensitive material or a X-ray sensitive material, but is only partially used as a printing photosensitive material. This is because the Dmax of the obtained image is low, the limb is poor, and the gradation is soft, so that the image quality is extremely poor as a photographic material for printing.

On the other hand, in recent years, with the development of lasers and light-emitting diodes, scanners and imagesetters having an oscillation wavelength of 600 to 800 nm have become widespread, and are suitable for these output devices, have high sensitivity, high Dmax, and have high sensitivity. The development of lumber was strongly desired. For example, JP-A-10-
Nos. 10672, 10-2037, 10-312
No. 82, No. 10-48772, etc., describe a photothermographic material containing an organic silver salt, a silver halide, a developer and a hydrazine derivative, whereby a high sensitivity, a high Dmax and a high print quality can be obtained. A photothermographic material suitable for the material has been proposed. In particular, Japanese Patent Application Laid-Open No. 10-48772 contains a hydrazine derivative and has been increasing in demand in recent years.
A photothermographic material for use in high-definition color printing, which is capable of coping with high-definition printing of 75 lines / inch or more and hardly causes color shift due to expansion and contraction of a support during thermal development, is disclosed. However, it has been found that these techniques are still insufficient for use in high-definition color printing. Not only physical properties such as adhesion of the photothermographic layer to the support, but also properties for use in printing, such as leg drop and high Dmax, are still insufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material in which the expansion and contraction of the support before and after thermal development is extremely small, the leg is good, the Dmax is high, and the adhesion to the support is good. Is to provide. Another object of the present invention is to provide a printing photosensitive material having good image quality and scratch resistance and free from color misregistration. Still another object of the present invention is to provide a photosensitive material for printing which is completely dry-processed and which can cope with color printing and high definition printing.

[0006]

The above object of the present invention is achieved by the following constitution.

[0007] 1. Organic silver salt, silver halide,
A photothermographic material containing a developer and a vinyl compound, wherein the photothermographic material is exposed imagewise and thermally developed to have a maximum density of 4.0 or more in an exposed portion and a density of 0 in an unexposed portion. .
A photothermographic material characterized in that the thermal dimensional change of the photothermographic material is less than 0.04% under a heat development condition of 2 or less.

[0008] 2. 2. The photothermographic material according to the item 1, wherein the vinyl compound is represented by the general formula (G).

3. 3. A processing method, wherein the photothermographic material according to 1 or 2 is subjected to a heat development process at a developing temperature of 100 ° C. to 130 ° C. for 5 seconds to 50 seconds.

Hereinafter, the present invention will be described in detail. With the above configuration according to the present invention, Dmax is high and Dmi is high.
It is possible to obtain a photothermographic material having a low n and a high contrast image, having less heat development unevenness at the time of heat development, and having good film adhesion to a support, and a processing method for processing the photothermographic material.

That is, a photothermographic material having an organic silver salt, a silver halide, a developer and a vinyl compound on a support is imagewise exposed, and the maximum density of the exposed area is 4.0 or more and the unexposed area is exposed. Is thermally developed under a thermal development condition in which the concentration of is less than or equal to 0.2, and the photothermographic material having a thermal dimensional change of less than 0.04% has a high Dmax and a low Dmin,
In addition, a high-contrast image can be obtained, heat development unevenness during heat development is small, and a photothermographic material having good film adhesion with a support can be obtained. Materials and processing methods can be provided.

The photothermographic material is exposed imagewise and heat-developed, and the heat-developable photosensitive material having a maximum density of 4.0 or more in the exposed portion and a density of 0.2 or less in the unexposed portion is preferably 90 or more.
5 to 90 seconds at 100 to 150 ° C., more preferably 100 ° C.
The temperature is from 5 to 50 seconds at ~ 130 ° C, and the temperature may change stepwise as a condition.

The heat treatment conditions and the heat treatment method for the support will be described later. To obtain the effects of the present invention, it is necessary to heat-treat the support used for the photothermographic material at a temperature in the range of 80 to 200 ° C. For example, the heat treatment is performed while transporting the support, and the transport tension is preferably 13
00 kPa / cm ² or less, more preferably 1000 kPa / cm ²
Pa / m ² or less, more preferably 400 kPa / c
It is preferred to transport in m ² or less.

The photothermographic material according to the present invention, having an organic silver salt, a silver halide, a developer and a vinyl compound on a support, which exhibits the above-mentioned thermal dimensional change rate, is why the photothermographic material is supported. It is not clear whether the film with the body can be significantly improved compared to what is conventionally known, but the vinyl compound contributes not only to the hardening effect but also to the improvement of the physical properties by some action. it is conceivable that. Compared with a conventional hydrazine compound, Dmax is high, Dmin is low, a high-contrast image is obtained, heat development unevenness during heat development is small, film adhesion to a support is good, and scratch resistance is high. It is possible to provide a photosensitive material for printing and a processing method, which has good properties and does not cause color shift.

[0015] For this reason, it is possible to provide a completely dry-processed photosensitive material for printing that can be handled by color printing and high-definition printing.

The photothermographic material of the present invention contains an organic silver salt. The organic silver salt is a reducible silver source, and is a silver salt of an organic acid or a heteroorganic acid, particularly a long-chain (10 to 30, preferably 15 to 25) aliphatic carboxylic acid and a nitrogen-containing heterocyclic ring. Silver salts of the compounds are preferred. The ligand has a total stability constant of 4.0 to 10.0 for silver ions.
Organic or inorganic complexes having the value of are also preferred. Examples of these suitable silver salts include RD17029 and 299
63, and the following may be mentioned.

Silver salts of organic acids, such as gallic acid, oxalic acid,
Silver salts such as behenic acid, stearic acid, arachidic acid, palmitic acid and lauric acid. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, and aldehydes with hydroxy-substituted aromatic carboxylic acids A silver salt or complex of a polymer reaction product, for example, a silver salt or complex of a reaction product of an aldehyde (formaldehyde, acetaldehyde, butyraldehyde, etc.) and a hydroxy-substituted acid (for example, salicylic acid, 3,5-dihydroxybenzoic acid); Silver salts or complexes of thiones, for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione, and 3
Silver salts or complexes such as -carboxymethyl-4-thiazoline-2-thione, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole;
Complexes or salts of silver and a nitrogen acid selected from 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole, silver salts such as saccharin and 5-chlorosalicylaldoxime, and silver mercaptides. Among them, preferred silver salts include silver behenate, silver arachidate and silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and includes a normal mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate, sodium arachidate, etc., the above-mentioned soap and silver nitrate are mixed by a controlled double jet method to produce an organic silver salt crystal. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably 0 μm or less and monodispersed.
The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. Average particle size is 0.05 μm to 10 μm, preferably 0.05 μm
To 5 μm, particularly preferably 0.05 μm to 1.0 μm.
The monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.

In the present invention, the tabular grains of the organic silver salt preferably have at least 60% of the total organic silver.
In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to make the organic silver salt into these shapes, the crystal of the organic silver salt is dispersed and pulverized with a ball mill or the like with a binder or a surfactant. Obtained by: Within this range, a photosensitive material having a high density and excellent image storability can be obtained.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.2 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained.

