JP3281623B2 - Development method of heat-developable image recording material and heat-developable image recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable image recording material and a method of developing the same, and more particularly, to a photolithographic process, and more particularly, to high-contrast photographic properties and excellent heat development suitability. And a developing method for the same.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic light-sensitive material is to scan an original drawing and to expose the silver halide photographic light-sensitive material on the basis of an image signal thereof, thereby obtaining a negative image or a positive image corresponding to the image of the original drawing. An image forming method based on a so-called scanner method for forming an image is known. Further, there is a demand for a scanner photosensitive material having a super-high contrast characteristic for a case of printing directly on a printing plate without going through a turning process after being output from a scanner to a film or a scanner light source having a soft beam profile.

There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technology for forming an image by thermal development is a system that can simplify environmental preservation and image forming means.

In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental protection and space saving.
Therefore, there is a need for a technology relating to a photothermographic material for photoengraving, which can be efficiently exposed by a laser scanner or a laser imagesetter and can form a clear black image having high resolution and sharpness. It has been. In these photosensitive heat developing materials,
By eliminating the use of solution processing chemicals, it is possible to provide customers with a simpler and more environmentally friendly thermal development processing system.

A method of forming an image by thermal development is described in, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075, and D.C. Crosta Bohr (Klos
terboer) "Heat treated silver system (T
hermally Processed SilverSystems) "(ImagingPros and Materials)
cesses and Materials) Neblette 8th edition, J.M. Sturge, V.S. Walworth, A .;
Edited by Shepp, Chapter 9, Section 279, 198
It is listed in 9 years. Such photosensitive materials are prepared by dispersing a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at normal temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

Conventionally, photothermographic materials of this type have been known, but most of these materials are exposed to light by applying a coating solution using an organic solvent such as toluene, methyl ethyl ketone (MEK) or methanol as a solvent. The active layer is formed. The use of an organic solvent as a solvent is disadvantageous not only in adverse effects on the human body in the manufacturing process but also in cost due to recovery of the solvent and the like.

Therefore, a method of forming a photosensitive layer (hereinafter also referred to as "aqueous photosensitive layer") using a coating solution of an aqueous solvent which does not have such a concern has been considered. For example, JP-A-49-52626 and JP-A-53-116144 disclose examples using gelatin as a binder. JP-A-50-151138 discloses an example using polyvinyl alcohol as a binder.

Further, Japanese Patent Application Laid-Open No. 60-61747 discloses an example in which gelatin and polyvinyl alcohol are used in combination. In WO 97/04355, a water-soluble or water-dispersible binder is used for an image forming layer and a protective layer is used for a protective layer. Examples using a water-soluble binder such as gelatin, polyvinyl alcohol, and a cellulose derivative are described. As another example, JP-A-58-28737 describes an example of a photosensitive layer using water-soluble polyvinyl acetal as a binder.

Certainly, when such a binder is used, the photosensitive layer can be formed using a coating solution of an aqueous solvent, and the advantages in terms of environment and cost are great. However,
When a polymer such as gelatin, polyvinyl alcohol, or water-soluble polyacetal is used as a binder, dehydration shrinkage and thermal expansion of the binder occur simultaneously during thermal development, which differs from the thermal expansion behavior of the support. Only unsuitable films are obtained for color printing to be used together.

On the other hand, devices and methods for thermally developing heat-developable recording materials are generally known, for example, Svendsen US Pat. No. 3,629,549 and Brewitz US Pat. No. 36480.
No. 19, U.S. Pat. No. 3,709,472 to Kreitz et al., Svendse.
n) U.S. Pat. No. 4,518,845. Sbendson U.S. Pat. Nos. 3,629,549 and 4,518,845 both disclose a developing device having a thermally insulated drum concentrically mounted within a heating member.

A sheet of film to be developed engages the drum and is driven around a heating member. However, this type of heat developing apparatus is not suitable for using a film having a relatively soft thermoplastic polymer binder in the outermost layer. That is, since the surface on the side supporting the emulsion is in contact with the insulating drum or the heating member, the outermost layer of the film is left with scratch marks and adhesion marks.

Another type of thermal developing device includes a heating drum that electrostatically charges the film during development so as to hold the film. In such an apparatus, the outermost layer of the film supporting the emulsion does not come into contact with the drum or other components, so that the above-mentioned scratch marks are not formed. However, the electrostatic devices used to hold the film on the drum during thermal development are not of a shape that is relatively complex and suitable for thermally developing large films.

[0013] Recently, International Publication WO97-1318 has been proposed.
In the heat developing machine disclosed in the specification of JP-A No. 1 (1993), a small-diameter roller is densely arranged on a heating drum, sandwiched between the drum and the small-diameter roller, and heated and transported. This method is considered relatively well and does not leave wrinkles or scratch marks on the film, but a heat-developable image recording material having a protective layer and a back layer using a latex of a polymer having a low glass transition temperature as a binder. When developing, the unevenness of the gloss caused by the adhesion to the drum surface and the adhesion to the small-diameter roller occurs, and in rare cases, the unevenness of the development density caused by the thermal expansion of the film occurs. I will.

Therefore, a water-based photosensitive material which is excellent in environmental and cost aspects, has a good coating surface quality, does not cause density unevenness during development, and is particularly suitable for thermal development which does not cause conveyance failure (jamming) in thermal development processing. As a processing method, the roller is driven by bringing the surface on the image forming layer side of the heat-developable image recording material into contact with the roller, and the surface of the back surface is brought into contact with the smooth surface and slipped, and the heat-developable image recording material is conveyed. The apparatus uses a heat-developable image recording material in which the ratio of the coefficient of friction between the surface on the image forming layer side and the roller surface to the coefficient of friction between the back surface and the smooth surface at the heat development processing temperature is 1.5 or more. A method of heat development was proposed (Japanese Patent Application No. 10-34).
6561). However, in the case of having a preheating section and a heat development processing section, when the friction coefficient between the surface of the back surface and the smooth surface is large, even if the friction coefficient ratio between the surface on the image forming layer side and the surface of the back surface is 1 .5 or more,
There is a problem that scratches and uneven density occur, and improvement thereof has been strongly desired.

[0015]

The object of the present invention is to provide an image free from unevenness in processing for photoengraving, in particular, for a scanner imagesetter, having good transportability and stable generation of no abrasions. An object of the present invention is to provide a heat-developable image recording material having a suitable heat-development processability and a method for developing the same.

[0016]

The inventor of the present invention has conducted intensive studies in order to solve the above-mentioned problems. As a result, the desired effect can be obtained by adjusting the linear velocity ratio between the preheating section and the heat development processing section. The inventors have found that the present invention can be obtained, and have provided the present invention.

That is, the present invention relates to a heat-developable image recording material having at least one image-forming layer on a support and at least one protective layer provided on the image-forming layer, comprising a pre-heating unit A development processing method of processing with a thermal development processing apparatus having a development processing section; the heat-developable image recording material is conveyed by a counter roller in a preheating section, and a surface on the side having the image forming layer in the thermal development processing section. Is brought into contact with a driving roller, and while the surface opposite to the side having the image forming layer (back surface) is brought into contact with a smooth surface while being slid and transported for development processing, the linear velocity (R the ratio of _a) and the linear velocity of the heat development section (R _B) (R _a /
R _B: hereinafter also referred to as a linear speed ratio) is 95.0% to 99.9
% Of a heat-developable image recording material. In the present specification, “to” is a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

In the method of the present invention, 10 to 40 mm / sec
It is preferable to carry out development processing at a linear velocity of c. Further, it is preferable that at least the surface of the roller of the heat development processing device that comes into contact with the surface of the heat development image recording material having the image forming layer is formed of rubber having a rubber hardness of 50 degrees or less, particularly silicone rubber. In addition, the smooth surface of the thermal development processing apparatus is made of an aromatic polyamide nonwoven fabric or Teflon.
It is preferably formed of a nonwoven fabric made of ^TM ( polytetrafluoroethylene: PTFE). Further, a smooth surface on the side that comes into contact with the surface (back surface) opposite to the image forming layer when the heat-developable image recording material is transported, and a surface of the heat-developable image recording material that contacts or faces the smooth surface. Processing is preferably performed by a heat development processing apparatus having a heat development processing unit having a clearance of 0 to 2 mm from the surface of the drive roller that comes into contact with the surface on the image forming layer side during transport.

The heat-developable image recording material to be processed by the development processing method of the present invention has a coefficient of friction (μe) between the surface having the image forming layer and the roller surface of the heat-development processing part at the temperature of the heat development processing. Thermal development image recording wherein the ratio (μe / μb) of the friction coefficient (μb) between the surface (back surface) opposite to the side having the image forming layer and the smooth surface of the thermal development processing section is 1.5 or more. Preferably, it is a material. Further, the heat-developable image recording material to be processed by the developing method of the present invention has a surface (back surface) opposite to the side having the image forming layer at the temperature of the heat developing process and a smooth surface of the heat-developed portion. A heat-developable image recording material having a coefficient of friction of 1.0 or less is preferable, and a heat-developable image recording material using a polymer latex as a binder for the image forming layer and the protective layer is preferable. Further, the heat-developable image recording material to be processed by the developing method of the present invention,
On the side opposite to the side having the image forming layer, a relative humidity of 20
% Is preferably a heat-developable image recording material having at least one conductive layer having a surface specific resistance of 1 × 10 ¹² Ω or less, and a back layer on the side opposite to the side having the image forming layer. And a heat-developable image recording material using a polymer latex as a binder for the back layer. The present invention also provides the heat-developable image recording material itself for processing by the development processing method of the present invention.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The method for developing a heat-developable image-recording material of the present invention comprises a method of developing a heat-developable image-recording material having at least one image forming layer on a support and at least one protective layer provided on the image forming layer. And a development processing method of performing processing using a thermal development processing apparatus having a preheating unit and a thermal development processing unit. In the present invention, in the heat development processing device, the roller is driven by bringing the surface on the image forming layer side of the heat-developable image recording material into contact with the roller in the pre-heating unit and in the heat development processing unit, and the back surface. Is brought into contact with a smooth surface and slid to transport the heat-developable image recording material. At this time, the linear velocity ratio between the preheating section and the heat development processing section was 95.0.
By performing the development processing under the conditions of% to 99.9%, scratches and density unevenness are eliminated, and stable thermal development suitability can be achieved. Line speed ratio is 96% ~
More preferably, the developing treatment is performed under the condition of 99.5%. If the linear velocity ratio is less than 95.0%, abrasion, jamming, and the like occur, causing poor transportability and unevenness in density. 99.
If it exceeds 9%, the transportability deteriorates, which is not preferable.

In the heat development processing apparatus (heat development machine) used in the present invention, the preheating section is conveyed by an opposing roller, and the heat development processing section is driven by the roller on the side having the image forming layer of the heat development image recording material. The type of the heat developing machine is not particularly limited as long as it is a heat developing machine that conveys the paper by sliding the opposite back surface to a smooth surface. As the heating means, the pre-heating unit may use a heat roller for both or one of the opposed rollers, and a plate heater or the like for the upper and / or lower parts of the pre-heating unit. A heat roller can be used as the drive roller on the side having the heat development, and a plate heater or the like can be used on the upper and / or lower part of the heat development processing section.

The preferred development temperature is from 80 to 250 ° C, more preferably from 100 to 140 ° C. The development time is preferably from 1 to 180 seconds, and more preferably from 10 to 90 seconds. As a method of preventing processing unevenness due to dimensional change during development processing due to heating of the heat-developable image-recording material, the image is not produced at a temperature of 80 ° C. to less than 115 ° C. (preferably 113 ° C. or less) for 5 seconds or more. After heating, a method of forming an image by performing heat development at 110 ° C. or higher (preferably 130 ° C. or lower) (a so-called multi-stage heating method) is effective. Temperature control accuracy is preferably within ± 3 ° C., more preferably ± 1 ° C., and even more preferably ± 1 ° C. at each site.
It is within 0.5 ° C.

The average linear velocity from insertion to discharge in the thermal development processor is preferably 10 to 50 mm / sec.
More preferably, it is 15 to 30 mm / sec. In particular,
The linear velocity of the preheating section and the heat development processing section is 10 to 40 m
m / sec.

At least the surface of the roller on the side having the image forming layer of the preheating section and / or the heat development processing section has
The rubber hardness (JIS K6301 spring hardness tester) is preferably 50 degrees or less, more preferably 20 degrees to 45 degrees, and still more preferably 0.5 mm or more, and preferably 1 mm or more. A roller coated with 10 mm rubber is used. As the rubber material, silicone rubber is preferably used.

The clearance between the smooth surface of the heat-developing portion of the heat-developing device and the surface of the drive roller in contact with or facing the smooth surface is preferably 0 to 2 mm, more preferably 0.0 mm. １．０1.0 mm.
If the clearance is less than 0 mm, poor conveyance of the heat-developable image recording material tends to occur, and if it exceeds 2 mm, the temperature control accuracy of the heat-development processing unit tends to deteriorate. Here, the smooth surface surface is a surface on the side where the back surface of the heat-developable image recording material comes into contact when the heat-developable image recording material is conveyed. When the surface of the smooth surface is formed of a material whose state changes, the surface includes such a material. For example, on the smooth surface where the nonwoven fabric is stuck to the surface layer, the tip of the nonwoven fabric becomes the smooth surface surface. The same applies to the surface of the drive roller.

The nip force of the first roller pair of the slow cooling section (C in FIG. 1) is preferably 5 to 50 g / cm, more preferably, a force for conveying the heat-developable image recording material. 15 to 30 g / cm.

FIG. 1 shows an example of the configuration of a heat developing machine used in the heat developing process of the heat-developable image recording material of the present invention. FIG. 1 is a side view of the heat developing machine. The heat developing machine shown in FIG. 1 carries a pair of carry-in rollers 11 (the lower roller is a heat roller) for carrying the heat-developable image recording material 10 into a heating section while correcting and preheating the heat-developable image recording material 10 in a planar shape, and the heat-developable image recording material 10 And a carry-out roller pair 12 that carries out the heat from the heating unit while correcting the surface to a flat shape. Thermally developed image recording material 10
Is developed while being transported from the carry-in roller pair 11 to the carry-out roller pair 12. The conveying means for conveying the photothermographic material 10 during the heat development is provided with a plurality of rollers 13 on the side where the surface having the image forming layer contacts, and the nonwoven fabric or the like on the side where the opposite back surface contacts. The bonded smooth surface 14 is provided. The back surface of the heat-developable image recording material 10 is conveyed by driving a plurality of rollers 13 which come into contact with the surface having the image forming layer, on the smooth surface 14. As the heating means, a heater 15 is provided at an upper portion of the roller 13 and a lower portion of the smooth surface 14 so as to be heated from both sides of the thermally developed image recording material 10. As a heating means in this case, a plate heater or the like can be used. Roller 13
Although the clearance between the heat-developable image recording material 10 and the smooth surface 14 varies depending on the member of the smooth surface, the clearance is appropriately adjusted. The clearance is preferably 0 to 2 mm as described above, more preferably 0.0 to 2 mm.
1.0 mm.

