JP2001117207A - Heat-developed image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-developed image forming method in which stable photographic performance is ensured by processing with an automatic heat processing machine independently of the situation of the image forming layer of a heat developable photosensitive material conveyed and any conveying method may be adopted after exposure. SOLUTION: When a latent image is formed with a laser beam in a heat developable photosensitive material for producing a printing plate containing photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrast enhancer and a binder and then heat development is carried out, a heat developing system having a mechanism for discriminating the information on the photosensitive material before development is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable image forming method suitable for a photothermographic material for printing plate making.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image. As this technique, for example, US Pat. Nos. 3,152,904 and 3,487,075
And D. "Dry Silver Photog" by Morgan
graphic Materials) "(Handbo
ok of Imaging Materials, M
arcelDekker, Inc. 48, 199
As described in 1) etc., an organic silver salt on a support,
Thermal developing materials containing photosensitive silver halide grains, a reducing agent and a binder are known.

[0003] These heat-developable materials are stable at room temperature, but are developed by heating to a high temperature (for example, 80 ° C to 140 ° C) after exposure. That is, heating produces silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent.

Incidentally, photosensitive silver halide, organic silver salts,
When a photothermographic material for printing plate making containing a reducing agent for silver ions and a binder, hydrazine or a quaternary onium salt is developed by a thermal developing machine, 1) operator error, 2) thermal development by a transport method after exposure. Often, the orientation of the image forming layer of the photosensitive material is reversed. Depending on whether the image forming layer is transported upward or downward during development with an automatic thermal developing machine, the thermal conductivity transmitted to the photothermographic material changes, and the characteristics of the photosensitive material change, causing a problem. . In particular, in the photothermographic material for printing plate making, the photographic performance varies depending on the transport method during development.

[0005] An important problem in the past is how to maintain the temperature during thermal development stably and uniformly to carry out development. For example, the following patent discloses the countermeasure. Regarding an automatic thermal developing machine, Japanese Patent Application Laid-Open No.
The heat-developable image forming method of developing at 50 ° C. is described in 9-29.
No. 2695, medical image is heated at 120 ± 10 ° C, ±
Methods of processing with a 3 ° C. width accuracy and a development time of 5 to 30 seconds, respectively, are disclosed. Also, JP-A-9-29
Nos. 7386, 9-297385 and 9-29738
No. 4 discloses a method for controlling the outer peripheral surface temperature of a heater drum. Japanese Patent Publication No. 10-500496 discloses a method of developing by heating a drum.
No. 97 discloses a method of heating and developing with a plurality of rollers, and JP-A No. 10-500506 discloses a temperature control device of a rotatable drum which is electrically heated and a temperature signal of a surface of a cylindrical drum is detected to generate a temperature signal. Dispensing devices are each disclosed.

However, in the prior art, the orientation of the image forming layer often fluctuates, and there is a problem that the photographic performance changes.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object the purpose of automatic thermal development regardless of the orientation of the image forming layer of the photothermographic material being conveyed. An object of the present invention is to provide a heat-developable image forming method which can obtain stable photographic performance by processing with a machine and does not select a transportation method after exposure.

[0008]

An object of the present invention is to provide a photothermographic material for printing plate making containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder. In forming a latent image and performing heat development, a heat development image forming method using a heat development system having a mechanism for discriminating information on a photosensitive material before development, the information on the photosensitive material to be discriminated is a size, The material information is front and back, the heat development system further has a mechanism for reversing the photosensitive material, printing plate making containing photosensitive silver halide, organic silver salt, reducing agent for silver ion, high contrast agent and binder Image forming method using a heat developing system having a mechanism for inverting the photosensitive material in forming a latent image of the photothermographic material for use with a laser beam and thermally developing the latent image. Developing at a temperature of 30 ° C. to 150 ° C. for a time of 1 second to 60 seconds at a temperature lower than the thermal developing temperature by 5 ° C. or more for 3 seconds to 30 seconds and post-heat developing; And a belt conveyor type horizontal transfer system.

Hereinafter, the present invention will be described in detail for each item.

<< Image Forming Method >> As a method of exposing and recording an image on a photothermographic material, for example, a method of directly photographing, a method of exposing through a film using a printer or a enlarger, and an exposing apparatus such as a copying machine are used. make use of,
A method in which an original image is scanned and exposed through a slit or the like, and a method in which image information is scanned and exposed by emitting a light emitting diode, various lasers (laser diode, gas laser, etc.) via an electric signal (Japanese Patent Laid-Open No. 2-129625, Image display devices such as CRT, liquid crystal display, electroluminescence display, plasma display, etc., which are described in Japanese Patent Application Nos. 3-338182, 4-9388, 4-281442. And exposing directly or through an optical system.

As a light source for recording an image on a photothermographic material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, and the like, US Pat. No. 4,500,626, and JP-A-2-53378. And the light source and the exposure method described in JP-A-2-54672 can be used. Alternatively, image exposure can be performed using a wavelength conversion element by combining a non-linear optical material with a light source such as a laser beam. The present invention focuses on the problem associated with the reversal of the front and back in a transport system after exposure by a laser imagesetter. Typical laser light sources include argon ion lasers, helium neon lasers and infrared semiconductor laser diodes.