The photosensitive silver halide used in the photothermographic material of the present invention can be produced by any method known in the field of photographic technology such as a single jet or double jet method in the presence of a protective colloid such as gelatin. For example, it can be prepared by any method such as an ammonia method emulsion, a neutral method and an acid method. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat.
No. 706,564, No. 3,706,565, No. 3,713,833, No. 3,748,143 and British Patent No. 1,362,970. A means for using a polymer other than gelatin, for example, a method for enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in British Patent No. 1,354,186; 076,
As described in the specification of JP-A-539, various means such as a method of omitting the use of a protective polymer by preparing photosensitive silver halide grains in the presence of a surfactant can be applied.

The silver halide grains function as an optical sensor. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals or non-normal crystals, such as spherical, rod-shaped, and plate-shaped grains. There is. The silver halide composition is not particularly limited, and the halide composition may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. In order to suppress white turbidity after image formation and obtain good image quality, the average particle size is preferably small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, and particularly preferably 0.1 μm to 0.1 μm. It is preferably from 02 μm to 0.08 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. If the crystal is not normal, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The particles are more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The amount of silver halide is 50% or less, preferably 25%, based on the total amount of silver halide and an organic silver salt described later. To 0.1%, more preferably between 15% to 0.1%.

The photosensitive silver halide used in the photothermographic material of the present invention may also be used in preparing an organic silver salt as described in British Patent 1,447,454. Halogen components such as ions coexist with organic silver salt-forming components, and silver ions are implanted into the components to produce organic silver salts almost simultaneously.

As still another method, a part of the organic silver salt is exposed to light by allowing a silver halide forming component to act on a previously prepared solution or dispersion of the organic silver salt or a sheet material containing the organic silver salt. It can also be converted to neutral silver halide.
The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak specific to silver halide. Silver halide-forming components confirmed to be effective by such tests include inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Are U.S. Pat. Nos. 4,009,039 and 3,45
7,075, 4,003,749, British Patent 1,498,956 and JP-A-53-270.
Nos. 27 and 53-25420, each of which is described in detail below.

(1) Inorganic halide: For example, a halide represented by MX _n (where M represents H, NH ₄ , and a metal atom, and n represents 1 when M is H and NH ₄ ) M
When is a metal atom, it represents the same value as its valence. Examples of the metal atom include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, manganese, iron, cobalt, nickel, rhodium, and cerium. Further, halogen molecules such as bromine water are also effective.

(2) Onium halides: quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, and quaternary phosphonium halides such as tetraethylphosphonium bromide And tertiary sulfonium halides such as trimethylsulfonium iodide.

(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like.

(4) N-halogen compounds: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-bromooxazolinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide,
1,3-dibromo-4,4-dimethylhydantoin, N
-Bromourazole and the like.

(5) Other halogen-containing compounds: for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is from 0.001 mol to 0.7 mol, preferably from 0.03 mol to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. Usually, the reaction temperature is -20 ° C to 70 ° C, the reaction time is 0.1 second to 72 hours,
The reaction pressure is preferably set at atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be achieved by a chromium compound or a combination thereof. The method and procedure of this chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, JP-A-51-224.
No. 30, No. 51-78319, and No. 51-81124. Further, when a part of the organic silver salt is converted into a photosensitive silver halide by a silver halide forming component, as described in US Pat. No. 3,980,482, sensitization is achieved. A low molecular weight amide compound may coexist.

In addition, these photosensitive silver halides may be used in order to prevent illuminance failure and to adjust the gradation.
Metals belonging to group III, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof, or a complex ion can be contained. It is particularly preferable to add as a complex ion. For example, Ir complex ion such as IrCl ₆ ^2- may be added due to illuminance failure.

Examples of the reducing agent used in the photothermographic material of the present invention include generally known reducing agents such as phenols, polyphenols having two or more phenol groups, naphthols and bisnaphthols. , 2
Polyhydroxybenzenes having at least two hydroxyl groups, 2
Polyhydroxynaphthalenes having at least two hydroxyl groups,
Ascorbic acids, 3-pyrazolidones, pyrazoline-
5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone monoethers,
Hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas, and the like. More specifically, for example, U.S. Patent Nos. 3,615,533 and 3,67.
9,426, 3,672,904, 3,7
No. 51,252, No. 3,782,949, No. 3,
Nos. 801,321, 3,794,488, 3,893,863, 3,887,376, 3,770,448, 3,819,382,
No. 3,773,512 and No. 3,839,048
No. 3,887,378, No. 4,009,03
9, No. 4,021,240, British Patent No. 1,48
No. 6,148 or Belgian Patent No. 786,086 and JP-A-50-36143, 50-36.
No. 110, No. 50-116023, No. 50-9971
No. 9, No. 50-140113, No. 51-51933
Nos. 51-23721, 52-84727 and JP-B-51-35851, and the present invention is appropriately selected from such known reducing agents. Can be used. As a selection method, the simplest method is to actually prepare a photothermographic material and evaluate the photographic performance of the photothermographic material to determine the superiority of the reducing agent used.

Among the above reducing agents, when a silver aliphatic carboxylate is used as the organic silver salt, preferred reducing agents include polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur. In particular, an alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) is provided at at least one of the positions adjacent to the hydroxy substitution position of the phenol group. Are polyphenols in which two or more of the phenol groups substituted by an alkylene group or sulfur, for example, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
5-trimethylhexane, 1,1-bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane,
1,1-bis (2-hydroxy-3,5-di-t-butylphenyl) methane, 2-hydroxy-3-t-butyl-5-methylphenyl- (2-hydroxy-5-methylphenyl) methane, 6,6'-benzylidene-bis (2,4-di-t-butylphenol), 6,6'-benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene-bis ( 2,4-dimethylphenol), 1,1-bis (2-hydroxy-
3,5-dimethylphenyl) -2-methylpropane,
1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5
U.S. Pat. Nos. 3,589,903 and 4,021,249 or British Patent 1,486,148 and JP-A-51-51933. No. 50-36110, No. 50
Polyphenol compounds described in JP-A-116023, JP-A-52-84727 or JP-B-51-35727, bisnaphthols described in U.S. Pat. No. 3,672,904, for example, 2,2'- Dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-
2,2'-dihydroxy-1,1'-binaphthyl, 6,
6'-dinitro-2,2'-dihydroxy-1,1'-
Binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl and the like, and further US Pat. No. 3,80
Sulfonamidophenols or sulfonamidonaphthols as described in US Pat. No. 1,321, for example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4
-Benzenesulfonamidophenol, 4-benzenesulfonamidonaphthol and the like.

The amount of the reducing agent used in the photothermographic material of the present invention varies depending on the type of the organic silver salt, the reducing agent, and other additives. 05 mol to 10 mol, preferably 0.1 mol to 3 mol
Molar is appropriate. Further, within this range, two or more of the above-mentioned reducing agents may be used in combination. In the present invention, it may be preferable to add and mix the reducing agent to the photosensitive solution immediately before coating and apply the reduced solution because the photographic performance fluctuation due to the stagnation time of the photosensitive solution is small.

The photothermographic material of the present invention contains the above-mentioned vinyl compound as a high contrast agent. As the vinyl compound, a compound represented by the general formula (G) is preferable. These vinyl compounds are preferable because they exhibit a greater effect in a heat development system than hydrazine derivatives, which are also known as contrast agents.