Surface Material of Roller 13 and Smooth Surface 1
The member No. 4 is durable at high temperature and is a heat-developable image recording material 1
The roller surface material is silicone rubber, and the smooth surface member is aromatic polyamide or Teflon ^™ ( polytetrafluoroethylene:
PTFE) is preferred. It is preferable to use a plurality of heaters as the heating means and to set the heating temperature freely.

The heating section is composed of a preheating section A having a carry-in roller pair 11 and a heat development processing section B having a heater 15. The preheating section A upstream of the heat development processing section B is provided. Is lower than the heat development temperature (for example, 10 to 50).
It is preferable that the temperature is set to be higher than the glass transition temperature (Tg) of the support of the photothermographic material 10 so that development unevenness does not occur.

A guide plate 16 is provided downstream of the thermal development processing section B, and a slow cooling section C having a pair of unloading rollers 12 and the guide plate 16 is provided. The guide plate 16 is preferably made of a material having low thermal conductivity, and is preferably cooled gradually. The cooling rate is preferably from 0.5 to 10C / sec.

The nip force of the discharge roller pair 12 is 5 to 5 as described above as a force for transporting the heat-developable image recording material.
0 g / cm, preferably 15 to 30 g / cm.
g / cm is preferred.

In the present invention, when the heat-developable image-recording material is subjected to heat-development, it is exposed to a high temperature of 110 ° C. or more, so that a part of the components contained in the heat-developable image-recording material,
Alternatively, some of the components decomposed by thermal development volatilize.
These volatile components may cause uneven development, corrode the components of the heat developing machine, precipitate at low temperatures, cause deformation of the screen as foreign matter, and adhere to the screen and become dirty. It is known to have a bad effect. In order to eliminate these effects, it is known to install a filter in the heat developing machine and optimally adjust the flow of air in the heat developing machine. .

For example, International Publication Nos. WO95 / 30933 and 97/21150, Japanese Translation of PCT International Publication No. 10-500
No. 496 discloses that a filter cartridge having a binding opening and a first opening for introducing volatile components and a second opening for discharging is used as a heating device for heating in contact with a film. Has been described. International Publication WO9
JP-A-6 / 12213 and JP-T-Hei 10-507403 describe a filter in which a heat-conductive condensation collector and a gas-absorbing particulate filter are combined.

Also, US Pat. No. 4,518,845,
Japanese Patent Publication No. 3-54331 describes a configuration having a device for removing vapor from a film, a pressure device for pressing the film against a heat transfer member, and a device for heating the heat transfer member. International Publication WO98 / 27458 describes removing a component that increases fog volatilizing from a film from the film surface. These can be appropriately and effectively combined and used in the developing method of the present invention.

Before carrying out the developing method of the present invention, the heat-developable image recording material must be exposed. The heat-developable image recording material may be exposed by any method, but it is preferable to use laser light as an exposure light source. As the laser light used in the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser, or the like is preferable. Further, a semiconductor laser and a second harmonic generation element can be used.

Some heat-developable image recording materials have low haze upon exposure and easily cause interference fringes. Examples of the technology for preventing the occurrence of interference fringes include a technology disclosed in Japanese Patent Application Laid-Open No. Hei 5-113548, in which a laser beam is obliquely incident on a heat-developable image recording material, and a technology disclosed in International Publication WO9.
A method using a multi-mode laser disclosed in Japanese Patent Application Laid-Open No. 5/31754 is known, and it is preferable to use these techniques.

To expose a heat-developable image recording material, use SPIE v
ol.169 Laser Printing 116-128 (197
9), JP-A-4-51043, International Publication WO95
It is preferable that the exposure is performed so that the laser beams overlap each other, as disclosed in US Pat.

The heat-developable image recording material to which the development processing method of the present invention is applied is a heat-developable image recording material having at least one image forming layer on a support and at least one protective layer provided on the image forming layer. It is a developed image recording material. The heat-developable image recording material to be processed in the present invention contains an organic silver salt on a support, and preferably further has an image forming layer containing a reducing agent and photosensitive silver halide, and at least an image forming layer is formed on the image forming layer. Preferably, one protective layer is provided. Also,
The heat-developable image recording material to be processed in the present invention preferably has at least one back layer on the side opposite to the image forming layer (back surface) with respect to the support.
A polymer latex is preferably used as a binder for the back layer. By using a polymer latex for these layers, aqueous coating using a solvent (dispersion medium) containing water as a main component becomes possible, which is advantageous in terms of environment and cost, and causes wrinkles during thermal development. No heat-developable image recording material is obtained. Further, by using a support which has been subjected to a predetermined heat treatment, a heat-developable image recording material having a small dimensional change before and after heat development can be obtained.

The polymer latex used as the binder is obtained by dispersing a water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used. For polymer latex, see "Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Polymer Publishing Association (1978))" and "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, published by Polymer Publishing) Publishing society (1993)), "Synthesis of synthetic latex (Souichi Muroi, published by Polymer Publishing Association (1
970))). The average particle size of the dispersed particles is 1 to 50000 nm, more preferably 5 to 1000 nm.
A range of about nm is preferable. There is no particular limitation on the particle size distribution of the dispersed particles, and those having a wide particle size distribution or those having a monodispersed particle size distribution may be used.

As the polymer latex, a so-called core / shell type latex other than a polymer latex having a normal uniform structure may be used. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

As for the glass transition temperature (Tg) of the polymer of the polymer latex used as the binder, the preferable temperature range differs between the protective layer, the back layer and the image forming layer. Since the protective layer and the back layer (especially the outermost layer) are in contact with various devices, the glass transition temperature is preferably 25 ° C. or more, particularly 25 ° C. to 100 ° C., from the viewpoint of film strength and prevention of adhesion failure. Has a glass transition temperature of -30 ° C to 40 ° C, and particularly preferably a glass transition temperature of 0 ° C to 40 ° C, in order to promote diffusion of a photographically useful material during thermal development and to obtain good photographic properties such as high Dmax and low fog. ° C. Further, the gel fraction of the polymer of the polymer latex used in the image forming layer is preferably 30% by mass to 90% by mass for the same reason. The gel fraction in this case was obtained by immersing a membrane sample formed at 70 ° C. in dry temperature in tetrahydrofuran (THF) at 25 ° C. for 24 hours using a polymer latex, quantifying insolubles, and calculating according to the following formula. It is.

Gel fraction (mass%) = [mass (g) of insoluble matter / mass (g) of membrane using polymer latex]
× 100

The minimum film forming temperature (MFT) of the polymer latex used in the present invention is preferably from -30 ° C to 90 ° C, more preferably from about 0 ° C to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film forming aid is an organic compound (usually an organic solvent) which is also called a temporary plasticizer and lowers the minimum film forming temperature of the polymer latex. For example, the above-mentioned "Synthetic Latex Chemistry (Souichi Muroi, published by Polymer Publishing Association (1970) ))"It is described in.

Examples of the polymer used in the polymer latex include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, and copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is 5 by weight average molecular weight.
000 to 1,000,000, preferably 10,000 to 10
About 0000 is preferable. If the molecular weight is too small, the mechanical strength as a binder is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

Specific examples of the polymer latex used as a binder for the heat-developable image recording material include methyl methacrylate / ethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, methyl Methacrylate / butyl acrylate copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / vinyl chloride / acrylic acid copolymer, vinylidene chloride / ethyl acrylate / acrylonitrile /
Methacrylic acid copolymer and the like can be mentioned. Such polymers are also commercially available, and the following polymers can be used. For example, as an example of an acrylic resin, Sebian A-4635, 46583, 4601 (all manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx81
1,814,821,820,857,857x2 (all made by Nippon Zeon Co., Ltd.), VONCORT R334
0, R3360, R3370, 4280, 2830, 2
210 (manufactured by Dainippon Ink and Chemicals, Inc.), Julimar ET-410, 530, SEK101-SEK301,
Examples of polyester resins such as FC30 and FC35 (all manufactured by Nippon Pure Chemical Co., Ltd.), Polysol F410, AM200, and AP50 (all manufactured by Showa High Polymer Co., Ltd.) include FINE.
TEX ES650, 611, 675, 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), WD-size, WMS
(Manufactured by Eastman Chemical Co., Ltd.) such as HYDRAN AP10, 20, 30, 4
0, VONDIC 1320NS (all manufactured by Dainippon Ink and Chemicals, Inc.) and other rubber-based resins such as LACSTAR
7310K, 3307B, 4700H, 7132C,
LQ-618-1 (all manufactured by Dainippon Ink and Chemicals, Inc.),
Nipol Lx416, 410, 430, 435, 2
507 (manufactured by Nippon Zeon Co., Ltd.), vinyl chloride resins such as Nipol G351 and G576 (manufactured by Nippon Zeon Co., Ltd.), and vinylidene chloride resin: L
Chemipearl S as an olefin resin such as 502, L513 (all manufactured by Asahi Kasei Kogyo Co., Ltd.), Aron D7020, D5040, D5071 (all manufactured by Toagosei Co., Ltd.)
120, SA100 (all manufactured by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone or as a blend of two or more as necessary.

Among these polymer latexes, acrylic-based, styrene-based, acryl / styrene-based, vinyl chloride-based, and vinylidene chloride-based polymer latexes are preferably used as the binder for the protective layer. Specifically, acrylic resin-based VONCOTRTR3370 , 4280, N
IPOL Lx857, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, methyl methacrylate / butyl acrylate copolymer, Nipol G576 of vinyl chloride resin, and Alon D5071 of vinylidene chloride resin are preferably used. More preferably, polymer latexes having different I / O values obtained by dividing the inorganic value by the organic value based on the organic conceptual diagram described in Japanese Patent Application No. 11-6872 can be used.

As a binder for the image forming layer, a styrene / butadiene polymer latex is preferably used. Specifically, a rubber-based resin, LACSTAR33
07B, Nipol Lx430, 435 are preferably used.

As the binder for the back layer, an acrylic, olefin or vinylidene chloride-based polymer latex is used. Specifically, an olefin such as an acrylic resin-based Julimer ET-410, Sebian A-4635, or Polysol F410 is used. Resin-based Chemipearl S12
0, vinylidene chloride-based L502, Alon D7020 and the like are preferable.

If necessary, a hydrophilic polymer such as polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose and hydroxypropylmethylcellulose may be added to the binder in an amount of 20% by mass or less of the whole binder. The amount of these hydrophilic polymers to be added is preferably 10% by mass or less of the total binder in the protective layer and the image forming layer.

The photographic constituent layer of the heat-developable image recording material is preferably prepared by applying an aqueous coating solution and then drying. However, the term "aqueous" as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating liquid is water. As components other than water of the coating solution, methyl alcohol, ethyl alcohol,
Water-miscible organic solvents such as isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, and oxyethyl phenyl ether can be used. .

The total amount of the binder for the protective layer is 0.2 to 1
0.0 g / m ² , more preferably 0.5 to 6.0 g / m ²
Is preferable. The total amount of the binder for the image forming layer is 0.2 to 30 g / m ² , more preferably 1.0 to 15 g.
/ M ² is preferred. The total amount of the binder for the back layer is 0.01 to 10.0 g / m ² , more preferably 0.0
A range of 5 to 5.0 g / m ² is preferred. To each layer, a crosslinking agent for crosslinking described in JP-A-2000-19678, a surfactant for improving coating properties, and the like may be added.

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

In the present invention, the coefficient of friction (μ) between the surface of the outermost layer on the side having the image forming layer of the heat-developable image recording material and the roller surface of the heat-development processor at the development processing temperature.
e) and the ratio of the coefficient of friction (μb) between the surface of the back surface outermost layer and the smooth surface of the heat developing machine is determined by the ratio of the heat-developable image-recording material in contact with the roller or the smooth surface member of the heat developing machine The coefficient of kinetic friction at a constant speed and a constant load is measured at the temperature of the heat development processing with the surface, and is determined by the following equation. Ratio of friction coefficient = dynamic friction coefficient (μe) between the roller member of the heat developing machine and the surface having the image forming layer / dynamic friction coefficient (μb) between the smooth surface member and the back surface of the heat developing machine

This value is 1.5 or more, and there is no particular upper limit, but it is about 30. Μb is 1.0
Hereinafter, it is preferably 0.8 to 0.05. The temperature of the heat development (excluding the heating temperature in the preheating) is usually constant, but the temperature of the heat development when changing the temperature is 80 ° C to 150 ° C, preferably 100 ° C to 130 ° C.
In this case, the friction coefficient ratio is calculated from μe and μb at the highest temperature.

In the present invention, the slipperiness of the outermost surface layer on the surface having the heat development processing machine member and the image forming layer and / or the opposite surface at the heat development processing temperature is determined by adding a slip agent to the outermost surface layer. It can be adjusted by changing the amount of addition. The slip agent in the present invention is not particularly limited, and any compound may be used as long as the compound reduces the friction coefficient of the object surface when it is present on the object surface, as compared with the case where it is not present.

Representative examples of the slip agent used in the present invention include, for example, US Pat. No. 3,042,522, British Patent No. 955,061 and US Pat. No. 3,080,317. No. 4,004,927
No. 4,047,958 and No. 3,
No. 489,567, British Patent 1,143,11
No. 8,454,043, and US Pat. No. 2,732,305.
No. 2,976,148, and No. 3,
No. 206,311, German Patent 1,284,29
No. 5, No. 1,284,294, etc., higher fatty acid type, alcohol type, acid amide type slip agents, British Patent No. 1,263,722, US Pat.
No. 933,516, metal soaps described in U.S. Pat. Nos. 2,588,765 and 3,121,0.
No. 60, UK Patent No. 1,198,387, etc., ester type and ether type slip agents, US Pat. Nos. 3,502,473 and 3,042,222.
And the like.

Specific examples of the slip agent preferably used include Cellsol 524 (main component carnauba wax), Polylon A, 393, H-481 (main component polyethylene wax), and Himicron G-110 (main component ethylene bisstearic acid). Amide), High Micron G-270
(Main component stearic acid amide) (all manufactured by Chukyo Yushi Co., Ltd.). Further, a compound represented by the following formula (W) is preferably used.

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In the formula (W), R represents an aliphatic group having 10 or more carbon atoms. M represents a cation. R is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group having 10 to 30 carbon atoms.

Representative substituents for R include, for example, halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), aryl group, heterocycle (heterocycle) group and quaternized nitrogen atom. A heterocyclic group (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a sulfonylcarbamoyl group, an acylcarbamoyl group, a sulfamoylcarbamoyl group, a carbazoyl group, an oxalyl group, An oxamoyl group, a cyano group, a thiocarbamoyl group, a hydroxy group, an alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy group unit), an aryloxy group, a heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group, acylamino group, sulfone Amide group, ureide group,
Thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group, (alkyl or aryl) sulfonyluureide Group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl,
Or heterocycle) thio group, (alkyl or aryl)
A sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric amide or a phosphoric ester structure, and the like. Can be These substituents may be further substituted with these substituents. Preferred substituents that R may have include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, a cyano group, and a nitro group. M is a monovalent cation, and is preferably an alkali metal cation such as Li ⁺ , Na ⁺ , and K ⁺ .