Semiconductor laser diodes are widely used in graphic arts as photographic recording elements in image forming apparatuses. The image forming apparatus typically uses a laser diode having an output of 5 to 250 mW. The use of laser diodes follows from the well-established use of lasers (argon ions, helium neon, etc.) common in silver halide based recording elements.

In the present invention, the exposure is preferably performed by laser scanning exposure, and there is no particular limitation as long as the angle between the exposed surface of the photosensitive material and the scanning laser beam is in the range of 1 to 90 °. The beam spot diameter on the exposed surface of the photosensitive material when the laser beam is scanned on the photosensitive material is preferably 300 μm or less, and is not particularly limited.
The exposure in the present invention may use a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi.

As a laser scanning method, there are an outer cylindrical scan, an inner cylindrical scan, and a plane scan. In outer surface cylindrical scanning, laser exposure is performed while rotating a drum around which a photosensitive material is wound around the outer surface, and rotation of the drum is used as main scanning and movement of laser light is used as sub-scanning. In the inner cylindrical scanning, the photosensitive material is fixed on the inner surface of the drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system, and a part of the optical system or Sub-scanning is performed in the axial direction by moving the whole in a straight line parallel to the axis of the drum. In the planar scanning, the main scanning of the laser beam is performed by combining a polygon mirror or a galvanometer mirror with an fθ lens or the like, and the sub-scanning is performed by moving the photosensitive material.
Outer cylinder scanning and inner cylinder scanning are easier to improve the accuracy of the optical system and are more suitable for high-density recording.

In the present invention, various exposure scanning methods,
Alternatively, the image forming layer of the photothermographic material may be directed upward or downward by a transport method after exposure (including a case where an operator manually transports the photothermographic material to the automatic thermal developing machine after exposure). Further, it is preferable to transmit the discrimination result after the exposure to a mechanism for inverting the photosensitive material.

In the present invention, it is preferable to provide a system for feeding back information obtained at the time of discrimination to the exposure system to vary the exposure energy. In this case, it is preferable to have 1) a system for storing the initial exposure energy amount to the photosensitive material, and 2) a system for varying the exposure energy based on the obtained information. More preferably, in addition to the above, it is preferable to have a manual input unit, a learning function (an automatic correction function, estimating a change in photosensitive material by reading information during running, and calculating an exposure energy amount, and the like).

It is preferable that information is fed back at any time, hourly, or daily, but these can be freely adjusted by an operator who uses the information.

The photosensitive material after laser exposure is developed by heat. As a heating means for heat development, a heating element described in JP-A-61-145544 such as a mode having a conductive heating element layer, a halogen lamp, a sheet heater, and the like can be used.

As a specific mode, 1) a method of placing the device in an oven at a constant temperature for a predetermined time, 2) a method of conveying the inside of the oven maintained at a constant temperature at a constant speed, and 3) heating to a constant temperature Media (metal roller, silicone rubber,
There is no particular limitation as long as it is a method of contacting urethane rubber, paper, a fluorinated medium or the like for a predetermined time. In addition, a preheating section may be provided before or after the developing section separately from the developing section. In this case, the conditions described in 1) to 3) are indispensable as in the former case. In the present invention, 1) and 2)
The horizontal transfer method in the form as described above is preferred. A conveyor type system is particularly preferable even in the horizontal transfer system.

The preferred temperature during thermal development is 30 ° C to 15 ° C.
0 ° C., but the preferred temperature range of the developing section is 10 ° C.
0-150 ° C, more preferably 100-140 ° C. In the present invention, it is preferable to include a step of performing a heat treatment at a temperature lower than the developing temperature by 5 ° C. or more before the developing section.
The temperature range is preferably from 100 to 120 ° C, and from 100 to 11 ° C.
5 ° C. is more preferred. The processing time of the thermal development is preferably 1 to 60 seconds, more preferably 5 to 50 seconds. The preferable processing time range of the developing section is 3 to 30 seconds, more preferably 5 to 30 seconds. A preferable processing time range of the preheating section is 3 to 30.
In seconds, 5 to 25 seconds are more preferable. In performing such thermal development, it is preferable that tension is not applied to the photosensitive material.
There is no particular limitation as long as it is 10 kg or less. However, care must be taken because applying too much tension may change the dimensions of the photosensitive material and cause problems.

Further, since the photosensitive material itself changes the heat transfer coefficient due to the delicate flow of air in the heat developing section and greatly changes the image reproducibility, the porosity in the heating section (preheating section + developing section) is changed. = Gap volume (cm ³ ) in heating section / volume (cm ³ ) in heating section) is preferably in the range of 0.002 to 0.3, more preferably 0.002 to 0.28.

As for the determination of the information of the photosensitive material, it is preferable to determine the type of the exposing machine and the transport method by specifically determining the size, and to transmit the result to a mechanism for reversing the photosensitive material. Alternatively, the front and back sides may be determined.