The general formula (G) will be further described.
Is a substituent whose Hammett's substituent constant σp can take a positive value. Specifically, a substituted alkyl group (eg, halogen-substituted alkyl), a substituted alkenyl group (eg, cyanovinyl), a substituted / unsubstituted alkynyl group (eg, trifluoromethylacetylenyl, cyanoacetylenyl), and a substituted aryl group (eg, cyanovinyl) Phenyl, etc.), substituted / unsubstituted heterocyclic groups (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atoms, acyl groups (acetyl, trifluoroacetyl, formyl, etc.), thioacetyl groups (thioacetyl, thioformyl, etc.), oxalyl Group (eg, methyl oxalyl), oxyoxalyl group (eg, ethoxyl), thiooxalyl group (eg, ethylthiooxalyl), oxamoyl group (eg, methyl oxamoyl), oxycarbonyl group (eg, ethoxycarbonyl), carboxyl group, thiocarbonyl group (eg, Ethylthiocarbonyl, etc.),
Carbamoyl group (methylcarbamoyl, phenylcarbamoyl, etc.), thiocarbamoyl group (ethylthiocarbamoyl, phenylthiocarbamoyl, etc.), sulfonyl group (methanesulfonyl, etc.), sulfinyl group (methanesulfinyl, etc.), oxysulfonyl group (ethoxysulfonyl, etc.), A thiosulfonyl group (such as ethylthiosulfonyl), a sulfamoyl group (such as sulfamoyl and methylsulfamoyl), an oxysulfinyl group (such as methoxysulfinyl), a thiosulfinyl group (such as methylthiosulfinyl), a sulfinamoyl group (such as methylsulfinamoyl), Sphinamoyl group (eg, methylsulfinamoyl), phosphoryl group (eg, bis (ethoxy) -phosphoryl), cyano group, nitro group, imidoyl group (acetimidoyl, N-phenyla) Tomidoyl), an N-acyl imidoyl group (such as N-acetyl imidoyl), an N-sulfonylimidoyl group (such as N-methanesulfonyl imidoyl), a dicyanoethylene group (such as 2,2-dicyanoethylene), and an ammonium group , A sulfonium group, a phosphonium group, a pyrylium group, and an immonium group.
Heterocyclic groups in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, etc. form a ring are also included. A substituent having a σp value of 0.30 or more is particularly preferred.

The alkyl group represented by W is methyl, ethyl, trifluoromethyl and the like, the alkenyl group is vinyl, halogen-substituted vinyl and cyanovinyl, the alkynyl group is acetylenyl and cyanoacetylenyl and the like. Examples of the group include nitrophenyl, cyanophenyl, and pentafluorophenyl, and examples of the heterocyclic group include pyridyl, pyrimidyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, and benzoxazolyl.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like are used. As the acyl group, unsubstituted alkanoyl such as formyl, acetyl, propionyl and cyclohexanecarbonyl, trichloroacetyl, trifluoroacetyl, methylthio Substituted alkanoyl such as acetyl, benzoyl, tolyl, substituted benzoyl such as dicyanobenzoyl, as the thioacyl group, a group such as thioacetyl, as the oxalyl group, ethyl oxalyl, methyl oxalyl, a group such as butyl oxalyl, as the oxyoxalyl group Is a group such as ethoxyoxalyl, methoxyethoxyoxalyl, 2,2,3,3-tetrafluoropropoxyoxalyl, as the thiooxalyl group, a group such as ethylthiooxalyl, and as the oxamoyl group, Substituted and unsubstituted oxamoyl groups such as tyl oxamoyl and methylthioethyl oxamoyl are substituted oxycarbonyl groups such as ethoxycarbonyl and methylthioethoxycarbonyl groups, and unsubstituted groups, and thiocarbonyl groups are methylthiocarbonyl and ethyl. And groups such as thiocarbonyl.

The carbamoyl group represented by W is, for example, an optionally substituted group such as methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl, pyridylcarbamoyl or piperidinylcarbamoyl, and the thiocarbamoyl group is ethylthiocarbamoyl. Phenylthiocarbamoyl, piperidinylthiocarbamoyl and the like, as a sulfonyl group, methanesulfonyl,
Groups such as ethanesulfonyl, butanesulfonyl, and trifluoromethanesulfonyl, sulfinyl groups include groups such as methanesulfinyl, oxysulfonyl groups include groups such as methoxysulfinyl and ethoxysulfinyl, and thiosulfonyl groups include ethylthiol. As a group such as sulfinyl, as a sulfamoyl group, a group such as sulfamoyl and methylsulfamoyl, as an oxysulfinyl group, a group such as methoxysulfinyl, and as a thiosulfinyl group, a group such as methylthiosulfinyl, a sulfinamoyl group As a group such as methylsulfinamoyl; and as the phosphoryl group, a group such as an alkoxyphosphoryl such as bis (ethoxy) -phosphoryl.

The alkoxy group represented by W is a group such as ethoxy and cyclohexyloxy; the aryloxy group is a group such as phenoxy; the heterocyclic oxy group is a group such as pyridyloxy; a mercapto group; Examples of the alkylthio group include groups such as ethylthio and cyclohexylthio, examples of the arylthio group include groups such as phenylthio, examples of the heterocyclic thio group include groups such as pyridylthio, and examples of the amino group and the alkylamino group include dimethylamino.
Groups such as 2-chloroethylamino, morpholino, and pyrrolidinyl; arylamino groups such as anilino; heteroarylamino groups such as pyridylamino group and benzimidazolylamino; acylamino groups such as acetamido and trifluoroacetamide; , A group such as heptafluorobutanamide, an oxycarbonylamino group is a group such as ethoxycarbonylamino, and a ureido group is methylureide, phenylureido, p
-Groups such as cyanophenylureido, sulfonamide groups such as methanesulfonamide and trifluoromethanesulfonamide, oxysulfonylamino groups such as ethoxysulfonylamino, and sulfamoylamino groups methyl sulfonyl. Examples include groups such as famoyl, phenylsulfamoyl, and 3-cyano-4-chlorophenylsulfamoyl.

Examples of the imidoyl group represented by W include groups such as acetimidoyl and N-phenylacetimidoyl, and examples of the N-acyl imidoyl group include N-acetyl-acetimidoyl and N-formyl- Groups such as formimidoyl, N-trifluoroacetyl-trifluoroacetimidoyl and the like, and N-sulfonylimidoyl groups such as N-methanesulfonylacetoimidoyl and N-trifluoromethylsulfonyl-formimidoyl;
Examples of the dicyanoethylene group include 2,2-dicyanoethylene, 2,2-dicyano-1-methylethylene, and 2,2-dicyanoethylene.
Dicyano-1-trifluoromethylethylene, 1,2,2
Examples of groups such as 2-tricyanoethylene and ammonium groups include groups such as trimethylammonio and pyridinio;
A group such as a -pyridinio group or a 2-imidazolio group, a sulfonium group such as a dimethylsulfonio group, a phosphonium group such as a triphenylphosphonio group,
Examples of the pyrylium group include a 2-pyranio group and the like. Among them, W is preferably an electron-withdrawing group having a positive σp value, more preferably 0.30 or more.