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

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The compound of the formula (W) used in the present invention is
It can be used by dissolving it in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like.

The compounds of the formula (W) may be used alone or in combination of two or more. The addition layer is not particularly limited as long as it is the outermost layer, but is preferably the outermost layer on the back surface. The amount of addition is represented by the coating amount per m ² of the recording material (total on both sides), and is 0.005 to 1.0 g.
/ M ² . Further, in the layer containing the compound of the formula (W), it is preferable that 75% by mass or more of the total binder is formed from a water-dispersible polymer latex. As the polymer latex, those described above can be used.

The amount of the slip agent used is 0.1 to 50% by mass, preferably 0.5 to 30% by mass of the binder amount of the added layer.

It is preferable to provide an undercoat layer containing a vinylidene chloride copolymer on both sides of the support of the heat-developable image recording material. At this time, the vinylidene chloride copolymer contains 70% by mass or more of a repeating unit of a vinylidene chloride monomer (hereinafter, also referred to as “vinylidene chloride monomer”).
When the amount of the vinylidene chloride monomer is less than 70% by mass, sufficient moisture-proof properties cannot be obtained, and the dimensional change over time after thermal development tends to increase. Further, the vinylidene chloride copolymer may contain a repeating unit of a carboxyl group-containing vinyl monomer (hereinafter, also referred to as “carboxyl group-containing vinyl monomer”) as another constituent repeating unit of the vinylidene chloride monomer. preferable. Including such a constitutional repeating unit is that a polymer (polymer) is crystallized only with a vinyl chloride monomer, and it is difficult to form a uniform film when a moisture-proof layer is applied. This is because a carboxyl group-containing vinyl monomer is indispensable for stabilizing the (polymer).

The vinylidene chloride copolymer has a viscosity of 70-99.
9% by weight, more preferably 85-99% by weight of vinylidene chloride monomer and 0.1-5% by weight, more preferably 0.1-5% by weight.
It is a copolymer containing 2 to 3% by mass of a carboxyl group-containing vinyl monomer. The carboxyl group-containing vinyl monomer used in the vinylidene chloride copolymer is a vinyl monomer having one or more carboxyl groups in a molecule, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, and citraconic acid. Can be mentioned.

The vinylidene chloride copolymer may contain, in addition to the vinylidene chloride monomer and the carboxyl group-containing monomer, a repeating unit of a monomer copolymerizable therewith.
Specific examples of these monomers include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, acrylamide, and styrene. These monomers may be used alone or in combination of two or more.

The vinylidene chloride copolymer used in the present invention has a weight average molecular weight of 45,000 or less, preferably 10,000 to 45,000. When the molecular weight is increased, the adhesiveness between the vinylidene chloride copolymer layer and the support layer such as polyester tends to be deteriorated.

The vinylidene chloride copolymer may be in the form of a solution in an organic solvent or in the form of an aqueous dispersion of latex, but the form of an aqueous dispersion of latex is preferred. In this case, a latex of polymer particles having a uniform structure or a latex of polymer particles having a so-called core-shell structure having different compositions in a core portion and a shell portion may be used.
The particle size and the like of the polymer particles in the latex are the same as those used for the binder of the image forming layer and the protective layer. The arrangement of the monomer units of the vinylidene chloride copolymer is not limited, and may be any of periodic, random, block, and the like.

Specific examples of the vinylidene chloride copolymer include the following. However, the numbers in parentheses indicate mass ratios. The average molecular weight indicates a mass average molecular weight. V-1 Latex of vinylidene chloride: methyl acrylate: acrylic acid (90: 9: 1) (average molecular weight 4200)
0) V-2 Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (8
7: 4: 4: 4: 1) latex (average molecular weight 400
00) V-3 vinylidene chloride: methyl methacrylate: glycidyl methacrylate: methacrylic acid (90: 6: 2:
2) latex (average molecular weight 38000) V-4 vinylidene chloride: ethyl methacrylate: 2-hydroxyethyl methacrylate: acrylic acid (90:
8: 1.5: 0.5) latex (average molecular weight 440)
00) V-5 core-shell type latex (core 90% by weight, shell 10% by weight) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (9
3: 3: 3: 0.9: 0.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (8
8: 3: 3: 3: 3) (average molecular weight 38000) V-6 core-shell type latex (core 70%, shell 30%) Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (9
2.5: 3: 3: 1: 0.5) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: methacrylic acid (90: 3: 3: 1: 3) (average molecular weight 20,000)

The vinylidene chloride copolymer may be used alone or in combination of two or more. The content of the vinylidene chloride copolymer in the heat-developable image recording material is 0.3 μm or more, preferably 0.3 μm to 4 μm, as a total film thickness per one side of the undercoat layer containing the vinylidene chloride copolymer.
m.

The vinylidene chloride copolymer layer as the undercoat layer is preferably provided as the first undercoat layer directly provided on the support, and is usually provided one layer on each side. May be provided in two or more layers.
When a multi-layer structure of two or more layers is used, the total amount of the vinylidene chloride copolymer may be in the above range.

As described above, since the vinylidene chloride copolymer layer is usually formed as a single layer, its thickness is preferably from 0.3 μm to 4 μm in order to obtain a good coated surface.
μm, more preferably 0.6 μm to 3 μm, and still more preferably 1.0 μm to 2 μm. Such a layer may contain a crosslinking agent, a matting agent, and the like in addition to the vinylidene chloride copolymer.

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

The support used for the heat-developable image-recording material has a thickness of from 130 to 130 to reduce internal strain remaining in the film at the time of biaxial stretching and to eliminate heat shrinkage distortion generated during heat development.
Polyester, particularly polyethylene terephthalate, which has been subjected to a heat treatment in a temperature range of 185 ° C. is preferably used.
Such a thermal relaxation treatment may be performed at a constant temperature within the temperature range, or may be performed while increasing the temperature.

The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. In the case where the transfer is carried out in the form of a web, the transfer tension of the support during the heat treatment is preferably relatively low, specifically, 7 kg.
/ Cm ² or less, particularly preferably 4.2 kg / cm ² or less. The lower limit of the transport tension at this time is not particularly limited, but is about 0.5 kg / cm ² .

Such a heat treatment is preferably carried out after a treatment for improving the adhesion of the image forming layer and the back layer to the support, an undercoat layer containing a vinylidene chloride copolymer, and the like are applied. . The dimensional change of the support after heating at 120 ° C. for 30 seconds after the heat treatment is −0.03% to + 0.01% in the machine direction (MD) and 0 to 0.04% in the transverse direction (TD). Is preferred.

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

The back layer or undercoat layer adjacent to the support of the heat-developable image recording material preferably contains a metal oxide in order to reduce dust adhesion. It is preferable that at least one of the layers provided on both sides of the body is a conductive layer. In particular, it is preferable that the back layer be a conductive layer. However, the conductive layer is preferably not the outermost back layer.
Here, the metal oxide used is disclosed in JP-A-61-2003.
No. 3, JP-A-56-82504 are particularly preferable.

The amount of the conductive metal oxide used is preferably 0.05 to ²⁰ g, and particularly preferably 0.1 to 10 g, per m ² of the heat-developable image recording material. The surface resistivity (surface resistivity) of the metal oxide-containing layer is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less in an atmosphere at 25 ° C. and a relative humidity of 20%.
Thereby, good antistatic properties can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually about 10 ⁷ Ω.

In the present invention, a better antistatic property can be obtained by using a fluorine-containing surfactant in addition to the above-mentioned metal oxide.

The preferred fluorine-containing surfactant used in the present invention has a fluoroalkyl group, a fluoroalkenyl group or a fluoroaryl group having 4 or more (usually 15 or less) carbon atoms, and an anionic group ( Sulfonic acid (salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cationic group (amine salt, ammonium salt,
Aromatic amine salts, sulfonium salts, phosphonium salts),
Surfactants having a betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue) No.

These fluorine-containing surfactants are disclosed in
-10722, British Patent No. 1,330,356, U.S. Patent Nos. 4,335,201 and 4,347,308, British Patent No. 1,417,
915, JP-A-55-149938 and JP-A-58-196544, British Patent No. 1,439,4.
No. 02, etc. Some of these specific examples are described below.

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The layer to which the fluorine-containing surfactant is added is not particularly limited as long as it is at least one layer of the heat-developable image recording material, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer, and a back layer. Can be. Among them, a preferable addition site is the surface protective layer, and either one of the image forming layer side and the back layer side may be used. However, it is more preferable that the compound is added to at least the image forming layer side surface protective layer. When the surface protective layer is composed of two or more layers, any of the layers may be used, or the surface protective layer may be further overcoated on the surface protective layer.

The amount of the fluorinated surfactant used may be 0.0001 to 1 g per m ² of the heat-developable image recording material, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003. ０．１0.1 g. Further, two or more kinds of fluorine-containing surfactants may be mixed.

The Beck smoothness is measured according to Japanese Industrial Standard (JIS).
It can be easily obtained according to P8119 “Method for testing smoothness of paper and paperboard with Beck tester” and TAPPI standard method T479.

The Beck smoothness of at least one of the surface having the image forming layer of the heat-developable image recording material and the surface of the outermost layer opposite to the surface, preferably both, is 2,000 seconds or less, more preferably 10 to 2,000 seconds. It is.

The Beck smoothness of the outermost surface layer of the heat-developable image recording material having the image forming layer and the outermost surface layer of the opposite surface are determined by the average particle size of fine particles called a matting agent contained in the layers on both surfaces. It can be controlled by variously changing the diameter and the amount of addition. The matting agent is preferably contained in the protective layer which is the outermost layer farthest from the support on the surface having the image forming layer, and is preferably contained in the back layer which is not the outermost layer on the opposite side.

In the present invention, the preferable average particle size of the matting agent is in the range of 1 to 10 μm. The preferable addition amount of the matting agent in the present invention is in the range of 5 to 400 mg / m ² , particularly 10 to 200 mg / m ² .

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic characteristics. Examples of inorganic matting agents include silicon dioxide, oxides of titanium and aluminum, carbonates of zinc and calcium, sulfates of barium and calcium, and silicates of calcium and aluminum. Examples include matting agents for organic polymers such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof.

In the present invention, the porous matting agent described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, JP-A-4-127142, page 3 upper right column An alkali surface-modified matting agent described in line 7 to page 5, lower right column, line 4, an organic polymer matting agent described in paragraphs [0005] to [0026] of JP-A-6-118542. It is more preferable to use

Further, two or more of these matting agents may be used in combination. For example, a combination of an inorganic matting agent and an organic matting agent, a combination of a porous matting agent and a non-porous matting agent, a combination of an amorphous matting agent and a spherical matting agent, mats having different average particle sizes. (For example, JP-A-6-1185)
No. 42, a combination of a matting agent having an average particle size of 1.5 μm or more and a matting agent having an average particle size of 1 μm or less)
and so on.

The photosensitive silver halide used in the present invention may be any of silver chloride, silver chlorobromide, and silver iodochlorobromide. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously.

The method for forming photosensitive silver halide in the present invention is well known in the art, and is described, for example, in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. The method described can be used. As a specific method that can be used in the present invention, a method of converting a part of the silver of the organic silver salt into photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt,
A method of preparing a photosensitive silver halide grain by adding a silver-supplying compound and a halogen-supplying compound to a gelatin or other polymer solution and mixing it with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm to 0.15 μm, and still more preferably 0 μm to 0.15 μm. 0.02 μm to 0.12 μm is preferred. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3:
1 is good. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited, but the ratio of the [100] plane, which has high spectral sensitization efficiency when a spectral sensitizing dye is adsorbed, is high. preferable. The ratio is preferably 50% or more.
% Or more, more preferably 80% or more. The ratio of the Miller index [100] plane is based on the adsorption dependency between the [111] plane and the [100] plane in the adsorption of the sensitizing dye.
T. Tani; J. Imaging Sci., 29, 165 (1985).

The photosensitive silver halide grains are the same as those in the periodic table.
It contains a metal or metal complex of Group VII or Group VIII (Groups 7 to 10). Rhodium, rhenium, ruthenium, osmium and iridium are preferred as the metal of Group VIII or Group VIII of the periodic table or the central metal of the metal complex. One of these metal complexes may be used,
Two or more complexes of the same metal and different metals may be used in combination. The preferred content is 1 nmol to 10 m per 1 mol of silver.
A molar range is preferred, and a range of 10 nmol to 100 μmol is more preferred. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalates and the like as ligands, for example, hexachlororhodium (III) complex salt, pentachloroacolodium (III) complex salt, tetrachlorodiacolate Rhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium (III) complex salt,
And trioxalatrodium (III) complex salts.
These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used to stabilize a solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg, KCl, NaCl, K
(Br, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The addition amount of these rhodium compounds is
1 × 10 per mole of silver halide^-8Mol ~ 5 x 10^-6Mole of
The range is preferably, particularly preferably 5 × 10^-8Mol ~ 1x
10 ^-6Is a mole. The addition of these compounds is
Each stage during the production of silver halide emulsion grains and before coating the emulsion
Can be suitably performed, but in particular,
And preferably incorporated into silver halide grains.
No.

Rhenium, ruthenium and osmium are in the form of water-soluble complex salts described in JP-A-63-2042, JP-A-1-285941, JP-A-2-20852, JP-A-2-20855 and the like. Is added. Particularly preferred is a six-coordinate complex represented by the following formula. [ML6] ^n- where M is Ru, Re, or O
represents s, L represents a ligand, and n represents 0, 1, 2, 3, or 4. In this case, the counter ion is not important and ammonium or alkali metal ions are used.

Preferred ligands include halide ligands, cyanide ligands, cyanide ligands, nitrosyl ligands, thionitrosyl ligands and the like.
Hereinafter, specific examples of the complex used in the present invention are shown, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ]
^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^- [RuCl ₅ (H ₂ O)]
^2- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) ₃ Cl ₃ ] ^2- [Ru (CO) Cl ₅ ] ^2- [Ru (CO) Br ₅ ]
^2- [OsCl ₆ ] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ]
^2- [Os (NS) Br ₅ ] ^2- [Os (O) ₂ (CN) ₄ ] ^4-

The addition amount of these compounds is 1
The range is preferably from 1 × 10 ^-9 mol to 1 × 10 ^-5 mol, and particularly preferably from 1 × 10 ^-5 mol to 1 × 10 ^-6 mol, per mol. These compounds can be appropriately added at the time of the production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and incorporate them into the silver halide grains. .

In order to add these compounds during silver halide grain formation and incorporate them into silver halide grains, an aqueous solution of metal complex powder or an aqueous solution dissolved together with NaCl and KCl is added to the aqueous solution during grain formation. Salt or a water-soluble halide solution, or as a third solution when the silver salt and the halide solution are mixed at the same time.
A method of preparing silver halide grains by a liquid simultaneous mixing method,
Alternatively, there is a method in which a required amount of an aqueous solution of a metal complex is charged into a reaction vessel during the formation of particles. Especially powder or Na
A method in which an aqueous solution dissolved together with Cl and KCl is added to a water-soluble halide solution is preferable.