As a method of determining the size of the photosensitive material, it is preferable to arrange the sensors in the width direction in the transport path and to determine the size by a mechanism for detecting when the photosensitive material passes.

The orientation of the image forming layer is determined by determining the front and back of the photosensitive material. As a method for determining the front and back sides, any method may be used as long as it is a method derived from the degree of matte on the front side. 2) a method of measuring and discriminating the surface roughness on the front and back, 3) the smoothness of the front and back can be judged on the basis of a suction property in vacuum for a certain time,
Preferably, the front and back are determined by the method 1). Note that the heat development system may include only means for determining the image forming surface, and may be manually inverted by an operator.

The mechanism for inverting the photosensitive material may be any method. When it is located before the automatic thermal developing machine, it is preferable that the automatic thermal developing machine is provided with a unit different from the automatic thermal developing machine, a single unit or a unit that is integrated with the exposing machine and is reversed after exposure. Further, when the unit is different from the automatic developing machine as described above, it is preferable that the film after the reversal is automatically conveyed by a belt conveyor or a roller in order to introduce the film into the automatic thermal developing machine, but it may be a manual operation. . The top-to-top time of the photosensitive material from the head of the reversing unit to the automatic machine introduction port is preferably 5 to 60 seconds, and more preferably 5 to 30 seconds.

When installed in the automatic thermal developing machine, any configuration is possible as long as heat of 100 ° C. or more is not transmitted from the developing section in the automatic thermal developing machine to the reversing unit, and the position is in front of the heating unit. Is a mandatory requirement.

Further, the heat developing system has only a mechanism for reversing the photosensitive material, and an operator who recognizes the front and back directions of the heat-developable photosensitive material after conveyance by the type of the exposure machine can determine the photosensitive material according to the determination result. May be activated.

The reversing unit is disclosed in Japanese Patent Application Laid-Open No. 8-188318.
Nos. 8-108978, 8-26531, 8
A reversing unit (switchback system) used in -50381 or the like can be used.

In the present invention, means for detecting the information of the developed image may be provided, and the information may be fed back to the exposure condition and the development condition. As the information, it is preferable to measure and detect the color, width, and density, and more preferably, it is density. When measuring color and density, it can be measured by an optical sensor (for example, an absorbance meter, a transmittance meter, or the like). The location of the optical sensor is not particularly limited as long as it is arranged after development. When measuring the density, it is preferable that the photosensitive material has a test chart such as a scale. However, the density may be measured to calculate Dmax and Dmin, and the data may be fed back based on the data. Dmin when development proceeds too much
Rises extremely or the developing temperature changes, D
It is possible to prevent max from changing.

When the width is measured, a sensor for detecting passage of the photosensitive material is provided at the width or length of the automatic developing machine, and the width or length of the photosensitive material is detected by converting from the transport speed and the passage time. Information can be obtained. The location of the sensor is not particularly limited as long as it is arranged before or after development. Preferably, either before or after the cost. More preferably after development.

In the present invention, the developing section is located adjacent to the heating section.
A temperature control mechanism is required to keep the temperature of the preheating section constant. To control the temperature, it is preferable to control and adjust the temperature using a thermostat or the like.

In the present invention, a temperature feedback system and an exposure feedback system may be provided.

As the temperature feedback system, it is preferable to have a system that varies the temperature in conjunction with the thermostat. In this case, it is preferable to have 1) a system for storing the initial development heating temperature, and 2) a system for varying the heating temperature based on the obtained information. More preferably, in addition to the above, it is preferable to have a manual input unit, a learning function (automatic correction function, reading of light-sensitive material information during running, estimating a change in light-sensitive material, calculating a heating temperature, and the like), and the like.

As for the feedback, it is preferable to feed back information as needed, hourly or daily, but these can be freely adjusted by the operator used.

The automatic thermal developing machine may be integrated with the exposure system, in which case the transport system is integrated with a bridge or the like. It is also possible to have a preheating section before the developing section. After the developing unit, a cooling unit may be provided to suppress the progress of development of the heat-developable photosensitive material or to control the curl of the support. When it has a cooling part, its temperature is preferably in the range of 10 to 80C, more preferably in the range of 20 to 60C.

In the present invention, it is preferable to have an ON / OFF mechanism for transporting the heat automatic developing machine when correcting the temperature and the exposure condition by feeding back after obtaining the information of the photosensitive material. This indicates that the operation is performed only when the signal of No is output from the information detection unit, and that the information is changed from ON to OFF, but a manual operation may be performed in some cases. in this case,
This is because it is useful when maintenance, malfunction or film transport failure occurs.