R represents a halogen atom (a fluorine atom, a chlorine atom,
Bromine atom), hydroxy group, alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, p-methoxyphenoxy group, o-chlorophenoxy group, etc.), heterocyclic oxy group (pyridyloxy group, etc.) Alkenyloxy group (allyloxy group, etc.), acyloxy group (acetoxy group, propionyloxy group, benzoyloxy group, etc.), alkoxycarbonyloxy group (ethoxycarbonyloxy group, butoxycarbonyloxy group, etc.), aminocarbonyloxy group (ethylcarbamoyl) Oxy group, propylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), mercapto group, alkylthio group (methylthio group, butylthio group, etc.), arylthio group (phenylthio group, p-methoxyphenylthio group, p-
Chlorophenyl group, etc.), heterocyclic thio group (pyridylthio group, etc.), alkenylthio group (allylthio group, etc.), acylthio group (acetylthio group, etc.), alkoxycarbonylthio group (methoxycarbonylthio group, ethoxycarbonylthio group, etc.), An aminocarbonylthio group (ethylcarbamoylthio group, propylcarbamoylthio group, phenylcarbamoylthio group, etc.), an organic or inorganic salt of a hydroxy group or a mercapto group (eg, sodium salt, potassium salt, silver salt, etc.), an amino group, Alkylamino group (group such as dimethylamino, 2-chloroethylamino, morpholino, and pyrrolidinyl), cyclic amino group (for example, pyrrolidino group), acylamino group (acetamide, trifluoroacetamide, heptafluorobutanamide, etc.), oxycarbonylamino Base Ethoxycarbonylamino, etc.),
Heterocyclic groups (5- to 6-membered nitrogen-containing heterocycles such as benztriazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, etc.), ureido groups (methylureido, phenylureido, p-cyanophenylureido, etc.), sulfone Represents an amide group (methanesulfonamide, trifluoromethanesulfonamide, etc.). X and W, and X and R may be bonded to each other to form a cyclic structure. (The ring formed by X and W is, for example, pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β
-Ketoractam and the like).

Further, among the substituents for R, a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group,
Organic or inorganic salts of a halogen atom, a hydroxy group or a mercapto group, for example, sodium salt, potassium salt, silver salt and the like. Among heterocyclic groups, a 5- to 6-membered nitrogen-containing heterocycle, for example, benztriazolyl Group, imidazolyl group,
Preferred are a triazolyl group, a tetrazolyl group and the like, more preferred are an organic or inorganic salt of a hydroxy group, an alkoxy group, a hydroxy group or a mercapto group, and a heterocyclic group, and particularly preferred are a hydroxy group, a hydroxy group and a mercapto group. Organic or inorganic salts of the group.

Of the above-mentioned X and W substituents, those having a thioether bond in the substituent are preferred.

Next, specific examples of the compound represented by the general formula will be shown below, but it should not be construed that the invention is limited thereto.

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

The layer to which the vinyl compound is added is a photosensitive layer containing silver halide and / or a layer adjacent to the photosensitive layer. The optimum amount of addition is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is preferably 10 ^-6 mol to 10 ^-1 per mol of silver halide. The molar ratio is preferably about 10 ^-5 mol to 10 ^-2 mol. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

These vinyl compounds can be used in 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, 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, a vinyl compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The photothermographic material of the present invention may contain a hydrazine derivative in addition to the above-mentioned vinyl compound, whereby the effect can be enhanced.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0082]

Embedded image

In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent;
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, for example, a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, in -G ₀ -D ₀ group represented by A _0, G ₀ is -CO
Group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. G ₁ is a mere bond, -O-
A group, —S— group or —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, They can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferable D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group, and the like. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent.

Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group. In the general formula [H],
A ₀ preferably contains at least one diffusion-resistant group or silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably -G ₀ -D ₀ group, and G ₀ represents-
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. Preferred G ₀ is -CO-
Group, -COCO- group, G ₁ is a mere bond,
—O—, —S— or —N (D ₁ ) —, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D ₁ are present in the molecule If so, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.), or an oxalyl group (Such as an ethoxalyl group).

The following are specific typical examples of the compound represented by the general formula [H].

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in columns 11 to 20 of US Pat. No. 5,545,505.
U.S. Pat. No. 5,464,738 column 9 to column 11
And compounds 1 to 12.

[0097] These hydrazine derivatives can be synthesized by a known method. When a hydrazine derivative is used, the added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The optimum amount of addition is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is preferably 10 ^-6 mol to 10 ^-1 per mol of silver halide. About 1 mole, especially 1
The range is preferably from 0 ^-5 mol to 10 ^-2 mol.

In the present invention, the following general formula (H-
It is also effective to use the hydrazine derivatives represented by 1) to (H-4) together with the general formula (G).

[0099]

Embedded image

R ₁₁ , R ₁₂ and R ₁₃ each independently represent a substituted or unsubstituted aryl group or heteroaryl group. R ₁₄ represents a heteroaryloxy group or a heteroarylthio group. A ₁ and A _{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents an alkylsulfonyl group, an oxalyl group or an acyl group.

R ₁₁ , R ₁₂ and R ₁₃ each independently represent a substituted or unsubstituted aryl group or heteroaryl group. Specific examples of the aryl group include phenyl, p-methylphenyl, naphthyl and the like. Can be
Specific examples of the heteroaryl group include a triazole residue, an imidazole residue, a pyridine residue, a furan residue, and a thiophene residue. R ₁₁ , R
₁₂ and R ₁₃ may be bonded via an arbitrary linking group. When R ₁₁ , R ₁₂ and R ₁₃ have a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a quaternary heterocyclic group containing a nitrogen atom ( For example, a pyridinio group), a hydroxy group, an alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a urethane Group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group,
Grade ammonium (alkyl, aryl, or heterocycle) thio, mercapto, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl, sulfo, sulfamoyl, acylsulfamoyl, (alkyl Or aryl) sulfonyluureido, (alkyl or aryl) sulfonylcarbamoyl, halogen, cyano, nitro,
And a phosphoric amide group. R ₁₁ , R ₁₂ and R ₁₃
Are preferably substituted or unsubstituted phenyl groups, and more preferably, all of R ₁₁ , R ₁₂ and R ₁₃ are unsubstituted phenyl groups.

R ₁₄ represents a heteroaryloxy group or a heteroarylthio group. Specific examples of the heteroaryloxy group include a pyridyloxy group, a pyrimidyloxy group,
Examples include an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group, a furyloxy group, a thienyloxy group, a pyrazolyloxy group, and an imidazolyloxy group. Specific examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Ethoxalyl). Preferably, A ₁ and A ₂ are both hydrogen atoms.

[0104]

Embedded image

R ₂₁ is a substituted or unsubstituted alkyl group,
Represents an aryl group or a heteroaryl group. R ₂₂ represents a hydrogen atom, an alkylamino group, an arylamino group, or a heteroarylamino group.

R_{twenty one}Is a substituted or unsubstituted alkyl group,
Represents an aryl group or a heteroaryl group,
Specific examples of the group include a methyl group, an ethyl group, and t-butyl.
Group, 2-octyl group, cyclohexyl group, benzyl group,
And a diphenylmethyl group. Aryl group and f
Specific examples of the teloaryl group include R₁₁, R₁₂And R ₁₃
And the same. Also, R_{twenty one}Has a substituent
Specific examples of the substituent in the case where₁₁, R₁₂as well as
R₁₃And the same substituents as mentioned above. R_{twenty one}Good as
Preferably, it is an aryl group or a heteroaryl group.
Is preferably a substituted or unsubstituted phenyl group.