To add to the surface of the particles, a required amount of an aqueous solution of a metal complex can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium, and pentachloronitrosyliridium. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used for stabilizing a solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) is used. Etc.) or alkali halides (eg, KCl, NaCl, KBr, NaB
r) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another iridium-doped silver halide grain during silver halide preparation.

Further, the silver halide grains used in the present invention include cobalt, iron, nickel, chromium, palladium,
It may contain metal atoms such as platinum, gold, thallium, copper and lead. For compounds of cobalt, iron, chromium and ruthenium, hexacyano metal complexes can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion,
Examples include, but are not limited to, hexacyanochromate ions and hexacyanoruthenate ions. The metal complex in the silver halide may be contained uniformly, may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration, and there is no particular limitation.

1 × 1 per mole of the above metal silver halide
0 ^-9 to 1 × 10 ^-4 mol is preferred. Further, in order to contain the above-mentioned metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added at the time of preparing particles.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method, but in the present invention, it may or may not be desalted. .

The silver halide emulsion is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination, for example,
Sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method, sulfur sensitization method and tellurium sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method Tellurium sensitization and gold sensitization are preferred.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Known compounds can be used as the sulfur sensitizer.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably from 10 ^-7 to 10 ^-2 mol per mol of silver halide. Yes, more preferably 1
0 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
JP-A-4-25832 and JP-A-4-1092
Compounds described in JP-A Nos. 40, 4-324855 and the like can be used. In particular, JP-A-4-324855
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in the publication.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in JP-A-5-3.
It can be tested by the method described in JP-A-13284. Examples of tellurium sensitizers include diacyl tellurides,
Bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, compounds having a P = Te bond, tellurocarboxylates, Te-organ Nyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellursulfonates, P-
Compounds having a Te bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Specifically, US Pat. Nos. 1,623,499 and 3,320,069
No. 3,772,031, British Patent No. 235,211, No. 1,121,496, No. 1,295,462, No. 1 , 3
No. 96,696, Canadian Patent No. 800,958, JP-A-4-324855, Japanese Patent Application No. 3-5.
No. 3693, No. 3-131598, No. 4
-129787, Journal of Chemical Society Chemical Communication (JC
hem.Soc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibi
d 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Per)
kin.Trans.) 1,2191 (1980); Patai (S.Patai)
Hen, The Chemistr of Organic Selenium and Tellurium Compounds
y of Organic Serenium and Tellunium Compounds),
Vol. 1 (1986), Vol. 2 (1987) can be used. In particular, JP-A-5-3
General formulas (II), (III) and (IV) in JP-A-13284
Are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, and gold sulfide, and 10 ^-7 to 10 ^-2 mol per mol of silver halide. Degrees can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physical ripening.

In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

The silver halide emulsion is disclosed in European Patent Application EP 2
A thiosulfonic acid compound may be added by the method disclosed in JP-A-93,917.

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

As a method for preparing silver halide, a so-called halide method in which a part of silver of an organic silver salt is halogenated with an organic or inorganic halide is also preferably used. The organic halide used here may be any compound as long as it is a compound which reacts with an organic silver salt to generate a silver halide. Examples of the organic halide include N-halogenimide (N-bromosuccinimide, etc.) and quaternary nitrogen halides (odorous compounds). Tetrabutylammonium bromide), an association of a quaternary nitrogen halide and a halogen molecule (pyridinium perbromide), and the like. As the inorganic halogen compound, any compound may be used as long as it is a compound which reacts with an organic silver salt to generate silver halide, and includes alkali metal or ammonium halides (sodium chloride, lithium bromide, potassium iodide,
Ammonium bromide, etc.), alkaline earth metal halides (calcium bromide, magnesium chloride, etc.), transition metal halides (ferric chloride, cupric bromide, etc.), metal complexes having halogen ligands (odor Sodium iridate, ammonium chloride rhodate, etc.), and halogen molecules (bromine, chlorine, iodine). Further, a desired organic / inorganic halide may be used in combination.

In the present invention, the amount of the halide to be added is preferably 1 to 500 mmol as a halogen atom per 1 mol of an organic silver salt, and more preferably 10 mmol.
Mole to 250 mmol is more preferred.

The organic silver salt which can be used in the present invention includes:
Relatively stable to light, but forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids,
Particularly (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms)
Silver salts of long chain fatty carboxylic acids are preferred. The ligand is 4.0
Complexes of organic or inorganic silver salts having a complex stability constant in the range of from 10.0 to 10.0 are also preferred. The silver donor can preferably comprise about 5 to 70% by weight of the imaging layer.
Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of the aliphatic carboxylic acid include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, and fumarate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphorate,
And mixtures thereof.

Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used.
Preferred examples of these compounds include silver salts of 3-mercapto-4-phenyl-1,2,4-triazole,
Silver salt of mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamide) benzothiazole, S-alkylthioglycolic acid (where the alkyl group has 12 carbon atoms)
-22), such as a silver salt of thioglycolic acid;
Silver salt of dithiocarboxylic acid such as silver salt of dithioacetic acid, silver salt of thioamide, silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, and silver salt of 2-mercaptobenzoxazole Silver salt,
A silver salt described in U.S. Pat. No. 4,123,274;
For example, a silver salt of a 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole, and a silver salt of a 3-, 5-mercaptothiazole derivative described in U.S. Pat. No. 3,301,678. Includes silver salts of thione compounds such as silver salt of (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione. Furthermore, compounds containing an imino group can also be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof,
For example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole, 1,2,4 as described in U.S. Pat. No. 4,220,709.
Silver salts of -triazole or 1-H-tetrazole, and silver salts of imidazole and imidazole derivatives. For example, various silver acetylide compounds as described in U.S. Pat. Nos. 4,761,361 and 4,775,613 can also be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. In the present invention, the short axis is 0.01 μm or more.
0.20 μm, major axis 0.10 μm to 5.0 μm is preferred, minor axis 0.01 μm to 0.15 μm, major axis 0.10 μm
m to 4.0 μm is more preferable. The organic silver salt particle size distribution is preferably monodisperse. Monodispersion means that the percentage of the value obtained by dividing the standard deviation of the length of each of the minor axis and major axis by the minor axis and major axis is preferably 100% or less, more preferably 80% or less, and still more preferably 50% or less. is there. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring the monodispersity, there is a method of obtaining the standard deviation of the volume-weighted average diameter of the organic silver salt, and the percentage (coefficient of variation) divided by the volume-weighted average diameter is preferably 100% or less,
It is more preferably at most 80%, further preferably at most 50%. As a measurement method, for example, the organic silver salt dispersed in a liquid is irradiated with laser light, and the particle size (volume weighted average diameter) obtained by obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained. Can be.

The organic silver salt which can be used in the present invention includes:
Preferably, desalting can be performed. The method for desalting is not particularly limited, and a known method can be used. However, a known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, or floc-forming water washing by a coagulation method can be preferably used.

For the purpose of obtaining fine particles having a small particle size and no aggregation, a method of preparing a solid fine particle dispersion using a dispersant is used for the organic silver salt which can be used in the present invention. The method of dispersing the organic silver salt into solid fine particles is carried out by using a known fine-granulating means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill, high-pressure homogenizer) in the presence of a dispersing aid. Used and can be mechanically dispersed.

When the organic silver salt is formed into solid fine particles using a dispersant, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, a maleic acid monoester copolymer, and acryloylmethyl Synthetic anionic polymers such as propanesulfonic acid copolymer, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, JP-A-52-92716, and International Publication WO88 / 04794. Surfactants described in Japanese Unexamined Patent Publication No. 7-350753, compounds described in Japanese Patent Application No. 7-350753, or known anionic, nonionic or cationic surfactants, and other polyvinyl alcohols, polyvinylpyrrolidone, carboxy Methylcellulose, hydroxypropyl Cellulose, known polymers such as hydroxypropyl methylcellulose, or a polymer compound existing in nature such as gelatin can be suitably selected and used.

It is a general method that the dispersing aid is mixed with the organic silver salt powder or the organic silver salt in a wet cake state before the dispersion, and then sent as a slurry to the dispersing machine. Heat treatment or treatment with a solvent may be performed in the combined state to form an organic silver salt powder or a wet cake. Before and after dispersion or during dispersion, p
H control may be used.

In addition to the mechanical dispersion, the particles may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersing agent. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after completion of the fine particle formation.

The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of the fine particles during storage, or stored in a highly viscous state by a hydrophilic colloid (for example, in a jelly state using gelatin). You can also do.
Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

The organic silver salt can be used in a desired amount, but is preferably 0.1 to 5 g / m ² , more preferably 1 to 5 g / m ² , expressed in terms of 1 m ^{2 of} the heat-developable image recording material.
3 g / m ² .

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

In a heat-developable image recording material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A-46-6074, JP-A-47-1238, JP-A-47-33621 and JP-A-49-46427. 49-115540
JP-A-50-34334, JP-A-50-14361
Nos. 0, 50-147711 and 51-32
632, 51-1023721, 51
JP-A-32324, JP-A-51-51933, JP-A-5-51933
JP-A-2-84727, JP-A-55-108654,
JP-A-56-146133, JP-A-57-82828, JP-A-57-82829, JP-A-6-3793, U.S. Pat.
679,426, 3,751,252, 3,751,255, 3,761,
No. 70, 3,782,949, and 3,
839,048, 3,928,686, 5,464,738, German Patent 2321
No. 328, European Patent 692732 and the like. For example, phenylamide oxime, 2
Amide oximes such as -thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2-bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of polyhydroxybenzene with hydroxylamine, reductone and / or hydrazine (eg, hydroquinone, bis (ethoxyethyl) hydroxylamine, piperidino Hexose reductone or a combination of formyl-4-methylphenylhydrazine); phenylhydroxamic acid, p
Hydroxamic acids such as -hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azines with sulfonamidophenols (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano Α-cyanophenylacetic acid derivatives such as -2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2-dihydroxy-1,1-binaphthyl, 6,6-dibromo-
Bis-β-naphthol as exemplified by 2,2-dihydroxy-1,1-binaphthyl and bis (2-hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (for example, , 2, 4
-Dihydroxybenzophenone or 2,4-dihydroxyacetophenone); 3-methyl-1-
5-pyrazolones, such as phenyl-5-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro Sulfonamide phenol reducing agents such as -4-benzenesulfonamidophenol and p-benzenesulfonamidophenol;
Phenylindane-1,3-dione and the like; chromans such as 2,2-dimethyl-7-tert-butyl-6-hydroxychroman; and 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine and the like 1,4-dihydropyridine; bisphenol (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 -Ethylidene-bis (2-t-butyl-6-methylphenol), 1,1-bis (2-
(Hydroxy-3,5-dimethylphenyl) -3,5,5
-Ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes such as benzyl and biacetyl. And ketones; 3-pyrazolidone and certain indane-1,3
-Dione; chromanol (such as tocopherol). Particularly preferred reducing agents include bisphenol,
Chromanol.

The reducing agent may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

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

In a heat-developable image recording material using an organic silver salt, a wide range of toning agents are disclosed in JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, and JP-A-49-5020. No. 49-91215, No. 49-91215, No. 50-2524, No. 50-32927, No. 50-67132, No. 50-67641, No. 50-11421.
No. 7, No. 51-3223, No. 51-2792
No. 3, No. 52-14788, No. 52-998
No. 13, No. 53-1020, No. 53-760
No. 20, No. 54-156524, No. 54-1
Nos. 56525, 61-183642, JP-A-4-56848, JP-B-49-10727, JP-A-54-20333, U.S. Pat.
Nos. 254, 3,446,648, 3,782,941, 4,123,282, 4,510,236, and British Patent 13
No. 80795 and Belgian Patent No. 842910. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide,
Pyrazolin-5-ones and cyclic imides such as quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides (e.g. N-hydroxy- 1,8-naphthalimide); cobalt complexes (e.g., cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole;
2,4-dimercaptopyrimidine, 3-mercapto-
Mercaptans exemplified by 4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides (for example, (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N ').
-Hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate)
And 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl-5 [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-. Oxazolidinedione; phthalazinone, phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3
Derivatives such as -dihydro-1,4-phthalazinedione;
Phthalazinone and phthalic acid derivatives (eg, phthalic acid, 4
Phthalazine, phthalazine derivatives or metal salts, or 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 6-isopropylphthalazine, 6-isobutylphthalazine, 5,7-
Derivatives such as dimethoxyphthalazine and 2,3-dihydrophthalazine; combinations of phthalazine with phthalic acid derivatives such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride;
Quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes, such as hexachlororhodium (II
I) ammonium acid, rhodium bromide, rhodium nitrate and potassium hexachlororhodate (III) and the like; inorganic peroxides and persulfates such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-
Benzoxazines such as 2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione
2,4-dione; pyrimidine and asymmetric-triazine (for example, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine and the like), azauracil,
And tetraazapentalene derivatives (for example, 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,
3a, 5,6a-tetraazapentalene, and 1,4
-Di (o-chlorophenyl) -3,6-dimercapto-
1H, 4H-2, 3a, 5, 6a-tetraazapentalene) and the like.

The color-toning agent may be added by any method such as a solution, a powder, and a solid fine particle dispersion. The dispersion of the solid fine particles is carried out by a known means for making fine (for example, a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill, etc.). When dispersing the solid fine particles, a dispersing aid may be used.

The substituted alkene derivatives, isoxazole derivatives and specific acetal compounds represented by the formulas (1) to (3), which are preferably used as nucleating agents in the present invention, will be described.

[0140]

Embedded image

In the formula (1), R¹, R^Two, R^ThreeIs it
Each independently represents a hydrogen atom or a substituent, and Z is an electron-withdrawing atom.
Represents a functional group. In the formula (1), R¹And Z, R^TwoAnd R^Three, R¹
And R ^TwoOr R^ThreeAnd Z are linked together to form a cyclic structure
May be formed. In the formula (2), R^FourRepresents a substituent
Represent. In the formula (3), X and Y each independently represent a hydrogen atom.
A and B are each independently
Coxy group, alkylthio group, alkylamino group, aryl
Roxy, arylthio, anilino, heterocyclic
Represents a xy group, a heterocyclic thio group, or a heterocyclic amino group.
You. In the formula (3), X and Y or A and B are mutually
To form a cyclic structure.

In the formula (1), when R ¹ , R ² and R ³ represent a substituent, examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom) and an alkyl group (Aralkyl, cycloalkyl,
Active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (including N-substituted nitrogen-containing heterocyclic group), heterocyclic group containing quaternized nitrogen atom (eg, pyridinio group) ), Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, imino group, imino group substituted with N atom, thiocarbonyl group, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl A group, a carbazoyl group, an oxalyl group, an oxamoyl group, a cyano group, a thiocarbamoyl group, a hydroxy group or a salt thereof, an alkoxy group (including a group having a repeating ethyleneoxy or propyleneoxy unit),
Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide Group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoylamino group , (Alkyl or aryl) sulfonyluureido, acylureido,
Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group,
An acylthio group, an (alkyl or aryl) sulfonyl group, an (alkyl or aryl) sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof,
Examples thereof include a phosphoryl group, a group having a phosphoric acid amide or a phosphoric ester structure, a silyl group, and a stannyl group. These substituents may be further substituted with these substituents.