<< Photothermographic Material >> Silver halide functions as an optical sensor. The smaller the average particle size is, the smaller the particle size is, preferably 0.1 μm or less, and more preferably 0.1 μm or less.
01 μm to 0.1 μm, especially 0.02 μm to 0.08 μ
m is preferred. 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. In the case of non-normal crystals, for example, in the case of spherical, 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 equation is 40 or less. More preferably, 30
Or less, particularly preferably 0.1 to 20 particles.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Another preferred form of silver halide is tabular grains. The term “tabular grains” as used herein means those having an aspect ratio = r / h of 3 or more, where the square root of the projected area is r μm and the vertical thickness is h μm. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is 0.
1 μm or less, preferably 0.01 μm
~ 0.08 µm is preferred.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion may be prepared by any method such as an acid method, a neutral method, and an ammonia method, and the method of reacting a soluble silver salt and a soluble halide salt includes a one-side mixing method, a simultaneous mixing method, and the like. May be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source.
Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

The photosensitive silver halide grains can be desalted by washing with water using a method known in the art such as a noodle method or a flocculation method. The photosensitive silver halide grains are preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source, especially a long chain (10 to 30, preferably 15 to 25, And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
It is described in. Preferred silver sources are 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 can be obtained by a forward 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.

The average particle size of the organic silver particles is 0.2 to 1.2 μm.
m, more preferably 0.35 to
1 μm. The organic silver particles are preferably monodispersed, and preferably have a monodispersity of 1 to 30.

In order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g to 2.2 g per m ² in terms of silver.

Examples of suitable reducing agents are described in US Pat.
No. 0,448, No. 3,773,512, No. 3,5
No. 93,863 and Research Disclo
Sure Nos. 17029 and 29996. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0047]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, t- butyl ).

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

[0050]

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[0051]

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The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

The photothermographic material of the present invention contains a high contrast agent, and the high contrast agent is preferably selected from the following hydrazine derivatives, quaternary onium salts, and vinyl compounds.

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

[0055]

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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 a 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, and 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably a -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)
A preferred G ₀ representing a (G ₁ D ₁ ) — group 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).

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

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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More preferred hydrazine derivatives are represented by the following formulas (H-1), (H-2), (H-3) and (H-4)
Or a compound represented by (H-5).

[0071]

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In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₁₄ represents a heterocyclic oxy group or a heteroarylthio group. A ₁ and A ₂ both represent a hydrogen atom or one is a hydrogen atom and the other is an acyl group, an alkylsulfonyl group or an oxalyl group.

[0073]

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In the formula, R ₂₁ represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. R ₂₂ represents hydrogen, an alkylamino group, an arylamino group, or a heteroarylamino group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0075]

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In the formula, G ₃₁ and G ₃₂ represent a — (CO) p- group,
C (= S)-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents an R ₃₃ — group or an iminomethylene group, and p is 1
Or an integer of 2, and 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 or an amino group. However, when G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. R ₃₁ and R ₃₂ represent a monovalent substituent. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0077]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₄₄ and R ₄₅ represent a substituted or unsubstituted alkyl group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0079]

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In the formula, R ₅₁ represents an alkyl group, alkenyl group, alkynyl group, aralkyl group, heterocyclic group, substituted amino group, alkylamino group, arylamino group, heterocyclic amino group, hydrazino group, alkoxy group, aryl group Oxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, heterocyclic thiocarbonyl group, carbamoyl A carbamoyloxy group, a carbamoylthio group, a carbazoyl group, an oxalyl group, an oxamoyl group, an alkoxyureido group, an aryloxyureido group, or a heterocyclic oxyureido group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

In the general formula (H-1), the aryl group represented by R ₁₁ , R ₁₂ and R ₁₃ is a phenyl group,
Examples include a methylphenyl group and a naphthyl group, and examples of the heteroaryl group include a triazole residue, an imidazole residue, a pyridine residue, a furan residue, and a thiophene residue. Further, R ₁₁ , R ₁₂ and R ₁₃ may be bonded via an arbitrary linking group. Examples of the substituent which R ₁₁ , R ₁₂ and R ₁₃ may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (a pyridinio group) Etc.), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, Carboxyl group, imide group, amino group, carboxamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Primary ammonium group, (alkyl, aryl or heterocycle)
Thio, mercapto, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl,
A sulfo group, a sulfamoyl group, an acylsulfamoyl group, an (alkyl or aryl) sulfonyluureido group,
(Alkyl or aryl) sulfonylcarbamoyl group,
Examples include a halogen atom, a cyano group, a nitro group, and a phosphoric amide group. All of R ₁₁ , R ₁₂ and R ₁₃ are preferably phenyl groups, and more preferably all are unsubstituted phenyl groups.

The heteroaryloxy group represented by R ₁₄ includes a pyridyloxy group, an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group,
A furyloxy group, a thienyloxy group, a pyrazolyloxy group, an imidazolyloxy group, and the like.Examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, Examples include a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

The acyl group represented by A ₁ or A ₂ includes:
Examples include an acetyl group, a trifluoroacetyl group, and a benzoyl group. Examples of the sulfonyl group include a methanesulfonyl group and a toluenesulfonyl group. Examples of the oxalyl group include an ethoxalyl group. Both A ₁ and A ₂ are preferably hydrogen atoms.

In the general formula (H-2), examples of the alkyl group represented by R ₂₁ 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. And an aryl group, a heteroaryl group, and a substituent which may be present include R
₁₁ is the same as R ₁₂ and R _13. R ₂₁ is preferably an aryl group or a heteroaryl group, and particularly preferably a phenyl group. The alkylamino group represented by R _22, methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, diethylamino group, etc. ethylmethylamino group. Examples of the arylamino group anilino Examples of the group and heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. Preferably the R ₂₂ is dimethylamino group or diethylamino group.