R ₂₂ represents a hydrogen atom, an alkylamino group, an arylamino group, or a heteroarylamino group. Specific examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, Examples include a dimethylamino group, a diethylamino group, and an ethylmethylamino group. Examples of the arylamino group include an anilino group, and examples of the heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. Preferably the R ₂₂ is dimethylamino group or diethylamino group.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2.

[0109]

Embedded image

R ₃₁ and R ₃₂ each represent a monovalent substituent. Examples of the monovalent substituent include the groups mentioned as the substituents of R ₁₁ , R ₁₂ and R ₁₃ . Examples include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, and an amino group. More preferably, it is an aryl group or an alkoxy group. Particularly preferred are those in which at least one of R ₃₁ and R ₃₂ is a tert-butoxy group, and another preferred structure is when R ₃₁ is a phenyl group.
₃₂ is a tert-butoxy group.

G ₃₁ and G ₃₂ represent a — (CO) p— group, and —C (=
S)-, a sulfonyl group, a sulfoxy group, -P (= O) R
Represents a ₃₃ -group or an iminomethylene group, p represents an integer of 1 or 2, R ₃₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Represents an amino group. However, when G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. G ₃₁ and G ₃₂ are preferably -CO
—, —COCO—, sulfonyl or —CS—, more preferably —CO— or mutually sulfonyl.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2. In the general formula (H-3), G ₃₁
And G ₃₂ are particularly preferably carbonyl groups or both are sulfonyl groups.

In the general formula (H-3), it is particularly preferable that at least one of R ₃₁ and R ₃₂ has the following structure.

-OC (CH ₃ ) ₃

[0115]

Embedded image

R₄₁, R₄₂And R₄₃Are replaced independently
Or an unsubstituted aryl or heteroaryl group
Represent. R₄₄, R₄₅Represents an unsubstituted or substituted alkyl group
You. A ₁, A_TwoAre both hydrogen atoms or one is a hydrogen atom
The other is an alkylsulfonyl group, an oxalyl group or an acyl
Represents a group.

R ₄₁ , R ₄₂ and R ₄₃ have the general formula (H-1)
Has the same meanings as R ₁₁ , R ₁₂ and R ₁₃ . R ₄₁ , R
_{Each of 42} and R ₄₃ is preferably a substituted or unsubstituted phenyl group, and more preferably, R ₄₁ and R ₄₂
And R ₄₃ are both unsubstituted phenyl groups.
R ₄₄ and R ₄₅ represent an unsubstituted or substituted alkyl group, and specific examples include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group,
And a diphenylmethyl group. R ₄₄ and R ₄₅ are preferably each an ethyl group.

A ₁ and A ₂ are those represented by the general formula (H-1)
₁ is the same as A _2. Hereinafter, these general formulas (H-1) to
Specific representative examples of the compound represented by (H-4) will be given.

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

The compounds represented by formulas (H-1) to (H-4) can be easily synthesized by known methods. For example, it can be synthesized with reference to US Pat. No. 5,464,738 or US Pat. No. 5,496,695.

When these hydrazine derivatives are used,
The addition layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The addition amount the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the optimum amount is a difference such as type of inhibitor, but not uniform, per mol of silver halide 10 ^-6 mol to 10 ^-1 mol, especially 10
A range of ^-5 mol to 10 ^-2 mol is preferred.

The hydrazine derivative can be dissolved in an appropriate organic solvent, or formed after forming an emulsified dispersion, or added by a method known as a solid dispersion method.

The photothermographic material of the present invention includes hydroxylamine compounds, alkanolamine compounds and ammonium phthalate compounds described in US Pat. No. 5,545,505, and US Pat. No. 5,545,507. Hydroxamic acid compounds of US Pat. No. 5,558,983
N-acyl-hydrazine compounds described in U.S. Pat. No. 5,545,515, acrylonitrile compounds described in U.S. Pat. No. 5,545,515, benzhydrol, diphenylphosphine, dialkylpiperidine and alkyl described in U.S. Pat. No. 5,937,449. It is preferable to add a hardening accelerator such as a hydrogen atom donor compound such as -β-ketoester. Among them, a quaternary onium compound represented by the following general formula (P) and an amino compound represented by the general formula [Na] are preferably used.

[0131]

Embedded image

In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Incidentally, R _{1 to} R ₄ may be connected to each other to form a ring.

[0133]

Embedded image

In the general formula [Na], R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group, Represents an unsaturated heterocyclic ring. R ₁₁ , R ₁₂ and R ₁₃ may form a ring. Particularly preferred are aliphatic tertiary amine compounds.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. Molecular weight 100 or more compounds are preferred in order to have a diffusion-resistant, still more preferably a molecular weight of 300 or more, include those having the same meaning as non-diffusible group in A ₀ in the general formula (H).
Further, preferred adsorbing groups include a heterocyclic ring, a mercapto group,
Examples include a thioether group, a thione group, and a thiourea group.

A nucleation accelerator more preferably than the nucleation accelerator represented by the general formula [Na] includes a compound represented by the following general formula [Na2].

[0136]

Embedded image

In the general formula [Na2], R¹, R^Two, R
^ThreeAnd R^FourRepresents a hydrogen atom, an alkyl group, a substituted alkyl
Group, alkenyl group, substituted alkenyl group, alkynyl group,
Substituted alkynyl, aryl, substituted aryl or saturated
Represents a sum or unsaturated hetero ring. These are linked to each other
Can be linked to form a ring. Also, R¹And R^Two, R ^Three
And R^FourAre not simultaneously hydrogen atoms. X is S, S
represents an e or Te atom. L¹And L^TwoIs a divalent linking group
Represents Specifically, the following groups or their combinations and
And suitable substituents (for example, alkylene group,
Nylene, arylene, acylamino, sulfone
And the like.

-CH _2- , -CH = CH-, -C ₂ H
₄ -, _{pyridinediyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, - S
-, - (CO) -, - (SO 2) -, - CH 2 N-.

The linking group represented by L ¹ or L ² preferably contains at least one or more of the following structures in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ )
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
_{[OCH 2 C (OH) HCH} 2] -.

The following are specific examples of the nucleation accelerator represented by the general formula [Na] or [Na2].

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

In the general formula (P), the substituent represented by R _{1 to} R ₄ is an alkyl group (a methyl group, an ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

The ring which can be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

R ₁ , R ₂ , R ₃ and R ₄ are preferably a hydrogen atom and an alkyl group. Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0151]

Embedded image

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R¹, R^TwoAnd R^FiveEach have 1 to 20 carbon atoms
Represents an alkyl group. Also, R¹And R ^TwoAre the same but different
May be. An alkyl group is a substituted or unsubstituted alkyl group.
Represents a kill group, and the substituent is A¹, A^Two, A^Three, A^FourPassing
And A^FiveAre the same as the substituents exemplified as the substituent for.