The electron-withdrawing group represented by Z in the formula (1) is a substituent whose Hammett's substituent constant σp can take a positive value, specifically, a cyano group, an alkoxycarbonyl Group, aryloxycarbonyl group, carbamoyl group, imino group, imino group substituted with an N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom,
Perfluoroalkyl group, perfluoroalkaneamide group, sulfonamide group, acyl group, formyl group, phosphoryl group, carboxy group, sulfo group (or salt thereof), heterocyclic group, alkenyl group, alkynyl group, acyloxy group, acylthio group , A sulfonyloxy group, or an aryl group substituted with these electron-withdrawing groups. Here, the heterocyclic group is an aromatic or non-aromatic, saturated or unsaturated heterocyclic group, for example, a pyridyl group, a quinolyl group, a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group. Groups, hydantoin-1-yl group, urazol-1-yl group, succinimide group, phthalimide group and the like. The electron-withdrawing group represented by Z in the formula (1) may further have an optional substituent.

In the formula (1), the electron-withdrawing group represented by Z is preferably a group having a total number of carbon atoms of 0 to 30, that is, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carbonyl group,
Imino group, imino group substituted by N atom, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acyloxy group, acylthio group, or any electron withdrawing And a phenyl group substituted with a functional group, more preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbonyl group, an imino group,
An imino group substituted with an N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a formyl group, a phosphoryl group, a trifluoromethyl group, or a phenyl group substituted with any electron-withdrawing group; Particularly preferably, a cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted by an N atom, an alkylsulfonyl group, an arylsulfonyl group,
An acyl group or a formyl group.

In formula (1), the substituent represented by R ¹ is preferably a group having a total carbon number of 0 to 30, specifically, an electron-withdrawing group represented by Z in the above formula (1). And an alkyl group, an alkenyl group, an alkoxy group,
Aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, arylamino group, heterocyclic amino group,
A ureido group, an acylamino group, a silyl group, or a substituted or unsubstituted aryl group, more preferably a group having the same meaning as the electron-withdrawing group represented by Z in the above formula (1);
A substituted or unsubstituted aryl group, alkenyl group, alkylthio group, arylthio group, alkoxy group, silyl group, or acylamino group, more preferably an electron-withdrawing group, aryl group, alkenyl group, or acylamino group.

When R ¹ represents an electron-withdrawing group, the preferred range is the same as the preferred range of the electron-withdrawing group represented by Z.

In the formula (1), the substituent represented by R ² and R ³ is preferably a group having the same meaning as the electron-withdrawing group represented by Z in the above formula (1), an alkyl group, a hydroxy group ( Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an anilino group, and a heterocyclic amino group , An acylamino group, a substituted or unsubstituted phenyl group and the like. R ² and R ³ are more preferably when one of them is a hydrogen atom and the other represents a substituent. The substituent is preferably an alkyl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group. Group, alkylamino group, anilino group, heterocyclic amino group, acylamino group (particularly perfluoroalkaneamide group), sulfonamide group, substituted or unsubstituted phenyl group, heterocyclic group, etc., and more preferably hydroxy group (Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group, and particularly preferably. Hydroxy group (or salt thereof), alkoxy group, or heterocyclic group A.

In the formula (1), Z and R ¹ , or R ²
It is also preferred that and R ³ form a cyclic structure. The cyclic structure formed in this case is a non-aromatic carbon ring or a non-aromatic hetero ring, and is preferably a 5- to 7-membered cyclic structure having a total carbon number including a substituent of 1 to 7. 4
0, more preferably 3-35.

Among the compounds represented by formula (1), one of the more preferable ones is that Z represents a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group, and R ¹ is Represents an electron withdrawing group, one of R ^{2 and} R ³ is a hydrogen atom, the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof),
An alkoxy group, an aryloxy group, a heterocyclic oxy group,
A compound representing an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, or a heterocyclic group.

Further, among the compounds represented by the formula (1),
One of the more preferred is Z and R¹Is linked to non
Forming an aromatic 5- to 7-membered cyclic structure,^TwoMa
Or R ^ThreeIs a hydrogen atom and the other is a hydroxy atom.
Group (or its salt), mercapto group (or its
Salt), alkoxy group, aryloxy group, heterocyclic oxo
Si group, alkylthio group, arylthio group, heterocyclic thio
A compound that represents a group, an amino group, or a heterocyclic group.

Here, the non-aromatic 5 formed by Z and R ¹
The 7-membered to 7-membered cyclic structure is specifically indane-1,3-
Dione ring, pyrrolidine-2,4-dione ring, pyrazolidine-3,5-dione ring, oxazolidine-2,4-dione ring, 5-pyrazolone ring, imidazolidine-2,4-dione ring, thiazolidine-2,4 A dione ring, an oxolane-2,4-dione ring, a thiolane-2,4-dione ring,
1,3-dioxane-4,6-dione ring, cyclohexane-1,3-dione ring, 1,2,3,4-tetrahydroquinoline-2,4-dione ring, cyclopentane-1,3
A dione ring, an isoxazolidine-3,5-dione ring,
Barbituric acid ring, 2,3-dihydrobenzofuran-3
-One ring, pyrazolotriazole ring (for example, 7H-pyrazolo [1,5-b] [1,2,4] triazole, 7H
-Pyrazolo [5,1-c] [1,2,4] triazole, 7H-pyrazolo [1,5-a] benzimidazole, etc.), pyrrolotriazole ring (for example, 5H-pyrrolo [1,2-b] [1 , 2,4] triazole, 5H-pyrrolo [2,1-c] [1,2,4] triazole and the like),
2-cyclopentene-1,4-dione ring, 2,3-dihydrobenzothiophen-3-one-1,1-dioxide ring, chroman-2,4-dione ring, 2-oxazoline-
5-one ring, 2-imidazolin-5-one ring, 2-thiazolin-5-one ring, 1-pyrrolin-4-one ring, 5-
Oxothiazolidine-2-thione ring, 4-oxothiazolidine-2-thione ring, pyrrolopyrimidinone ring, 1,3
-Dithiolane ring, thiazolidine ring, 1,3-dithiethane ring, 1,3-dioxolane ring and the like, among which indane-1,3-dione ring, pyrrolidine-2,4-dione ring, pyrazolidine-3,5- A dione ring, a 5-pyrazolone ring, a barbituric acid ring, a 2-oxazolin-5-one ring and the like are preferable.

Examples of the substituent represented by R ⁴ in the formula (2) are the same as those described for the substituents R ^{1 to} R ^{3 in} the formula (1).

In formula (2), the substituent represented by R ⁴ is preferably an electron-withdrawing group or an aryl group.
When R ⁴ represents an electron-withdrawing group, it preferably has a total carbon number of 0.
To 30 or less of the following groups: cyano group, nitro group, acyl group, formyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, perfluoroalkyl group, phosphoryl Group, imino group, sulfonamide group, or heterocyclic group, further cyano group, acyl group, formyl group, alkoxycarbonyl group,
A carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonamide group, and a heterocyclic group are preferred.

[0154] When R ⁴ represents an aryl group, preferably a total carbon number of 0 to 30, a substituted or unsubstituted phenyl group, the substituent, R ^1, R ^2, R ³ of formula (1) When represents a substituent, the same as those described as the substituent can be mentioned, but an electron-withdrawing group is preferable.

As the substituents represented by X and Y in the formula (3), the same substituents as those described for the substituents R ^{1 to} R ^{3 in} the formula (1) can be mentioned. The substituent represented by X or Y is preferably a group having 1 to 50 total carbon atoms, more preferably a group having 1 to 35 total carbon atoms, and is a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Imino group, imino group substituted by N atom, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group,
Arylsulfonyl group, nitro group, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, acylamino group, acyloxy group, acylthio group, heterocyclic group,
Preferred are an alkylthio group, an alkoxy group, an aryl group, and the like. More preferably substituted with a cyano group, nitro group, alkoxycarbonyl group, carbamoyl group, acyl group, formyl group, acylthio group, acylamino group, thiocarbonyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, imino group, N atom Imino group, a phosphoryl group, a trifluoromethyl group, a heterocyclic group, or a substituted phenyl group, and particularly preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, Examples include an acylthio group, an acylamino group, a thiocarbonyl group, a formyl group, an imino group, an imino group substituted with an N atom, a heterocyclic group, and a phenyl group substituted with any electron-withdrawing group.

It is also preferable that X and Y combine with each other to form a non-aromatic carbon ring or a non-aromatic hetero ring. At this time, the formed ring is preferably a 5- to 7-membered ring, and specifically, a non-aromatic 5- to 7-membered ring which can be formed by bonding Z and R ¹ of the formula (1) to each other. The same examples are given, and their preferred ranges are also the same. These rings may further have a substituent, and the total carbon number is preferably 1 to 40, more preferably 1 to 35.

In the formula (3), the groups represented by A and B are
It may further have a substituent, preferably the total number of carbon atoms
1 to 40, more preferably a group having 1 to 30 carbon atoms in total.
You. In the formula (3), A and B are
More preferably, the ring structure is formed. At this time
The cyclic structure formed is a 5- to 7-membered non-aromatic heterocyclic
A ring is preferable, and its total carbon number is 1 to 40, and further 3 to
30 is preferred. In this case, an example in which A and B are connected (-
AB-), for example, -O- (CH _Two)_Two-O
-, -O- (CH_Two)_Three-O-, -S- (CH_Two)_Two-S
-, -S- (CH _Two)_Three-S-, -S-ph-S-, -N
(CH_Three)-(CH_Two)_Two-O-, -N (CH_Three)-(CH
_Two)_Two-S-, -O- (CH_Two)_Two-S-, -O- (C
H_Two)_Three-S-, -N (CH_Three) -Ph-O-,-N (C
H_Three) -Ph-S-,-N (ph)-(CH_Two)_Two-S-
And so on.

The compounds represented by the formulas (1) to (3)
An adsorptive group that adsorbs to silver halide may be incorporated. A ballast group or a polymer commonly used in immobile photographic additives such as couplers may be incorporated, and a cationic group (specifically, a group containing a quaternary ammonium group, or A nitrogen-containing heterocyclic group containing a graded nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocyclic) thio group,
Alternatively, it may contain a dissociable group that can be dissociated by a base (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.). Examples of these groups include, for example, JP-A-63-29751, U.S. Pat. No. 4,385,108, and 4,4,108.
59,347, JP-A-59-195233, JP-A-59-200231, and JP-A-59-20104.
No. 5, No. 59-201046, No. 59-20
Nos. 1047, 59-201048, 59
JP-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, and JP-A-63-23424.
No. 5, JP-A-63-234246, and JP-A No. 2-2.
No. 85344, JP-A-1-100530, JP-A-7-234471, JP-A-5-333466
JP, JP-A-6-19032, JP-A-6-19
031, JP-A-5-45761, U.S. Pat. No. 4,994,365, U.S. Pat. No. 4,988,604, JP-A-3-259240, and JP-A-7-56.
No. 10, JP-A-7-244348, German Patent 4006032 and the like.

Next, specific examples of the compounds represented by the formulas (1) to (3) are shown below. However, the present invention is not limited to the following compounds.

[0160]

Embedded image

[0161]

Embedded image

[0162]

Embedded image

[0163]

Embedded image

The compounds represented by the formulas (1) to (3) can be easily synthesized by known methods. For example, US Pat. No. 5,545,515 and US Pat.
No. 5339, U.S. Pat.No. 5,654,130,
International Publication WO-97 / 34196, or Japanese Patent Application No. Hei 9-
The compound can be synthesized with reference to the methods described in JP-A-354107, JP-A-11-133546 and JP-A-11-95365.

The compounds represented by the formulas (1) to (3)
One type may be used alone, or two or more types may be used in combination. In addition to the above, US Pat. No. 5,545,515, US Pat. No. 5,635,339, US Pat.
0, U.S. Pat. No. 5,705,324 and U.S. Pat. No. 5,686,228;
372, Japanese Patent Application No. 9-354107, JP-A-11-133546, JP-A-11-19373.
JP, JP-A-11-109546, JP-A-11-109546
-95365, JP-A-11-95366,
Compounds described in JP-A-11-149136 may be used in combination.

Further, according to the present invention, a method disclosed in
Various hydrazine derivatives described in JP-A-61270 can be used in combination.

The compounds represented by the formulas (1) to (3)
It can be used by dissolving it in water or a suitable organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve the compound. An emulsified dispersion can be prepared and used. Alternatively, the compound powder can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

The compounds represented by the formulas (1) to (3)
It may be added to the image forming layer side of the support, that is, to the image forming layer or any other layer on the layer side, but it is preferably added to the image forming layer or a layer adjacent thereto. The addition amount of the compounds represented by the formulas (1) to (3)
1 × 10 ^-6 to 1 mol is preferable for 1 mol of silver, and 1 × 1 ^-6
0 ^{-5 to} 5 × 10 ^-1 mol is more preferable, and 2 × 10 ^-5 to 2 mol is preferable.
× 10 ^-1 mol is most preferred.

Further, according to the present invention, a method disclosed in
Various hydrazine derivatives described in JP-A-61270 can be used in combination. The hydrazine derivative preferably used as a nucleating agent in the present invention has the following formula (H)
Are preferred.

[0171]

Embedded image

In the formula, R ²⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ¹⁰ represents a hydrogen atom or a block group, and G ¹ represents —CO—, —COCO—, —C (= S)
_{-, - SO 2, -SO -} , - PO (R 30) - group (. R ³⁰ is selected from the same range as the groups defined in R ^10, may be different from R ^10), or an iminomethylene Represents a group.
A ¹ and A ² are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group,
Represents an arylsulfonyl group or an acyl group. m ¹ is 0 or 1, and when m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group.

Next, the hydrazine derivative represented by the following formula (H) and used in the present invention will be described. The aliphatic group represented by R ²⁰ in the formula (H) is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 30 carbon atoms.

R²⁰The aromatic group represented by is a single ring or
Condensed ring aryl group such as benzene ring, naphthalene
Phenyl and naphthyl groups derived from a ring
You. R ²⁰The heterocyclic group represented by is a monocyclic or condensed ring
Saturated or unsaturated, aromatic or non-aromatic
In the telocyclic group, examples of the hetero ring in these groups include
For example, pyridine ring, pyrimidine ring, imidazole ring, pyra
Zole ring, quinoline ring, isoquinoline ring, benzimida
Zole ring, thiazole ring, benzothiazole ring, thiof
Benzene ring, triazine ring, morpholine ring, piperidine ring,
Examples include a piperazine ring and a benzo [1,3] dioxole ring.
I can do it. R²⁰May be substituted with any substituent
No. R²⁰Are preferably an aryl group and an alkyl
Or an aromatic heterocyclic group, more preferably
Is a substituted or unsubstituted phenyl group, having 1 to 3 carbon atoms.
It is a substituted alkyl group or an aromatic heterocyclic group.