In the general formula (H-3), the monovalent substituent represented by R ₃₁ and R ₃₂ has R ₁₁ , R ₁₂ and R ₁₃ described in the general formula (H-1). The substituents may be the same as those described above, but are preferably an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or an amino group, more preferably an aryl group or an alkoxy group, and particularly preferably R ₃₁ is a phenyl group. Wherein _R32 is a tert-butoxycarbonyl group. G ₃₁ and G ₃₂ are preferably -CO-
Group, a -COCO- group, a sulfonyl group or a -CS- group, and more preferably, both are a -CO- group or a sulfonyl group.

In formula (H-4), R ₄₁ , R ₄₂ and R ₄₃ are the same as R ₁₁ , R ₁₂ and R ₁₃ in formula (H-1).
Is synonymous with Preferably, all are phenyl groups, and all are unsubstituted phenyl groups. R ₄₄ , R ₄₅
Examples of the substituted or unsubstituted alkyl group represented by are a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, a diphenylmethyl group, and the like. Is the case.

The specific examples of the compounds represented by formulas (H-1) to (H-5) are shown below, but it should not be construed that the invention is limited thereto.

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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 1
Compounds 1 to 12 described in 1. These hydrazine derivatives can be synthesized by a known method.

The layer to which the hydrazine derivative and the vinyl compound described later are added is a photosensitive layer containing silver halide and / or a layer adjacent to the photosensitive layer. The optimum amount of these additives is not uniform depending on the grain 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 mol per mol of silver halide. ^-1 mol, especially 1
The range is preferably from 0 ^-5 mol to 10 ^-2 mol.

As the quaternary onium compound, a compound represented by the following formula (P) is preferably used.

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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.

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 may be formed by linking R _{1 to} R ₄ 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.

[0111] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as 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].

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, which 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.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

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.

[0118] 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.

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The substituents R ₅ and R ₆ of the phenyl group 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 for the phenyl group has been reported 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.

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound is described in Chemical Reviews vol. 55
p. 335-483 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.

The quaternary onium compound may be used alone or
More than one species may be used in combination. The compound may be added to any of the constituent layers of the photosensitive material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, further to the photosensitive layer and / or an adjacent layer thereof.

As the vinyl compound, those represented by the following general formula (G) are preferred.

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In the general formula (G), X and R are represented in a cis form, but the general formula (G) includes a trans form of X and R. This is the same in the structural representation of a specific compound.

In the formula, X represents an electron-withdrawing group, and W is 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. Group, thiooxalyl group, oxamoyl group, oxycarbonyl group, thiocarbonyl group, carbamoyl group, thiocarbamoyl group,
Sulfonyl group, sulfinyl group, oxysulfonyl group,
Thiosulfinyl group, sulfamoyl group, oxysulfinyl group, sulfinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group, N-sulfonylimino group, dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, pyrylium group Represents an immonium group.

R is a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group,
Organic or inorganic salts of an alkylthio group, an arylthio group, a heterocyclic thio group, an alkenylthio group, an acylthio group, an alkoxycarbonylthio group, an aminocarbonylthio group, a hydroxy group or a mercapto group (for example, sodium salt, potassium salt, silver salt) Etc.), an amino group, an alkylamino group, a cyclic amino group (for example, a pyrrolidino group), an acylamino group, an oxycarbonylamino group, a heterocyclic group (5-
A 6-membered nitrogen-containing heterocycle, for example, a benztriazolyl group,
Imidazolyl group, triazolyl group, tetrazolyl group, etc.), ureido group, and sulfonamide group. X and W,
X and R may be bonded to each other to form a cyclic structure. Examples of the ring formed by X and W include pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β-ketolactam and the like.

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, cyano groups, acyl groups (acetyl, trifluoroacetyl, formyl, etc.),
Thioacetyl group (thioacetyl, thioformyl, etc.), oxalyl group (methyloxalyl, etc.), oxyoxalyl group (ethoxalyl, etc.), thiooxalyl group (ethylthiooxalyl, etc.), oxamoyl group (methyloxamoyl, etc.), oxycarbonyl group (ethoxycarbonyl, etc.) etc),
Carboxyl group, thiocarbonyl group (such as ethylthiocarbonyl), carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group (such as ethoxysulfonyl), thiosulfonyl group (such as ethylthiosulfonyl), sulfamoyl group, and oxysulfinyl Group (such as methoxysulfinyl), thiosulfinyl group (such as methylthiosulfinyl), sulfinamoyl group,
Sphinamoyl group, phosphoryl group, nitro group, imino group, N-carbonylimino group (N-acetylimino, etc.), N-sulfonylimino group (N-methanesulfonylimino, etc.), dicyanoethylene group, ammonium group, sulfonium group, phosphonium Groups, a pyrylium group, and an immonium group, and a heterocyclic group in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, and the like form a ring is also included. 0.30 as σp value
The above substituents are particularly preferred.