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0156] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0157]

Embedded image

The phenyl substituents R ₅ and R ₆ of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value at the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, and
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

[0162]

Embedded image

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

Embedded image

[0169]

Embedded image

[0170]

Embedded image

[0171]

Embedded image

The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews 55 p. 33
The method described in 5-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

In the present invention, compounds represented by the following formulas (A-1) to (A-4) can be used as a development accelerator.

[0175]

Embedded image

In the general formula (A-1), R₅₁Is archi
Group, alkenyl group, alkoxy group, alkylthio group,
Amide group, aryl group, aralkyl group, aryloxy
Group, arylthio group, anilino group or heterocyclic group
You. In the general formula (A-2), R₆₁, R₆₂Is hydrogen field
, Alkyl, alkenyl, aryl, aralkyl
Group, aliphatic or aromatic heterocyclic group, cycloaliphatic group
Represent. In the general formula (A-3), R₇₁Is hydroxya
Represents a alkyl group;₇₂, R₇₃Are each independently a hydrogen source
, An alkyl group,-(CH_Two) N-N-R₇₄(R₇₅)
(N is an integer of 1 to 10, R₇₄, R₇₅Are each independently water
Element atom, alkyl group). General formula (A-4)
And R₈₁Is hydrazino, alkylamino, sulfonyl
Ruamino group, ureido group, oxycarbonylamino group,
Represents an alkynyl group or an unsubstituted amino group. R₈₂Is water
Represents an atom, an alkyl group, an aryl group, or a heterocyclic group.
X is a hydrogen atom, an alkyl group, a carbamoyl group or
Represents an oxycarbonyl group. R ₈₁And R₈₂Is combined with 5
A seven to seven membered ring may be formed.

The addition amount of these compounds is about 1 × 10 ⁻⁸ to 1 mol, preferably 1 × 10 ⁻⁸ mol per mol of silver halide.
It is 10 ^-7 to 1 × 10 -1 mol. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

The photothermographic material of the present invention may contain the following compounds as development accelerators.

2-mercaptobenzimidazole, 2-
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, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4
-Thiadiazole, 3-amino-5-mercapto-1,
2,4-triazole, 4-hydroxysil-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-
4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole and the like.

Phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5
Cyclic imides such as -one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate) ); 3-mercapto-1,
2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4
-Triazole and 2,5-dimercapto-1,3,
Mercaptans exemplified by 4-thiadiazole; N-
(Aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-
2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives, and certain photobleaching agents (eg, N, N'-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8 −
(3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and (2-tribromomethylsulfonyl)-(benzothiazole));
Ethyl-5-[(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-
Oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone, 2,3-dihydro-1,4-phthalazinedione and the like A combination of phthalazinone and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); phthalazine, a phthalazine derivative or a metal salt, or 4- (1-naphthyl) ) Derivatives such as phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetra Chlorophthalic anhydride) A quinazolinedione, benzoxazine or naphthoxazine derivative; a rhodium complex which functions not only as a color tone regulator but also as a source of halide ions for silver halide formation in situ, such as ammonium hexachlororhodate (III), bromide Rhodium, rhodium nitrate and hexachlororhodium (II
I) potassium salts and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide;
Benzoxazines such as 1,3-benzoxazine-2,4-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 (eg, 3,6-dimercapto) -1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene and 1,4-di (o-chlorophenyl)
-3,6-dimercapto-1H, 4H-2,3a, 5
6a-tetraazapentalene) and the like.

Of these, acid anhydrides are preferably used in the present invention. Acid anhydrides that can be particularly preferably used in the present invention include A-CO 2 formed by dehydration condensation of two molecules of a monocarboxylic acid.
Including those having a —O—CO—B structure in the molecule, A and B in the formula may be a substituent having a linear molecular structure or a substituent having a cyclic structure. Further, it may have an annular structure in which a part of these A and B are bonded. Also, A-SO ₂ -O-CO-B, A in which sulfonic acid is dehydrated and condensed.
—SO ₂ —O—SO ₂ —B may be used. The linear one is formed by dehydration of two molecules of aliphatic monocarboxylic acid. For example, acetic anhydride, propanoic anhydride, butanoic anhydride, pentanoic anhydride, caproic anhydride, lauric anhydride, anhydride Examples thereof include stearic acid, sebacic anhydride, arachidic anhydride, and behenic anhydride, and the aliphatic carboxylic acid preferably has 1 to 30 carbon atoms. Examples of the substituent having a cyclic structure include an aryl group and a heteroaryl group, and an aromatic carboxylic acid, for example, benzoic anhydride,
Pyridine carboxylic anhydride or derivatives thereof are included. Examples of those having a cyclic structure in which A and B are partially bonded include dibasic acid anhydrides such as phthalic anhydride and naphthalic anhydride.

A general example is shown below, but the present invention is not limited to this.

[0183]

Embedded image

In the present invention, it is preferable that at least one non-photosensitive layer is formed on the photosensitive layer. Further, in order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side as or opposite to the photosensitive layer, or a dye or pigment may be included in the photosensitive layer.

The photosensitive layer may have a multi-layer structure of a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. May be contained in any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

Suitable binders for use in the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) ), Li (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be dissolved in water or an organic solvent or in the form of an emulsion to cover and form the photothermographic layer, the non-photosensitive layer, and the like.

Such a photothermographic material may contain an antifoggant. As the antifoggant, for example, those described in U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-57234 are preferable.

When the photothermographic material of the present invention is used in a laser image setter, a He-Ne laser (633 nm) and a red semiconductor laser (670 n) are used.
m), infrared semiconductor laser (780 nm, 830 nm)
It is preferable to carry out the above.

The photothermographic material of the present invention can be provided with a dye-containing layer as an antihalation layer.
400 for He-Ne laser and red semiconductor laser
exposure wavelength in the range of at least 0.1 nm to 750 nm.
The dye is added so as to have an absorption of 3 or more, preferably 0.8 or more. 750nm-1 for infrared semiconductor laser
The dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range of 500 nm. One or more dyes may be used in combination. These dyes can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the opposite side of the photosensitive layer.
Further, a light or heat decolorable dye may be used.

The support used in the present invention has a thermal dimensional change rate of 0.04% or less under the heat development conditions where the maximum density of the exposed portion is 4.0 or more and the density of the unexposed portion is 0.2 or less.
Less than 4% support. The support is more preferably at most 0.03%, still more preferably at most 0.02%. The lower this change rate is, the better, but the lower limit is about 0.001% at present. A support exceeding this range is not preferred because the adhesion to the image forming layer on the support tends to deteriorate. Examples of preferred supports include polycarbonate (PC), polyethylene terephthalate (PET), and polyether sulfone (PE).
S), supports such as polyarylate (PAr), polyetheretherketone (PEEK), polysulfone (PSO), and syndiotactic polystyrene (SPS), and heat-treated supports thereof, and polyethylene naphthalate (PEN) ) Is heat-treated. Among them, PC, PET and those obtained by heat-treating them or those obtained by heat-treating PEN are preferable.
PET heat-treated with C is preferred.

Incidentally, the thermal dimensional ratio is usually determined in the longitudinal direction (M
D) and the width direction (TD), and it is preferable that both directions are less than 0.04%, but the case where either one is less than 0.04% is also included in the present invention.