[0175] When R ²⁰ represents a substituted alkyl group having 1 to 3 carbon atoms, R ²⁰ is more preferably a substituted methyl group, more disubstituted methyl or trisubstituted methyl group is preferred. When R ²⁰ represents a substituted methyl group, preferred specific examples include a t-butyl group, a dicyanomethyl group, a dicyanophenylmethyl group, a triphenylmethyl group (trityl group), a diphenylmethyl group, a methoxycarbonyldiphenylmethyl group, and a cyano group. Examples thereof include a diphenylmethyl group, a methylthiodiphenylmethyl group, and a cyclopropyldiphenylmethyl group, and among them, a trityl group is most preferable.

When R ²⁰ represents an aromatic heterocyclic group, preferred hetero rings include a pyridine ring, a quinoline ring, a pyrimidine ring, a triazine ring, a benzothiazole ring, a benzimidazole ring, a thiophene ring and the like. In the formula (H), R ²⁰ is most preferably a substituted or unsubstituted phenyl group.

In the formula (H), R ¹⁰ represents a hydrogen atom or a block group, and the block group is specifically an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group) or an aromatic group (a single group). Ring or fused ring aryl group),
Represents a heterocyclic group, an alkoxy group, an aryloxy group, a substituted or unsubstituted amino group or a hydrazino group.

R ¹⁰ is preferably an alkyl group (a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group). , Pyridiniomethyl, difluoromethoxymethyl, difluorocarboxymethyl, hydroxymethyl, methanesulfonamidomethyl, benzenesulfonamidomethyl, trifluorosulfonamidomethyl, trifluoroacetylmethyl, dimethylaminomethyl, phenylsulfonyl Methyl group, o-hydroxybenzyl group, methoxymethyl group, phenoxymethyl group,
4-ethylphenoxymethyl group, phenylthiomethyl group, t-butyl group, dicyanomethyl group, diphenylmethyl group, triphenylmethyl group, methoxycarbonyldiphenylmethyl group, cyanodiphenylmethyl group, methylthiodiphenylmethyl group, etc.), alkenyl group (C 1-
10 alkenyl groups such as vinyl, 2-ethoxycarbonylvinyl, 2-trifluoro-2-methoxycarbonylvinyl, 2,2-dicyanovinyl, 2-
Cyano-2-methoxycarbonylvinyl group, 2-cyano-2-ethoxycarbonylvinyl group, 2-acetyl-2
-Ethoxycarbonylvinyl group, etc.) and aryl groups (monocyclic or condensed-ring aryl groups containing a benzene ring are particularly preferred; for example, phenyl, perfluorophenyl, 3,5-dichlorophenyl, 2-methanesulfone) An amidophenyl group, a 2-carbamoylphenyl group,
4,5-dicyanophenyl group, 2-hydroxymethylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2-chloro-5-octylsulfamoylphenyl group), heterocyclic group (5-6 membered saturated or unsaturated, containing at least one nitrogen, oxygen and sulfur atom)
A monocyclic or condensed heterocyclic group such as morpholino, piberidino (N-substituted), imidazolyl, indazolyl (4-nitroindazolyl), pyrazolyl, triazolyl, benzimidazolyl, tetrazolyl, Pyridyl group, pyridinio group, quinolinio group, quinolyl group, hydantoyl group, imidazolidinyl group, etc.),
An alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, a 2-hydroxyethoxy group, a benzyloxy group, a t-butoxy group, etc.), an amino group (an unsubstituted amino group, and a 1 to 10 carbon atoms) An alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group (including a nitrogen-containing heterocyclic amino group containing a quaternized nitrogen atom) is preferable.
6,6-tetramethylpiperidin-4-ylamino group,
Propylamino group, 2-hydroxyethylamino group, 3
-Hydroxypropylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group,
N-benzyl-3-pyridinioamino group and the like). R
^The group represented by ¹⁰ may be substituted with any substituent.

Of the groups represented by R ¹⁰ , preferred are a hydrogen atom, an alkyl group and an alkenyl group when R ²⁰ represents a phenyl group or an aromatic heterocyclic group and G ¹ is a —CO— group. A alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, or an aryl group, and most preferably a hydrogen atom or an alkyl group. When R ¹⁰ represents an alkyl group, the substituent is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, a sulfonamide group, an amino group, an acylamino group, or a carboxy group. .

R ²⁰ represents a substituted methyl group, and G ¹ represents-
In the case of a CO— group, R ¹⁰ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group (unsubstituted amino group, alkylamino group, arylamino group, heterocyclic amino group). And more preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylamino group, an arylamino group, and a heterocyclic amino group. When G ¹ is a —COCO— group, regardless of R ²⁰ , R ¹⁰ is preferably an alkoxy group, an aryloxy group, or an amino group, particularly a substituted amino group, specifically, an alkylamino group, an arylamino group, or a saturated amino group. Alternatively, an unsaturated heterocyclic amino group is preferred.

When G ¹ is a —SO ₂ — group, R ¹⁰ is preferably an alkyl group, an aryl group or a substituted amino group, regardless of R ²⁰ . In the formula (H), G ¹ is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group.

In the formula (H), A ¹ and A ² represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group, or a sum of substituent constants of Hammett is -0.5 or more) Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants becomes -0.5 or more, or a linear group. , A branched or cyclic, substituted or unsubstituted aliphatic acyl group, and A ¹ and A ² are most preferably hydrogen atoms.

In the formula (H), m ¹ represents 1 or 0. When m ¹ is 0, R ¹⁰ represents an aliphatic group, an aromatic group or a heterocyclic group. When m ¹ is 0, R ¹⁰ is particularly preferably a phenyl group, a substituted alkyl group having 1 to 3 carbon atoms, or an alkenyl group. Of these, for the phenyl group and the substituted alkyl group having 1 to 3 carbon atoms, its preferred range is the same as the preferable ranges of R ²⁰ as described above.
When R ¹⁰ is an alkenyl group, preferably R ¹⁰ is a vinyl group, and is a substituent selected from the following substituents: a cyano group, an acyl group, an alkoxycarbonyl group, a nitro group, a trifluoromethyl group, a carbamoyl group and the like. Vinyl groups having one or two groups are particularly preferred. In particular,
Examples thereof include a 2,2-dicyanovinyl group, a 2-cyano-2-methoxycarbonylvinyl group, a 2-cyano-2-ethoxycarbonylvinyl group, and a 2-acetyl-2-ethoxyquincarbonylvinyl group. m ¹ is preferably 1.

In the formula (H), R^TenIs G¹-R^TenPart of
From the residual molecule, and -G¹-R ^TenIncluding partial atoms
That cause a cyclization reaction that produces a cyclic structure
And a hydrazine derivative represented by the formula (H).
The conductor has an adsorptive group that adsorbs to silver halide.
It may be incorporated. R of formula (H)^TenOr R²⁰To
Is used in immobile photographic additives such as couplers.
Incorporates commonly used ballast groups or polymers
And R in formula (H)^TenOr R
²⁰May have a plurality of hydrazino groups as substituents.
Often, the compound represented by the formula (H) is hydrazino
Represents a multimer for the group. Further, R of the formula (H)^TenAlso
Is R²⁰Has a cationic group (specifically, a quaternary
A group containing an ammonium group or a quaternized nitrogen atom
Including nitrogen-containing heterocyclic group), ethyleneoxy group or
Groups containing repeating units of a propyleneoxy group, (alkyl
, Aryl, or heterocycle) thio group or base
Dissociable groups (carboxy group, sulfo group,
Acylsulfamoyl group, carbamoylsulfamoyl
And the like) may be contained. These examples include
For example, JP-A-63-29751, U.S. Pat.
No. 5108, No. 4459347, and
JP-A-59-195233, JP-A-59-200231
Bulletin, JP-A-59-201045, JP-A-59-20104
No. 6, No. 59-201047, No. 59-20
Nos. 1048 and 59-201049,
Nos. 61-170733 and 61-270744
Bulletin, JP-A-62-948, JP-A-63-234244
Bulletin, JP-A-63-234245, JP-A-63-234424
6, JP-A-2-285344, JP-A-1-
No. 100530, JP-A-64-86134,
JP-A-4-16938, JP-A-5-97091
Publication, International Publication WO95-32452, International Publication
WO95-32453, JP-A-9-23526
No. 4, JP-A-9-235265, Kaihei 9-2
JP-A-35266, JP-A-9-235267,
JP-A-9-179229, JP-A-7-234471
JP, JP-A-5-333466, JP-A-6-1
No. 9032, JP-A-6-19031, JP-A-Hei.
No. 5-45761, U.S. Pat. No. 4,994,365
Japanese Patent No. 4,988,604;
JP-A-259240, JP-A-7-5610, JP-A-7-5610
JP-A-7-244348, German Patent No. 4006032
And the like.

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

[0186]

[Table 1]

[0187]

[Table 2]

[0188]

[Table 3]

[0189]

[Table 4]

The hydrazine derivative used in the present invention is
One type may be used alone, or two or more types may be used in combination. In addition to the above, the following hydrazine derivatives are also preferably used. (In some cases, they can be used in combination.) The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following patents.

That is, JP-A-10-10672, JP-A-10-161270, and JP-A-10-6289.
No. 8, JP-A-9-304870, JP-A-9-304
No. 304872, JP-A-9-304871,
JP-A-10-31282, US Patent No. 54966
95. All hydrazine derivatives described in EP-A-74320A.

The hydrazine nucleating agent may be water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be used by dissolving it.

Further, by a well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve and dissolve mechanically. An emulsified dispersion can be prepared and used. Alternatively, the powder of the hydrazine derivative can be dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine-based nucleating agent may be added to the layer on the image forming layer side with respect to the support, that is, to the image forming layer or any other layer on the layer side. Preferably, it is added to the layer.

The addition amount of the hydrazine-based nucleating agent is preferably 1 × 10 ⁻⁶ to 1 mol per 1 mol of silver, and 1 × 10 ⁻⁵ × 1 mol.
0 ^-1 mol is more preferred, and 2 × 10 ^-5 to 2 × 10 ^-1 mol is most preferred.

Any sensitizing dye may be used as long as it can spectrally sensitize the silver halide grains in a desired wavelength region when adsorbed on the silver halide grains. As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Holographic polar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17643, Section IV-A (1.
December 978, p. 23), Item 1831X (1979)
August, p. 437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate making cameras can be advantageously selected.

As an example of spectral sensitization to red light, He-
For so-called red light sources such as Ne lasers, red semiconductor lasers and LEDs, the compounds of I-1 to I-38 described in JP-A-54-18726 and JP-A-6-753 are disclosed.
No. 22, compounds I-1 to I-35 and JP-A-7-287338, compounds I-1 to I-34, and dyes 1 to 3 described in JP-B-55-39818.
20, I-1 described in JP-A-62-284343.
To I-37 and the compounds I-1 to I-34 described in JP-A-7-287338 are advantageously selected.

For semiconductor laser light sources in the wavelength range of 750-1400 nm, various known dyes, including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes, are spectrally advantageously sensitized. Can be done. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolinedione nucleus, a barbituric acid nucleus,
It also includes acidic nuclei such as thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, US Pat.
1,279, 3,719,495,
No. 3,877,943, British Patent 1,466.
Nos. 201, 1,469,117, 1,422,057, JP-B-3-10391, JP-A-6-52387, and JP-A-5-34143.
No. 2, JP-A-6-194787, JP-A-6-3011
The dyes may be appropriately selected from known dyes as described in JP-A-41.

Particularly preferred structures of the dyes used in the present invention are cyanine dyes having a thioether bond-containing substituent (for example, JP-A-62-58239, JP-A-3-13838, and JP-A-3-138842). JP-A-4-255840, JP-A-5-72659, JP-A-5-72661, JP-A-6-222491, JP-A-2-230506, and JP-A-6-258557.
JP-A-6-317868 and JP-A-6-32442
5, JP-A-7-500926, U.S. Pat. No. 5,541,054), and a dye having a carboxylic acid group (for example, see JP-A-3-1634).
No. 40, No. 6-301141, U.S. Pat.
441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524).
JP-A-51-127719, JP-A-52-808
No. 29, 54-61517, 59-21
Nos. 4846, 60-6750 and 63-1
59841, JP-A-6-35109, 6
-59381, 7-146537 and 7
Dyes described in JP-A-146537, JP-T-55-50111, British Patent 1,467,638, and US Pat. No. 5,281,515.

As dyes for forming a J-band, US Pat. Nos. 5,510,236 and 3,871,
The dye described in Example 5 of JP-A-887, JP-A-2-96;
No. 131 and JP-A-59-48753 are disclosed and can be preferably used in the present invention.

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. In particular, combinations of sensitizing dyes are frequently used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are
Research Disclosure 176, 17643 (published December 1978), page 23, IV, J, or JP-B-49-
No. 25500, No. 43-4933, JP-A-5
Nos. 9-19032 and 59-192242.

The sensitizing dyes can be added to the silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,2 3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent.

Further, as disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid. To the emulsion, Japanese Patent Publication No.
No. 23389, No. 44-27555, No. 57
As disclosed in -22091 and the like, a method of dissolving a dye in an acid and adding this solution to an emulsion, or adding an acid or a base to an emulsion as an aqueous solution in the presence of an acid or a base,
U.S. Pat. Nos. 3,822,135 and 4,006
No. 025/105, and a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in JP-A-53-102733 and JP-A-58-105141. A method in which a dye is directly dispersed in a hydrophilic colloid as disclosed in JP-A-51-74624, and a compound for red-shifting is disclosed as disclosed in JP-A-51-74624. A method of dissolving the dye by using the solution and adding this solution to the emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion at any stage in the preparation of the emulsion which has been found to be useful.
For example, US Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756 and 4,225,666, JP-A-58-18.
As disclosed in the specifications such as JP-A Nos. 4142 and 60-196749, the timing before silver halide grain formation and / or before desalination, during and / or after desalination of silver halide, and the like. Until the start of ripening,
As disclosed in the specification of JP-A-8-113920 and the like, at any time during the process immediately before or during chemical ripening, and at any time after the chemical ripening and before coating, before the emulsion is coated. May be done. Also, U.S. Pat. No. 4,225,666, JP-A-58-7629.
As disclosed in the specification of Japanese Patent Application Laid-Open Publication No. H10-163, the same compound may be used alone or in combination with a compound having a different structure. The compound may be added in portions such as before aging or during the process and after completion, or may be added by changing the kind of compound to be added and the combination of compounds.

The amount of the sensitizing dye used in the present invention may be a desired amount according to the performance such as sensitivity and fog.
1 per mole of silver halide in the image forming layer (photosensitive layer)
It is preferably from 0 ^-6 to 1 mol, more preferably from 10 ^-4 to 10 ^-1 mol.