Examples of the alkyl group represented by W include methyl, ethyl, trifluoromethyl and the like, examples of the alkenyl group include vinyl, halogen-substituted vinyl and cyanovinyl, and examples of the alkynyl group include 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. W is σ
A p-value is preferably a positive electron-withdrawing group, and more preferably, the value is 0.30 or more.

Of the above substituents for R, preferably a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group,
Halogen atom, an organic or inorganic salt of a hydroxy group or a mercapto group, and a heterocyclic group, more preferably a hydroxy group, an alkoxy group, an organic or inorganic salt of a hydroxy group or a mercapto group, a heterocyclic group, Particularly preferred is an organic or inorganic salt of a hydroxy group, a hydroxy group or a mercapto group.

Among the substituents of X and W, those having a thioether bond in the substituent are preferable.

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

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The binder suitable for the photothermographic material according to the present invention is transparent or translucent and generally colorless, and includes 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) ) Kind, po (Urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). Although it may be hydrophilic or hydrophobic, in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after thermal development. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, and cellulose acetate butyrate are particularly preferably used.

In the photothermographic material according to the present invention, various surfactants can be used as a coating aid. Among them, fluorine-based surfactants improve the charging characteristics,
It is preferably used to prevent spot-like coating failure.

The photothermographic material according to the present invention can contain a color tone agent for suppressing the color tone of silver, if necessary. Examples of suitable toning agents that can be employed are Research Disclo
Sure No. 17029. In addition, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development to control development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like.

The photothermographic material according to the present invention may contain an antifoggant.

A sensitizing dye can be used in the photothermographic material according to the present invention. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
m17643 IV-A (p.23, December 1978),
Item 1831X (August 1978, p. 437)
Or cited in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. These additives and the other additives mentioned above are
h Disclosure Item 17029 (19
June 1978 p. Compounds described in 9 to 15) can be preferably used.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent image deformation after development. , Polyethylene naphthalate). A heat-treated plastic support can also be used.

Among them, a preferred support is a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene-based polymer having a syndiotactic structure.

The thickness of the support is preferably 100 to 150 μm. Preferably it is 110 to 130 μm. The thinner the layer, the better the heat transfer from the backing layer side. However, if the thickness is less than 110 μm, the layer is rapidly heated and the development unevenness is deteriorated. If the thickness is more than 150 μm, the heat capacity of the support becomes too high and the development is not sufficiently performed under the desired development conditions.

The support is preferably heat-treated, and the purpose is to shrink it in advance by the heat treatment.
For example, polyethylene phthalate (PET)
190 ° C is good. Since the glass transition point is 80 ° C., there is no meaning below 80 ° C., and when it is 80 ° C. or more and less than 100 ° C., shrinkage is not sufficient. If the temperature exceeds 190 ° C., there is a risk that the softening will be severe and the melting will occur.

[0181]

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

Example 1 (Preparation of Subbed PET Support) A commercially available biaxially stretched heat-fixed PET film having a thickness of 120 μm was coated on both surfaces with 8 W /
m ² · m of corona discharge treatment, the following undercoating coating liquid a-1 is applied to one side to a dry film thickness of 0.8 μm, and dried to form an undercoating layer A-1, and vice versa. On the side surface, the following antistatic coating solution b-1 was applied with a dry film thickness of 0.8 μm
And dried to form an antistatic subbing layer B-
It was set to 1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g polystyrene fine particles (average particle diameter 3 μm) 0.05 g colloidal silica (average particle diameter 90 μm) 0 0.1 g Finished to 1 L with water << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) Styrene ( 20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g hexa Styrene-1,6-bis (ethyleneurea) subsequently finished into 1L with 0.8g water, the undercoat layer A-1 and the upper surface undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating solution a-2 for lower undercoat >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 L with water << Lower upper coating liquid b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5g (C-6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish to 1L with water

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(Heat Treatment of Support) In the undercoat drying step of the undercoated support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of Emulsion A) In 900 ml of water, 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved and adjusted to a temperature of 35 ° C. and a pH of 3.0.
g of an aqueous solution containing sodium chloride, potassium bromide and potassium iodide in a molar ratio of (60/38/2) and [Ir (NO) Cl ₅ ] salt in an amount of 1 × 10 ⁻⁶ per mole of silver. The mol and rhodium chloride salt were added by the controlled double jet method at 1 × 10 ⁻⁶ mol per mol of silver while keeping 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 the pAg was adjusted to 6.5 to perform reduction sensitization to obtain an average particle size of 0.06 μm.
The coefficient of variation of the projected diameter area with a monodispersity of 10% is 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and desalting treatment was performed.

(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) 15.1 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 a solution of polyvinyl butyral (number average molecular weight 3000) in methyl ethyl ketone (17) was prepared.
544 g and toluene 107 g were gradually added and mixed, and then at 30 ° C., 1 ° C. and 4000 psi with a media disperser using a 0.5 mm-size ZrO ₂ bead mill.
Dispersion was performed for 0 minutes.