These supports may contain organic and inorganic fine particles. Preferred fine particles include silica, alumina, calcium carbonate, titania, calcium chloride, cross-linked polymethyl methacrylate particles, cross-linked polystyrene particles, and the like. The preferred particle size is 0.02 to 3
μm or less, and a preferable addition amount is 10 to 1000 ppm. The Young's modulus of these supports is preferably 2000 to 8000 N / mm ² , more preferably 300 to
0 to 6000 N / mm ² .

The heat treatment of the support is performed before coating the photosensitive layer. Such a heat treatment is performed at 80 to 200 ° C, more preferably at 100 to 180 ° C, and still more preferably at 110 to 180 ° C.
It is preferable to carry out the heat treatment at a constant temperature within this temperature range, or to carry out the heat treatment while raising or cooling the temperature. Of these, heat treatment at a constant temperature or while cooling is preferable. This heat treatment time is 1 minute to 200 hours. If the time is less than 1 minute, a sufficient effect cannot be obtained. If the time exceeds 200 hours, the effect is saturated, and the support is likely to be colored or embrittled, and the working efficiency is reduced.

The heat treatment of the support may be carried out while transporting the support in a roll form or a web form. When heat treatment is performed in the form of a roll, 1. A method in which a roll is heat-treated in a thermostat from room temperature (low-temperature winding method); The method may be carried out by any method such as a method in which the film is heated to a predetermined temperature during web transport and then rolled and heat-treated (high-temperature winding method). The method of (1) requires time to raise and lower the temperature, but has the advantage of requiring less capital investment. The method of (1) requires a high-temperature winding facility, but has the advantage that the time for raising the temperature can be omitted.

In the heat treatment in the form of a roll, due to the heat shrinkage stress during the heat treatment, surface defects such as wrinkles due to tightening of the winding and a cut end of the winding core are likely to occur. For this reason, it is desirable to take measures such as applying knurls to both ends of the support and slightly raising only the ends so as to prevent the cut end of the winding core from appearing. The width of the knurl is 2 to 50 mm, more preferably 5 to 30 mm, still more preferably 7 to 20 mm, and the height is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, and most preferably 2 to 20 μm. The knurl may be pressed in one direction or in both directions, and the temperature at the time of application is preferably Tg or more. In addition, the absolute humidity of the atmosphere at the time of performing such a heat treatment is 2 kg / air of air from the viewpoint of blocking during the heat treatment.
It is better to carry out with 2 g or less, more preferably 16 g or less, further preferably 8 g or less. Although there is no particular lower limit for this absolute humidity, the content of water per kg of air is usually 0.1%.
g.

The winding tension per unit width of the roll is such that the initial tension is 300 to 7500 kPa and the tension at the end of winding is 30.
0 to 7500 kPa is preferable. Below this range, the roll is liable to undergo slack deformation due to its own weight during heat treatment due to gentle winding. On the other hand, above this value, wrinkles due to tight winding are likely to occur. A more preferred range of the initial tension is 50
0 to 4000 kPa, and a more preferable range of the winding end is 200 to 3500 kPa. It is more preferable that the winding is performed while the initial tension is larger than the winding end tension.

In the present invention, the transfer tension of the support at the time of heat treatment is 1300 kPa or less, more preferably 1000 kPa or less.
In particular, the pressure is preferably set to 400 kPa or less. Then, the thermal dimensional change rate of the support is remarkably reduced, and the adhesion between the photosensitive material and the support is also improved.

The diameter of the core of the present invention is 100 to 100.
Preferably it is 600 mm. If the diameter is smaller than this, the heat treatment generates spots and wrinkles. 60
If it exceeds 0 mm, it becomes bulky and inconvenient in storage and transportation, which is not practical. Preferably, the diameter is 150-
It is 450 mm, more preferably 200 to 400 mm. Preferably, the cross section of the winding core is a perfect circle.

It is preferable that the material of these winding cores has a sufficient elastic modulus during the heat treatment and is not easily deformed by the heat shrinkage stress of the support.
A core made of (fiber reinforced plastic) is preferred.

On the other hand, when heat treatment is performed in the form of a web, a heat treatment zone is required. However, a better surface state of the support can be obtained as compared with heat treatment in the form of a roll, which is more preferable. The transport tension at this time is preferably 10 to 1300 kPa, more preferably 30 to 1000 kPa, and still more preferably 50 to 40 kPa.
0 kPa. Such a low tension must be achieved especially in the heat treatment zone, and a suction drum is set before and after the heat treatment zone. During this time, it is necessary to convey at a low tension, and to wind up the subsequent winding process with a higher tension. More preferred. Winding is preferably performed after sufficiently cooling with a chilling roll or the like in order to reduce dimensional change. Further, the force applied to the support includes not only the winding tension but also a stress accompanying thermal contraction generated by itself. For this reason,
It is more preferable to measure the heat shrinkage in advance, and control so that the feeding amount becomes larger than the winding amount by the measured amount. Such heat treatment is preferably performed for 1 minute to 60 minutes, more preferably 3 minutes to 30 minutes, still more preferably 5 minutes to 15 minutes. Since a long heat treatment zone is required to increase the heat treatment time, it is preferable to divide the heat treatment into two or more heat treatments.

[0202] These heat treatments are preferably performed after the undercoating. This is because the dimensional change rate tends to increase due to the tension in the undercoating step. In addition, by including the matting particles in the undercoat layer, the flatness at the time of the roll heat treatment can be improved.

[0203]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

As a support, a PET base having a thickness of 125 μm without heat treatment and a heat-treated support were used. Where PE
T is the transport tension at the time of transport 1500 kPa, 1000 kP
a, 400 kPa, which was changed. And
A heat treatment was performed at 130 ° C. for 15 minutes while transporting each at 20 m / min.

Example 1 (Preparation of silver halide emulsion A) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0, and then silver nitrate 74 was prepared.
g of an aqueous solution containing 370 ml of sodium chloride, potassium bromide, potassium iodide and [Ir (NO) Cl ₅ ] salt in a molar ratio of (60/38/2) at 1 × 10 ⁻⁶ per mol of silver.
370 ml of an aqueous solution containing 1 × 10 ⁻⁶ mol per mol of silver and rhodium chloride was added by a controlled double jet method while maintaining the pAg at 7.7. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 8 with NaOH, and pAg6.
By adjusting the particle size to 5, reduction sensitization was performed, and the average grain size was adjusted to 0.1.
06 μm, variation coefficient of projected diameter area with monodispersity of 10% 8
%, And a [100] face ratio of 87% were obtained. Emulsion A was prepared by subjecting this emulsion to coagulation sedimentation using a gelatin coagulant and desalting.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A) 1.51 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later, 1M silver nitrate solution 14
7 ml was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion has formed, the water is removed and an additional 6
After washing with water and removing water several times, it was dried.

(Preparation of Photosensitive Emulsion) The prepared preform emulsion was divided, and 544 g of a solution of polyvinyl butyral (average molecular weight: 3,000) in methyl ethyl ketone (17% by mass) and 107 g of toluene were gradually added and mixed. 30 ° C. at 27.58 MPa by a media disperser using a ZrO ₂ bead mill having a diameter of 0.5 mm.
Dispersion was performed for 10 minutes.

(Preparation of Photothermographic Material) The following layers were simultaneously coated on both sides of the support to prepare a photothermographic material sample. The drying was performed at 60 ° C. for 15 minutes.