In the present invention, the silver halide emulsion and / or
And organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and stabilized against reduced sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors which can be used alone or in combination are the thiazoniums described in U.S. Pat. Nos. 2,131,038 and 2,694,716. salt,
U.S. Pat. Nos. 2,886,437 and 2,
Azaindene described in US Pat. No. 4,444,605, mercury salt described in US Pat. No. 2,728,663, urazole described in US Pat. No. 3,287,135, US Pat. No. 3,235 Sulfocatechol described in U.S. Pat. No. 6,652,652, oxime, nitrone, nitroindazole described in British Patent No. 623,448, polyvalent metal salt described in U.S. Pat. No. 2,839,405, U.S. Pat. U.S. Pat. No. 2,566,263.
, Platinum and gold salts described in US Pat. No. 4,597,915 and U.S. Pat.
Halogen-substituted organic compounds described in U.S. Patent Nos. 8,665 and 4,442,202.
Nos. 128,557 and 4,137,079
No. 4,138,365 and 4,459,350, and the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The antifoggant preferably used in the present invention is an organic halide.
Nos. 9624, 50-120328, 51
JP-A-121332, JP-A-54-58022, JP-A-56-70543, JP-A-56-99335,
JP-A-59-90842, JP-A-61-129842, JP-A-62-129845, and JP-A-6-2081.
Nos. 91, 6-208193, 7-562
No. 1, No. 7-2781, No. 8-15809, U.S. Pat. No. 5,340,712, No. 5,
Compounds such as those disclosed in 369,000 and 5,464,737.

The antifoggant may be added by any method such as a solution, a powder, and a dispersion of solid fine particles. In the case of a water-insoluble substance, it is preferably added as a dispersion of solid fine particles using water as a dispersion medium. Dispersion of solid fine particles can be performed by a known micronizing means (eg, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.).
Done in When dispersing the solid fine particles, a dispersing aid may be used.

Although not required to practice the present invention,
Mercury (II) as an antifoggant in the emulsion layer (image forming layer)
It may be advantageous to add a salt. Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The added amount of mercury used in the present invention is as follows.
It is preferably in the range of 1 nmol to 1 mmol, more preferably 10 nmol to 100 μmol per mol.

The heat-developable image recording material of the present invention may contain benzoic acids for the purpose of increasing the sensitivity and preventing fog. The benzoic acid used in the present invention may be any benzoic acid derivative. Examples of a preferred structure include those described in US Pat. Nos. 4,784,939 and 4,152,160.
JP-A-9-329865, JP-A-9-329865
Compounds described in JP-A-329864 and JP-A-9-281637 are exemplified. The benzoic acid may be added to any part of the image forming material, but it is preferable to add the benzoic acid to the layer having the image forming layer (photosensitive layer), and to add it to the organic silver salt containing layer. Is more preferred. The benzoic acid may be added at any time during the preparation of the coating solution, and when added to the organic silver salt-containing layer, may be added at any time from the preparation of the organic silver salt to the preparation of the coating solution, but after the preparation of the organic silver salt. To just before application.
The benzoic acid may be added by any method such as powder, solution, and fine particle dispersion. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent. The benzoic acid may be added in any amount, but is preferably from 1 μmol to 2 mol, more preferably from 1 mmol to 0.5 mol, per 1 mol of silver.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic or fused aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms), alkoxy ( For example, it may have a substituent selected from the group consisting of one or more carbon atoms, preferably those having 1 to 4 carbon atoms, and aryl (which may have a substituent). Good. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 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-quinoline thiol,
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-hydrokilo-2
-Mercaptopyrimidine, 2-mercaptopyrimidine,
4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-
Mercapto-5-phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, 3-
(5-mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N '-[3- (5-mercaptotetrazolyl) phenyl] urea, 2-mercapto-4-phenyloxazole, 2- [3- (9 -Carbazolyl) propylimino] -3- (2-mercaptoethyl) benzothiazoline and the like, but the present invention is not limited thereto.

The addition amount of these mercapto compounds is 0.000 per mole of silver in the emulsion layer (image forming layer).
It is preferably in the range of 1 to 1.0 mol, more preferably,
The amount is from 0.001 to 0.3 mole per mole of silver.

In the image forming layer of the present invention, a polyhydric alcohol (for example, glycerin and diol of the type described in US Pat. No. 2,960,404) as a plasticizer and a lubricant, US Pat. , 588, 765
And the fatty acid or ester described in JP-A No. 3,121,060 and the silicone resin described in British Patent No. 955,061.

The pH of the coating solution for the image forming layer is 5.5 to 7.8.
The acid used for the adjustment is preferably an acid containing no halogen.

The heat-developable image recording material of the present invention has an image forming layer containing at least one silver halide emulsion on one side of a support and a back layer on the other side.
It is preferably a so-called single-sided image recording material.

In the present invention, the back layer preferably has a maximum absorption in a desired range of about 0.3 to 2.0.
If the desired range is 750 to 1400 nm, 7
The optical density at 50 to 360 nm is 0.005 to
It is preferably less than 0.5, more preferably an antihalation layer having an optical density of less than 0.001 to less than 0.3. The desired range is 750n
m or less, the maximum absorption in the desired range before image formation is 0.3 to 2.0, and 360 absorption after image formation.
It is preferable that the antihalation layer has an optical density of 750 nm to less than 0.005 to less than 0.3. The method for lowering the optical density after image formation to the above range is not particularly limited. For example, Belgian Patent No. 733,70
As described in the specification of JP-A No. 6, there is a method of decreasing the concentration by dyeing by heating, and a method of decreasing the concentration by decoloring by light irradiation described in JP-A-54-17833.

When an antihalation dye is used in the present invention, such a dye has a desired absorption in a desired range, has a sufficiently low absorption in the visible region after treatment, and has a preferable absorbance spectrum shape of the back layer. Any compound may be used as long as is obtained. For example, the following are disclosed, but the present invention is not limited thereto.
As a single dye, JP-A-59-56458, JP-A-2-216140, JP-A-7-13295 and JP-A-7-11432, U.S. Pat. No. 5,380,6
No. 35, JP-A-2-68539, No. 13
1st line, lower left column of page to 9th line, lower left column of page 14, 3-24
No. 539, page 14, lower left column to page 16, lower right column.
-139136, 53-132334,
JP-A-56-501480, JP-A-57-16060, JP-A-57-68831, and JP-A-57-101835
JP-A-59-182436, JP-A-7-36
No. 145, No. 7-199409, Japanese Patent Publication No. 48
-33692, 50-16648, JP-B-2-41734, U.S. Patent 4,088,497.
No. 4,283,487, No. 4,54
Nos. 8,896 and 5,187,049.

The heat-developable photographic emulsion constitutes one or more layers on a support. One layer comprises an organic silver salt, a silver halide, a developer and a binder, and a toning agent,
Optional additional materials such as coating aids and other auxiliaries must be included. The two-layer construction is such that the first emulsion layer (usually the layer adjacent to the support) contains an organic silver salt and silver halide and the second layer or both layers do not contain some other components. No. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The composition of the multicolor photothermographic material may include a combination of these two layers for each color,
Also, as described in U.S. Pat. No. 4,708,928, all components may be contained in a single layer. In the case of a multi-dye, multi-color photosensitive heat-developable photographic material, each emulsion layer is generally provided between each emulsion layer (light-sensitive layer) as described in U.S. Pat. No. 4,460,681. By using functional or non-functional barrier layers, they are kept distinct from one another.

[0220] A backside resistive heating layer as disclosed in US Patent Nos. 4,460,681 and 4,374,921.
r) can also be used in photosensitive heat-developable photographic imaging systems.

A hardener may be used for each layer such as an image forming layer, a protective layer and a back layer of the heat-developable image recording material. Examples of the hardener include polyisocyanates described in U.S. Pat. No. 4,281,060 and JP-A-6-208193, and U.S. Pat. No. 4,791,042.
Epoxy compounds described in the specification and the like, vinylsulfone compounds described in JP-A-62-89048 and the like are used.

A method for obtaining a color image using the heat-developable image recording material in the present invention is described in JP-A-7-13295.
There is a method described on page 10, left column, line 43 to 11 left column, line 40. Examples of color dye image stabilizers include British Patent No. 1,326,889 and U.S. Pat.
Nos. 432,300, 3,698,909, 3,574,627 and 3,57.
3,050, 3,764,337 and 4,042,394.

The photothermographic emulsions of the present invention can be prepared by various coating operations including dip coating, air knife coating, flow coating or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. Can be coated.
If desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761,791 and GB 837,095.

Additional layers in the heat-developable image recording material of the present invention, such as a dye-receiving layer for receiving a moving dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques And a known primer layer. The heat-developable image recording material is preferably capable of forming an image with only one heat-developable image recording material, and it is preferable that a functional layer such as an image receiving layer, which is necessary for image formation, does not become another material.

[0225]

The present invention will be described more specifically with reference to the following examples. The materials, amounts, proportions,
The processing content, processing procedure, and the like can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. <Example 1><< Preparation of silver halide emulsion A >> 11 g of phthalated gelatin, 30 mg of potassium bromide, and 10 mg of sodium benzenethiosulfonate were dissolved in 700 ml of water, and p
After adjusting the H to 5.0, 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 mol / l of potassium bromide, (N
An aqueous solution containing 5 × 10 ⁻⁶ mol / L of H ₄ ) ₂ RhCl ₅ (H ₂ O) and 2 × 10 ⁻⁵ mol / L of K ₃ IrCl ₆ was maintained at a pAg of 7.7 by a control double jet method. Over 30 minutes. Then, while maintaining 476 ml of an aqueous solution containing 55.5 g of silver nitrate and an aqueous solution of a halogen salt containing 1 mol / l of potassium bromide and 2 × 10 ^-5 mol / l of K ₃ IrCl ₆ at a pAg of 7.7, a control double jet method was used. 28 minutes 30 minutes
The addition was made over a second period. Thereafter, the pH was lowered to cause coagulation and sedimentation, followed by desalting treatment.
The pH was adjusted to 5.9 and pAg to 8.0 by adding 3.7 g.
The obtained particles were cubic particles having an average particle size of 0.08 μm, a projected area variation coefficient of 9%, and a (100) plane ratio of 90%.

The thus-obtained silver halide grains were heated to 60 ° C., and 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, and 3 minutes later, 154 μmol of sodium thiosulfate was added, followed by ripening for 100 minutes. After adding 5 × 10 ^-4 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, the temperature was lowered to 40 ° C. Thereafter, the temperature was maintained at 40 ° C., and 12.8 × 10 ⁻⁴ mol of sensitizing dye A, 6.4 × 10 ⁻³ mol per mol of silver halide.
Moles of compound B are added with stirring and after 20 minutes 30
The mixture was rapidly cooled to ℃ to complete the preparation of silver halide emulsion A.

[0227]

Embedded image

<< Preparation of Organic Acid Silver Dispersion A >> 6.1 g of arachidic acid, 37.6 g of behenic acid, 700 ml of distilled water, t
ert-butanol 70 ml, 1N-NaOH aqueous solution 1
23 ml were mixed and reacted by stirring at 75 ° C. for 1 hour.
The temperature was lowered to 5 ° C. Then, an aqueous solution 11 of 22 g of silver nitrate
2.5 ml was added over 45 seconds, allowed to stand for 5 minutes, and cooled to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate became 30 μS / cm. The solid content thus obtained was treated as a wet cake without drying, and the solid content was 100 g.
5 g of polyvinyl alcohol (trade name: PVA-217) and water were added to the corresponding wet cake to make the total amount 500 g, and the mixture was preliminarily dispersed by a homomixer.

Next, the pre-dispersed stock solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² , and the mixture was treated three times to obtain an organic acid silver dispersion A. The organic acid silver particles contained in the organic acid silver dispersion thus obtained had an average minor axis of 0.04 μm,
Needle-shaped particles having an average major axis of 0.8 μm and a variation coefficient of 30%. Particle size measurements were made by Malvern Instruments Ltd.
Performed with MasterSizerX. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature. Thus, an organic acid silver dispersion A having a silver behenate content of 85 mol% was prepared.

<< 1,1-bis (2-hydroxy-3,5)
Preparation of Solid Fine Particle Dispersion of -Dimethylphenyl) -3,5,5-trimethylhexane (Reducing Agent) >> 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,
For 20 g of 5,5-trimethylhexane, 3.0 g of MP-203 (manufactured by Kuraray Co., Ltd.) and water 7
After adding 7 ml, the mixture was stirred well and left as a slurry for 3 hours. Then, 0.5 mm zirconia beads were added to 3
60 g was prepared and put into a vessel together with the slurry, and dispersed for 3 hours with a disperser (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) to prepare a dispersion of solid fine particles of a reducing agent. As for the particle diameter, 80% by mass of the particles is 0.3 μm or more.
It was 1.0 μm.

<< Preparation of Solid Fine Particle Dispersion of Tribromomethylphenyl Sulfone >> 0.5 g of hydroxypropylmethylcellulose, 0.5 g of compound C and 88.5 g of water were added to 30 g of tribromomethylphenylsulfone, and the mixture was stirred well. The slurry was left for 3 hours. Thereafter, a solid fine particle dispersion of tribromomethylphenylsulfone (antifoggant) was prepared in the same manner as in the preparation of the reducing agent solid fine particle dispersion. As for the particle size, 80% by mass of the particles was from 0.3 μm to 1.0 μm.

<< Preparation of Image Forming Layer Coating Solution >> The following binder, material, and silver halide emulsion A were added to 1 mol of silver of the organic acid silver dispersion A prepared above, and water was added. Thus, a coating solution was prepared. The pH of the coating solution is 7.5
７ 7.7.

Binder; LACSTAR 3307B 406 g as solid content (manufactured by Dainippon Ink and Chemicals, Incorporated; glass transition temperature of 17 ° C. with SBR latex) 1,1-bis (2-hydroxy-3,5-dimethyl) Phenyl) -3,5,5-trimethylhexane 119 g as solids tribromomethylphenylsulfone 21.6 g as solids sodium benzenethiosulfonate 0.44 g benzotriazole 1.25 g polyvinyl alcohol (MP manufactured by Kuraray Co., Ltd.) -203) 20 g isopropylphthalazine 0.10 mol sodium dihydrogen orthophosphate 0.13 g Compound D 9.38 g Nucleating agent: Compound Example C-62 0.9 g Dye A 783 nm Optical density 0.3 Liquid amount Silver halide emulsion A 0.05 mol as Ag amount

[0234]

Embedded image

<< Preparation of Coating Solution for Lower Layer of Protective Layer >> Polymer latex of methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (% by mass) (solid Concentration: 30% by mass; Compound E as a film-forming auxiliary was 15% by mass based on the solid content of the polymer, and the I / O value was 0.1%.
49) 25 g of water was added to 150 g, and then 5
1.3 g of a 5% by mass aqueous solution, 50 g of a 5% by mass aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235) as a thickener, and 0.1 g of a matting agent (polystyrene particles having an average particle diameter of 7 μm) were added. Prepared. Coating solution p
H was 6.5-7.0.