The following layers were simultaneously coated on both sides of the support to prepare a sample. The drying was performed at 60 ° C. for 15 minutes.

(Coating on Back Side) A liquid having the following composition was coated on layer B-2 of the support so as to have a dry film thickness of 5 μm.

Cellulose acetate butyrate 15 ml / m ² (10% methyl ethyl ketone solution) Dye-A 7 mg / m ² Dye-B 7 mg / m ² Matting agent: monodispersity 15% Average particle size 8 μm monodisperse silica 90 mg / m ² _{C 8 F 17 (CH 2 CH} 2 O) 12 C 8 F 17 50mg / m 2 C 8 F 17 -C 6 H 4 -SO 3 Na 10mg / m 2

[0195]

Embedded image

(Coating on Photosensitive Layer Side) A solution having the following composition was coated on the A-2 layer of the support so that the coated silver amount was 1.8 g / m ² . The dry film thickness was 15 μm.

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 Oxidizing agent ( 10 ml methanol solution) 1.2 ml 2-4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml hydrazine Derivative H-26 0.4 g Hardening agent P-51 0.3 g Phthalazine 0.6 g 4-Methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate with an average particle size of 3 μm 0.1 g A-4 (20% 20.5 ml isocyanate compound Product (Desmodur N3300, manufactured by Mobay Corporation) 0.5 g

[0198]

Embedded image

Surface protective layer: A solution having the following composition was simultaneously coated on the photosensitive layer in a dry film thickness of 2.7 μm.

[0200] Acetone 5 ml / m ² methyl ethyl ketone 21 ml / m ² Cellulose acetate butyrate 2.3 mg / m ² methanol 7 ml / m ² phthalazine ^{250mg / m 2 A-4 (} 20% methanol solution) 10 ml / m ² Matting agent: Single Monodisperse silica having a degree of dispersion of 10% and an average particle size of 4 μm 5 mg / m ² CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ OCH ₂ CH ₂ SO ₂ CH = CH ₂ 35 mg / m ² Fluorine surfactant C ₁₂ F ₂₅ ( CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 10 mg / m ² C ₈ F ₁₇ -C ₆ H ₄ —SO ₃ Na 10 mg / m ² << Exposure and development treatment >> Thereafter, an image setter equipped with a 780 nm semiconductor laser NEC F
Solid exposure was performed using a T-280R type with an energy of -logE.

<< Automatic Thermal Developing Machine >> Evaluation was performed by using an automatic thermal developing machine having cross sections of the developing section shown in FIGS. Exposure and development were performed at 23 ° C and 50% R.
We went in a room conditioned to H.

FIGS. 1 to 3 are cross-sectional views of examples of the heating unit. 1A and 1B show a horizontal transport type using a transport roller, in which a heat medium 2 is arranged so as to surround the photosensitive material transported in the direction → and the transport roller 1. FIG. 2 (a)
Is a horizontal transport type using a belt conveyor 3,
A heat medium 2 having a gap is set only in a region where the photosensitive material is conveyed, and has a preheating portion. FIG.
(B) shows a case where the preheating section is carried by a roller and the heat developing section is carried by a belt conveyor. FIG. 2C shows a combination of the belt conveyor conveyance and the roller conveyance in the heat developing section. FIG. 3 shows a state in which a roller group 91 is arranged around the periphery of the heat drum 53, the photosensitive material to be conveyed is pressed against the heat drum and heated, and the whole is covered with the heat medium 2,
Heating from the back is also performed.
An intermittent roller group 92 is arranged on three peripheral edges to perform preheating.

<< Reversing Unit >> FIG. 4 shows a reversing unit used in this embodiment. FIG. 4A shows normal conveyance when the image forming surface is on the setting side, and the photosensitive material conveyed in the right direction is guided by the conveyance roller pair 40 and introduced into the conveyance path toward the automatic thermal developing machine. The sheet is sent to the discharge roller pair 42 by the drive roller pair 41, and is discharged as it is without turning over. At this time, the flapper (path switching means) 44 rotatable around the support shaft 43 forms a discharge path.

FIG. 4B illustrates a switchback mechanism in the case of turning over. → The photosensitive material carried in from the direction is introduced into the carry-in port 45 formed by the rotation of the flapper 44, guided by the carry roller pair 46, and formed in the carry path formed by the second flapper 47 and the guide member 48. Then, the sheet is conveyed by the guide roller pair 49 to the switchback path including the switchback roller pair 50. When the photosensitive material passage detecting means 51 and the photosensitive material detecting means 52 detect the passage of the rear end of the photosensitive material and the leading end of the photosensitive material, the switchback roller pair 50 rotates in the reverse direction, and starts to reversely transport the photosensitive material in the carrying-in direction. At the same time, the second flapper 47 rotates to form a discharge path, and the photosensitive material having passed through the guide roller pair 49 is turned upside down and sent to the discharge roller pair 42 through the discharge path to be discharged.