<Back Side Coating> A solution having the following composition was applied on the support so that the dry film thickness was 2.5 μm.

Cellulose acetate butyrate 90 g Dye D2-1 0.42 g Dye D3-5 0.42 g Matting agent: Monodispersity 15% Average particle size 8 μm Monodisperse silica 5.4 g C ₈ F ₁₇ (CH ₂ CH ₂ O _{) 12 C 8 F 17 3g C} 9 F 17 -C 6 H 4 -SO 3 Na 1g methylethylketone 900g

[0212]

Embedded image

<Coating on the Photosensitive Layer Side> (Lower Layer of Photosensitive Layer) A solution having the following composition was coated on the support coated with the back layer so as to have a thickness of 2 μm.

Butyral resin (Sekisui Chemical BM1) 10 g Methyl ethyl ketone 90 g (Photosensitive layer) A solution having the following composition was placed on the lower layer of the photosensitive layer at a thickness of 10 μm.
Was applied so as to have a film thickness.

Preform emulsion 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Developer (1 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane in 20% methanol solution) 10 ml 2,4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml Tribromomethylsulfoquinoline (5% methanol solution) 17 ml Development accelerator P-51 0.3 g Vinyl compound (described in Table 1) 0.2 g Hydrazine compound (described in Table 1) 0.4 g Phthalazine 0.6g 4-Methylphthalic acid 0.25g Tetraclo Calcium carbonate phthalate 0.2g average particle size 3μm 0.1g A-4 (20% methanol solution) 20.5 ml isocyanate compound 0.5 g (Mobay Corp., Desmodur N3300)

[0216]

Embedded image

(Protective Layer) A solution having the following composition was simultaneously applied to the upper layer of the photosensitive layer so that the dry film thickness became 2 μm.

[0218] Acetone 50g methylethylketone 210g cellulose acetate butyrate 23g matting agent: monodisperse degree of 10% average particle size 4μm monodisperse silica _{0.05g CH 2 = CHSO 2 CH 2} CH 2 OCH 2 CH 2 SO 2 CH = CH 2 0 0.35 g fluorinated surfactant C ₁₂ F ₂₅ (CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 0.01 g C ₈ F ₁₇ —C ₆ H ₄ —SO ₃ Na 0.01 g Sample No. Nos. 1-27 were produced. However, the sample No. With respect to 20 to 27, the addition amounts of the vinyl compound and the hydrazine compound contained in the photosensitive layer were halved. The following evaluation was performed using the above samples.

<< Exposure and development treatment >> Thereafter, 780 nm
300 using a Dolev 2dry manufactured by Scitex, an image setter equipped with a semiconductor laser
Exposure the halftone dots to change the exposure amount in 5% steps with a line,
Thermal development was performed at 120 ° C. for 25 seconds.

<< Measurement of Density >> The maximum density and the density of the unexposed area were measured using a density measuring machine (Xrite).

<< Evaluation of Hardening >> A 5% halftone dot of the exposed and heat-developed sample was visually observed with a 100-power loupe to evaluate the halftone dot image quality. The one without any fringe was ranked 5 and the rank dropped as fringes were seen. A rank of less than 3 ranks is not practical.

<< Evaluation of Thermal Development Unevenness >> The sample was separately exposed and thermally developed so that the color density became 1.0. Using this sample, development unevenness was visually evaluated. When there was no unevenness, it was set to 5, and as the unevenness appeared, the rank was lowered. Less than three ranks are not practical. Table 1 shows the results.

<< Evaluation of Coating with Film >> A commercially available cellotape (registered trademark) was attached to the emulsion surface of the developed sample, and the sample was vigorously peeled off. An object whose film surface did not peel at all was ranked as 5 ranks, and was ranked according to the degree of peeling. Less than 3 is not practical.

[0224]

[Table 1]

The sample to which the tension during the heat treatment was applied was small, and the sample to which the vinyl compound was added was smaller than the sample to which the thermal hydrazine compound was added, in terms of the dimensional change rate, high contrast, maximum density, unexposed portion density, heat development unevenness, and film development. It can be seen that the attachment is good. Further, the effect of the combined use of the vinyl compound and the hydrazine compound was also confirmed.

Example 2 This example was carried out under the same conditions as in Example 1 except that the developing conditions were changed. Table 2 shows the results.

[0227]

[Table 2]

According to Table 2, the heat development conditions were from 100 ° C. to 1 ° C.
It can be seen that a sample having a thermal dimensional change within the range of the present invention in the range of 5 to 50 seconds at 30 ° C. has good performance.

Example 3 Samples 301 to 318 were produced in the same manner as in Example 1.
However, for each sample, a heat-treated support was used at a transport tension of 400 kPa during the heat treatment, and the vinyl compound and hydrazine compound used for the photosensitive layer and the acid anhydride further added are shown in Table 3. Indicated.

[0230] Evaluations were made on the samples, which were stored at 23 ° C and 48% RH for 3 days after storage, and those stored at 50 ° C and 48% RH for 3 days. The exposed area density was measured and compared.

[0231]

[Table 3]

In the present invention, it can be seen that the one to which the acid anhydride was added was stable in that the maximum density and the unexposed portion density after storage at a high temperature were unchanged.

[0233]

According to the present invention, a photothermographic material for printing and a processing method of a completely dry processing which can cope with color printing and high definition printing are obtained.

Claims (3)

[Claims] 1. A photothermographic material containing an organic silver salt, a silver halide, a developer and a vinyl compound on a support. The photothermographic material is exposed imagewise and thermally developed. Part has a maximum density of 4.0 or more and the unexposed part has a density of 0.
A photothermographic material characterized in that the thermal dimensional change of the photothermographic material is less than 0.04% under a heat development condition of 2 or less. 2. The photothermographic material according to claim 1, wherein the vinyl compound is represented by the following general formula (G). Embedded image [Wherein, X represents an electron-withdrawing group. W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxyoxalyl group, a thiooxalyl group, an oxamoyl group, an oxycarbonyl group, or a thiocarbonyl group. Group, carbamoyl group, thiocarbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfonyl group,
Thiosulfonyl group, sulfamoyl group, oxysulfinyl group, thiosulfinyl group, sulfinamoyl group, phosphoryl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Amino group, alkylamino group, arylamino group, heteroarylamino group, acylamino group, oxycarbonylamino group,
Sulfonamide group, oxysulfonylamino group, ureido group, sulfamoylamino group, nitro group, imidoyl group, N-acylimidoyl group, N-sulfonylimidoyl group, dicyanoethylene group, ammonium group, sulfonium group, phosphonium group Represents a pyrylium group. R is a halogen atom, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, alkenyloxy group, acyloxy group, alkoxycarbonyloxy group, aminocarbonyloxy group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group , Alkenylthio, acylthio, alkoxycarbonylthio, aminocarbonylthio, organic or inorganic salts of hydroxy or mercapto, amino, alkylamino, cyclic amino, acylamino, oxycarbonylamino, hetero Represents a ring group, a ureido group, or a sulfonamide group. X and W, and X and R may be bonded to each other to form a cyclic structure. ] 3. A processing method comprising subjecting the photothermographic material according to claim 1 to a thermal development process at a development temperature of 100 ° C. to 130 ° C. for 5 seconds to 50 seconds.