<< Preparation of Coating Solution for Upper Layer of Protective Layer >> Polymer latex of methyl methacrylate / butyl acrylate = 73/27 (% by mass) (solid content concentration: 30% by mass; To 15 g of 15% by mass, I / O value = 0.55), 2.5 g of a 5% by mass aqueous solution of compound F, 2.5 g of carnava wax (Cerozol 524 manufactured by Chukyo Yushi Co., Ltd.) and 30% by mass of aqueous dispersion of 2.5%
g and 46 g of a 5% by mass aqueous solution of polyvinyl alcohol (PVA-235, manufactured by Kuraray Co., Ltd.) as a thickener, a matting agent (polystyrene particles having an average particle diameter of 7 μm) 0.3
g, and 25 g of a 10% by mass aqueous solution of compound G
Was added to prepare a coating solution. The pH of the coating solution is 2.5 to
3.0.

[0237]

Embedded image

<< Preparation of PET Support with Back / Undercoat Layer >> (1) Support Using terephthalic acid and ethylene glycol, IV (intrinsic viscosity) = 0.66 (phenol / tetrachloroethane = PE (measured at 25 ° C. in 6/4 (mass ratio))
T was obtained. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and then quenched to prepare an unstretched film having a thickness of 120 μm after heat setting. . This is longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then stretched by a tenter.
Lateral stretching was performed 5 times. The temperatures at this time are
110 ° C and 130 ° C. Thereafter, at 240 ° C., 20
After heat setting for 2 seconds, relaxation was 4% in the lateral direction at the same temperature.
Then, after slitting the chuck portion of the tenter, knurling was performed on both ends, and the film was wound at 4.8 kg / cm ² . Thus, a roll having a width of 2.4 m, a length of 3500 m, and a thickness of 120 μm was obtained.

(2) Undercoat layer (a) Polymer latex V-5 A core-shell type latex having a core of 90% by mass and a shell of 10% by mass, and a core of vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acryl. Acid = 93/3/3 / 0.9 / 0.1 (mass%) Shell part Vinylidene chloride / methyl acrylate / methyl methacrylate / acrylonitrile / acrylic acid = 88/3/3/3/3 (mass%) mass Average molecular weight 38000 Solid content 3.0 g / m ² 2,4-Dichloro-6-hydroxy-s-triazine 23 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 1.5 mg / m ²

(3) Undercoat layer (b) Alkali-treated gelatin (Ca ⁺⁺ content 30 ppm, jelly strength 230 g) 83 mg / m ² Compound A 1 mg / m ² Compound H 2 mg / m ² Methylcellulose 4 mg / m ² Compound I 3 mg / m ²

(4) Conductive layer Jurimar ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 96 mg / m ² gelatin 72 mg / m ² Compound A 0.2 mg / m ² Polyoxyethylene phenyl ether 5 mg / m ² Sumitex resin M-3 18 mg / m ² (water-soluble melamine compound manufactured by Sumitomo Chemical Co., Ltd.) Dye A (optical density at 780 nm ≧ 1.0) 25 mg / m ² SnO ₂ / Sb (9/1 mass ratio, needle-like fine particles) (Major axis / minor axis = 20-30, manufactured by Ishihara Sangyo Co., Ltd.) 230 mg / m ² Matting agent (polystyrene, average particle size 2.4 μm) 0.5 mg / m ² Compound J 2 mg / m ²

(5) Backing layer a Julimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) 95 mg / m ² Compound J 2 mg / m ² Sumitex Resin M-3 3 mg / m ² (water-soluble melamine compound Sumitomo Chemical Co., Ltd.) Carnava wax (Cerosol 524: manufactured by Chukyo Yushi Co., Ltd.) 3 mg / m ²

(6) Back layer b Same formulation as undercoat layer (a)

(7) Back layer c Polymer latex-c (Tg ≒ 45 ° C.) (methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 59/9/26/5/1 (mass) % Copolymer)) 1000 mg / m ² Lubricant A 37 mg / m ² Sumitex Resin M-3 (water-soluble melamine compound manufactured by Sumitomo Chemical Co., Ltd.) 218 mg / m ² Surfactant; Compound Example F-5 8 mg / m ² compound example F-3 7 mg / m ² matting agent (copolymer over methyl methacrylate / acrylic acid = 97/3 (mass%), an average particle diameter of 5 [mu] m) 11 mg / m ²

[0245]

Embedded image

An undercoat layer (a) and an undercoat layer (b) were sequentially applied to one side of the support, and each was dried at 180 ° C. for 4 minutes. Then, the conductive layer and the back layers a, b, and c are sequentially applied to the opposite surfaces to which the undercoat layer (a) and the undercoat layer (b) have been applied, respectively, and dried at 180 ° C. for 30 seconds to form a back / undercoat layer. The attached PET support was prepared. The PET support with the back / subbing layer prepared in this way was
It was placed in a heat treatment zone with a total length of 30 m set at 0 ° C. and transported under its own weight at a tension of 1.4 kg / cm ² and a transport speed of 20 m / min. Then, pass through the zone of 40 ℃ for 15 seconds, 10kg
/ Cm ^{2 at} a winding tension.

<< Preparation of heat-developable image recording material (sample) >> The conductive layer and the back layers a, b, c / undercoat layer (a),
Undercoat layers (a) and (b) of a PET support provided with (b)
The image forming layer and the lower layer and the upper layer of the protective layer were coated on the side with the mark, and the amount of silver applied was 1.6 g / m ² , and the lower layer was coated with 1.5 g of solid polymer latex.
g / m ² , and the upper layer was simultaneously multi-layer coated to 2.5 g / m ² and dried at 70 ° C. for 3 minutes to prepare a sample. The Beck smoothness of the prepared sample was 1 for the surface having the image forming layer.
000 seconds, the surface on the opposite side is 650 seconds, and the surface resistivity of the conductive layer is 4 × under the conditions of 25 ° C. and 20% relative humidity.
It was 10 ⁹ Ω.

<Evaluation> The obtained samples were evaluated as follows. (1) Coefficient of friction a) Coefficient of friction between the heat-developed part roller and the surface of the heat-developable image recording material having the image forming layer A 20 g load is applied to a member having the same surface material and outer diameter as the roller and having a width of 2 cm. Then, the frictional resistance (Fe) at 120 ° C. (thermal development processing temperature) when the surface having the image forming layer of the thermal development image recording material was moved at a speed of 19 mm / sec was measured. The coefficient of friction was determined. Coefficient of friction (μe) = Fe (g) / 20 (g)

B) Coefficient of friction between the smooth surface of the heat-developed portion and the back surface of the heat-developable image recording material: A smooth surface member (nonwoven fabric) having a size of 2 cm × 3.5 cm,
Under the same conditions as in a) under a load of 40 g, the frictional resistance (F
b) was measured, and the friction coefficient (μb) was determined in the same manner as in a).

(2) Suitability for Heat Developing Machine Processing Using the heat developing apparatus shown in FIG. 1, the surface materials of the roller 11 above the preheating section A and the roller 13 of the heat developing section B are made of silicone rubber (rubber hardness). 40 degrees, thickness 1.
5 mm), the smooth surface 14 in the Teflon ^TM nonwoven fabric, 9
The sample exposed to the halftone dot image of 0% was subjected to a heat development process under the following heat development conditions by setting the linear velocity ratio between the preheating section A and the heat development processing section B as shown in Table 5, and performing the heat development processing. Transportability and processing unevenness were evaluated.

The clearance between the surface of the roller 13 and the surface of the smooth surface 14 in the heat development processing section B was 0.4 mm. The nip force of the roller pair 12 in the cooling section C was 24 g / cm as a force for conveying the heat-developable image recording material.
The heating time in the preliminary heating section A is 11 to 24 seconds,
The heating time in the heat development processing section B was 16 to 28 seconds.

(Transportability) 5: Passing without generation of scratches 4: Passing with slight scratching 3: Passing with scratching 2: Passing long with scratching 1: Jamming and impossibility * Not more than 4 points practically Usable level (processing unevenness) 5: no processing unevenness 3: weak processing unevenness 1: strong processing unevenness The level between 5 and 3 is 4 and the level between 3 and 1 is 2
It is. * 3 or more points can be used practically

(Heat Development Conditions) 1) Pre-heating section A (a transport roller pair 11
(The temperature of the heat roller when f is set to f) Loading roller pair 11: a 75 ° C (± 0.5 ° C) (heat roller) b 90 ° C (± 0.5 ° C) c 105 ° C (± 0.5 ° C) d 117 ° C (± 0.5 ° C) e 121 ° C (± 0.5 ° C) f 121 ° C (± 0.5 ° C)

2) Thermal development processing section B (temperature of upper and lower plate heaters when heaters 15 are set to ac from upstream) Heater 15; upper part / lower part of a = 122 ° C./122° C. upper part b Lower part = 122 ° C / 122 ° C c Upper part / lower part = 122 ° C / 122 ° C (± 0.3 ° C for all)

3) Cooling Unit C The unloading roller pair 12 (heat roller temperature) 112 ° C. (± 0.5 ° C.) Cooling rate 120 ° C./min The results obtained are shown in Table 5. As is clear from Table 5, by setting the linear velocity ratio between the preheating section A and the heat development processing section B within the range of the present invention, it is possible to obtain an image having good transportability and no development processing unevenness. I understand.

[0256]

[Table 5]

Example 2 The friction coefficient (μ) shown in Table 6 was changed by changing the amount of the lubricant A applied to the back layer c in Example 1.
The sample of b) was prepared, and the heat developing machine processing suitability was evaluated in the same manner as in Example 1 by changing the smooth surface 14 of the heat developing machine of FIG. 1 to an aromatic polyamide nonwoven fabric. A sample having a coefficient of friction (μb) of 1.0 or less between the back surface of the heat-developable image recording material and the member of the smooth surface 14 of the heat developing machine has good transportability and can provide an image without development processing unevenness. It can be seen that the effect of the present invention is improved.

[0258]

[Table 6]

<Example 3> Sample Nos. 2 to 6 of Examples 1 and -3 described in Japanese Patent Application No. 10-346561 were used.
Samples were prepared in the same manner as in Sample Nos. 8 to 12, and as a result of evaluating suitability for processing with a heat developing machine under the same conditions as Sample Nos. 8 to 12 in Example 1 of the present invention, the transportability was good as in Example 1, An image without development processing unevenness was obtained.

<Example 4> In the sample No. 10 of Example 1, the clearance between the roller 13 and the smooth surface 14 of the heat development processing section B of the heat development processing apparatus of FIG. The nip force of the discharge roller pair 12 in the cold part C was adjusted to 25 g / cm as the transfer force, and the transferability and the processing unevenness were evaluated in the same manner as in Example 1. The processing unevenness was evaluated in the same manner as in Example 1, and the transportability was evaluated based on the ratio of the number of passing sheets to the number of processed sheets (50 sheets). Table 7 shows the results. As is clear from Table 7, the clearance between the roller and the smooth surface in the heat development processing section was 0.0 to 1.0.
In the case of mm, it is found that there is no unevenness in the transportability and the heat development process, and it is particularly favorable.

[0261]

[Table 7]

<Example 5> Based on Japanese Patent Application Laid-Open No. 10-48772, the sample No. 101 to 120 and the sample No. of Example-2. Create 201-214,
With respect to the obtained sample, the thermal processing machine of Example 1 was used to evaluate the suitability for thermal processing under the heat treatment conditions of Sample No. 10. As a result, an image having good transportability and having no unevenness in the developing process was obtained. Was done.

<Example 6> Based on Japanese Patent Application Laid-Open No. 11-511571, Examples 1 to 12 and Comparative Examples 1 to 3 were performed.
The sample was prepared, and the obtained sample was evaluated for heat processing performance under the heat treatment conditions of Sample No. 10 using the heat processing apparatus of Example 1, and as a result, the transferability was good, and An image without unevenness was obtained.

[0264]

According to the present invention, an image having no processing unevenness is obtained, the transportability is good, and the occurrence of scratches is eliminated.

[Brief description of the drawings]

FIG. 1 is a side view showing a configuration of a heat developing machine used in an embodiment.

[Explanation of symbols]

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

Claims (11)

(57) [Claims] 1. A heat-developable image recording material having at least one image-forming layer on a support and at least one protective layer provided on the image-forming layer is preheated and heat-developed. Wherein the heat-developable image recording material is conveyed by an opposing roller in a pre-heating unit, and the surface on the side having the image forming layer in the heat-development processing unit is driven by a driving roller. Contact
The linear velocity (R _A ) of the pre-heating unit and the heat development processing unit are used for transporting and developing the surface (back surface) opposite to the side having the image forming layer while contacting the smooth surface with the smooth surface. Of the linear velocity (R _B ) of (R _A / R _B ) is 95.0
% To 99.9% of the heat-developable image recording material. 2. The method for developing a heat-developable image recording material according to claim 1, wherein the developing process is performed at a linear velocity of 10 to 40 mm / sec. 3. The heat development processing device according to claim 1, wherein at least the surface of the roller of the heat development processing device which is in contact with the surface having the image forming layer is made of rubber having a rubber hardness of 50 degrees or less.
Development processing method of the heat-developable image recording material. 4. The method according to claim 3, wherein at least the surface of said roller is formed of silicone rubber. 5. The method for developing a heat-developable image recording material according to claim 1, wherein said smooth surface is formed of an aromatic polyamide nonwoven fabric or a polytetrafluoroethylene nonwoven fabric. 6. A heat-developable image recording material comprising a smooth surface which is in contact with the surface (back surface) opposite to the image forming layer during transport, and which is in contact with or opposed to the smooth surface. The clearance between the surface of the drive roller that contacts the surface on the image forming layer side when the recording material is conveyed is 0 to 2 mm
The method for developing a heat-developable image recording material according to any one of claims 1 to 5, wherein the heat-development is performed by a heat development processing apparatus having a heat development processing section. 7. A heat-developable image-recording material to be processed by the method of any one of claims 1 to 6, wherein a surface having an image forming layer at a temperature of the heat-development process and a heat-developable portion (Μe) and the ratio (μe) of the friction coefficient (μb) between the surface opposite to the side having the image forming layer (back surface) and the smooth surface of the heat-developed portion.
/ Μb) is 1.5 or more. 8. The coefficient of friction between the surface (back surface) on the side opposite to the side having the image forming layer and the smooth surface of the heat development section at the temperature of the heat development processing is 1.0 or less. Heat developed image recording material. 9. The heat-developable image recording material according to claim 7, wherein a polymer latex is used as a binder for the image forming layer and the protective layer. 10. On the side opposite to the side having the image forming layer, 2
The surface resistivity is 1 × 10 ¹² under the condition of 5 ° C. and 20% relative humidity.
7. The battery according to claim 7, which has at least one conductive layer having a resistance of Ω or less.
9. The heat-developable image recording material according to any one of items 9 to 9. 11. The heat-developable image recording material according to claim 7, further comprising a back layer on the side opposite to the side having the image forming layer, wherein a polymer latex is used as a binder for the back layer.