<< Evaluation of unevenness in processing stability >> 440 mm × 61
Dmin, Dm at the position of the photosensitive material when a photosensitive material having a size of 0 mm is manufactured and passed one by one using an exposure machine and a developing machine.
The rate of change of ax was evaluated. That is, the difference between the maximum Dmin value and the minimum Dmin is measured at nine points shown in FIG.
Change rate, the difference between the maximum Dmax value and the minimum Dmax is Dmax
The change rate was used. Note that the development tip is on the side of measurement points 1 to 3.

<< Evaluation of Image Reproducibility >> Ten sheets of the photothermographic material prepared as described above were exposed and developed by an automatic thermal developing machine shown in the evaluation table, and the sensitometric image obtained was evaluated. Of the sensitivity was expressed as a percentage. The sensitivity here is a relative value of a reciprocal of an exposure amount giving a density of 1.0.

<< Dependency by Exposure Machine Type >> The FT-280R type manufactured by NEC, which is an image setter machine, has different front and back sides after transport depending on the size of the photosensitive material. The adopted system flow was selected from the following embodiments.

<< Embodiment Flow According to the Present Invention >> 1) After exposure by an image setter, the operator receives the result of the discrimination by the front / back discrimination unit and turns over as necessary, and transports it to an automatic thermal developing machine to carry out thermal development. After exposure by the image setter, discrimination information by the front / back discrimination unit is transmitted to the reversing unit, and the reversing unit reverses the photosensitive material as necessary based on the information.
Automatically transported to an automatic thermal developing machine and subjected to thermal development 3) In flow 2), an integrated reversing unit and automatic thermal developing machine are used 4) In flow 2), front / back discrimination unit, reversing unit and automatic thermal developing 5) Before exposure by the image setter, the operator inputs the front / back discrimination information to the device where the reversing unit and the automatic thermal developing machine are integrated. 6) The front / back discrimination unit in the flow 4) 7) In step 2), a unit in which a front / back discrimination unit and a reversing unit are integrated is used. 8) A front / back discrimination unit that discriminates according to the size of the photosensitive material is used as a pre-process before the imagesetter exposure. And the discrimination information is transmitted to the device in which the reversing unit and the automatic thermal developing machine are integrated. 9) In the flow 5), the reversing unit and The developing machine is a separate device, and if necessary, the photosensitive material is
10) In flow 9), a front / back discrimination unit for discriminating according to the size of the photosensitive material is provided in a process before the imagesetter exposure.

For comparison, 11) after exposure with an image setter, heat development using an automatic thermal developing machine as it is; 12) after exposure using an image setter, reverse by a reversing unit, and then heat development using an automatic thermal developing machine. Was.

Tables 1 and 2 show the above results. Regarding the evaluation, exposure and development were repeated three times while changing the size of the photosensitive material so that the front and back after the conveyance were different, and the average was taken.

[0211]

[Table 1]

[0212]

[Table 2]

[0213]

According to the present invention, stable photographic performance can be obtained by processing with an automatic thermal developing machine, and the transport method after exposure is not limited.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a horizontal transfer type heating unit using a transfer roller.

FIG. 2 is a cross-sectional view of an example of a horizontal transfer type heating unit using a belt conveyor.

FIG. 3 is a cross-sectional view of an example of a heating unit that uses both a heat drum and a heat medium.

FIG. 4 is a diagram illustrating an example of a mechanism of a reversing unit.

FIG. 5 is a diagram showing measurement points for processing stability unevenness evaluation.

[Description of Signs] 1 transport roller 2 heat medium 3 belt conveyor 40, 46 transport roller pair 41 drive roller pair 42 discharge roller pair 43 support shaft 44, 47 path switching means 48 guide member 49 guide roller pair 50 switchback roller pair 51 Photosensitive material passage detecting means 52 Photosensitive material detecting means 53 Heat drum 83 Preheat drum

Claims (9)

[Claims] 1. A method for forming a latent image with a laser beam on a photothermographic material for printing plate making containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder, followed by thermal development. A heat development image forming method using a heat development system having a mechanism for determining information on a photosensitive material before development. 2. The method according to claim 1, wherein the information on the photosensitive material to be determined is a size. 3. The heat-developable image forming method according to claim 1, wherein the information of the photosensitive material to be determined is front and back. 4. The heat development image forming method according to claim 3, wherein the heat development system further has a mechanism for reversing the photosensitive material. 5. A method for forming a latent image with a laser beam and thermally developing a photothermographic material for printing plate making containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions, a contrasting agent and a binder. A heat development image forming method, comprising using a heat development system having a mechanism for reversing a photosensitive material. 6. Temperature 30 ° C. to 150 ° C., time 1 second to 60
3. The method according to claim 1, wherein the development is performed within a range of seconds.
6. The heat-developable image forming method according to 3, 4, or 5. 7. The method according to claim 1, wherein the heat treatment is carried out at a temperature lower than the heat development temperature by 5 ° C. or more for 3 seconds to 30 seconds and post-heat development is performed. Thermal development image forming method. 8. The heat development image forming method according to claim 1, wherein a horizontal conveyance type automatic heat development machine is used. 9. The heat development image forming method according to claim 8, wherein the method is a belt conveyor type horizontal conveyance system.