JPH117100A - Heat-developable image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable image recording material low in manufacturing cost and superior in heat stability and small in influence to the environment and yet high in quality by using a specified polyester for a support and forming a layer containing an organic silver salt with a specified coating solution. SOLUTION: At least one of the layers formed on the support contains at least one kind of organic silver salt and it is formed with the coating solution using a solvent composed mainly of water. The polyester of the support is made by a naphthalenedicarboxylic acid as a dicarboxylic acid component in an amount of >=30 mol.%, and heat treating it at 80 deg.C-220 deg.C, in the temperature range of 50 deg.C-up to its glass transition point, preferably, in a transportation tension of 0.04-6 kg/cm<2> , thus permitting this support to be superior in heat resistance, and the recording material using this to retain an excellently plane image-forming face after heat development and to obtain a high-quality image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable image recording material, and more specifically, to a heat-developable photosensitive material (
Hereinafter, it may be referred to as a heat development sensitive material).

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat.
No. 075, and D.A. Morgan and B.A. Sherry (Sh
ely) "Heat treated silver system (Therma
lly Processed Silver Systems ”(Imaging Pr
ocesses and Materials) Neblette 8th edition, Sturge
(Sturge), V.S. Walworth, A .; Shepp, page 2, 1969).
Such a photothermographic material comprises a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent, which are usually (organic) binders. It is contained in a dispersed state in the matrix. Photothermographic materials are stable at room temperature, but when heated to a high temperature (for example, 80 ° C or higher) after exposure, silver is generated through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. I do. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. In such a photothermographic material, mercury has been used in order to ensure the preservability, but there has been a problem of environmental destruction.

In recent years, in the medical field and the printing field, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental protection and space saving. Thus, photosensitivity for medical diagnostics, printing and photographic applications, which can be efficiently exposed by a laser imagesetter or laser imager and can form black images with high resolution and sharpness There is a need for technology relating to thermally developed photographic materials. These photothermographic materials can eliminate the use of solution processing chemicals and provide a simpler and more environmentally friendly thermal development system to customers.

On the other hand, semiconductor laser technology, which has made rapid progress in recent years, has made it possible to reduce the size of medical image output devices. Naturally, technology for infrared-sensitive heat-developable silver halide photographic materials that can use a semiconductor laser as a light source was also developed, and spectral sensitization technology was used in Japanese Patent Publication Nos. 3-10391 and 6-52387.
No., JP-A-5-341432, JP-A-6-94781, JP-A-6-30
The antihalation technology is disclosed in JP-A-7-13295 and US Pat. No. 5,380,635.

Conventionally, such a photothermographic material has been produced by applying a photosensitive layer containing a thermoplastic hydrophobic polymer mainly containing an organic solvent such as ketones, but uses a large amount of the organic solvent. Therefore, it becomes a factor that causes environmental problems, or the cost for recovery is extremely high, and it is difficult to increase the efficiency of manufacturing by simultaneous multi-layer coating, resulting in high cost. A possible photothermographic material has been desired. further,
In recent years, there has been a demand for higher efficiency of photothermographic materials, and the development process has been conducted at a higher temperature and in a shorter time, and improvement in heat resistance has been desired. In addition, application using an organic solvent as a main component can only use a solvent-resistant support, which narrows the range of choice of the support and is an obstacle to satisfying heat resistance. Was.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a low production cost, excellent thermal stability, low environmental impact,
Moreover, it is to provide a high-quality heat-developable image recording material.

It is a further object of the present invention to provide a high-quality photothermographic material having a low production cost, excellent thermal stability, low environmental impact and high quality.

[0008]

This object has been achieved by the following means. (1) In a heat-developable image recording material having at least one layer containing at least one organic silver salt on a support, the support contains at least 30 mol% of naphthalenedicarboxylic acid as a dicarboxylic acid component, and has a temperature of 80 ° C. Heat development using a polyester heat-treated at a temperature of at least 220 ° C. or lower, wherein the layer containing the organic silver salt is formed from a coating solution containing water as a main component of a solvent. Image recording material. (2) A heat-developable image recording material having at least one layer containing at least one kind of organic silver salt on a support, wherein the support is made of polyethylene terephthalate which has been heat-treated at 80 ° C to 220 ° C. The heat-developable image recording material, wherein the layer containing the organic silver salt is formed from a coating solution containing water as a main component of a solvent. (3) In a heat-developable image recording material having at least one layer containing at least one organic silver salt on a support, the support contains at least 30 mol% of naphthalenedicarboxylic acid as a dicarboxylic acid component, and has a temperature of 50 ° C. A heat-developed image using a polyester heat-treated at a temperature lower than the glass transition temperature, wherein the layer containing the organic silver salt is formed from a coating solution containing water as a main component of a solvent. Recording material. (4) In a heat-developable image recording material having at least one layer containing at least one kind of organic silver salt on a support, the support uses a polyarylate-based polymer and contains the organic silver salt. A heat-developable image recording material, wherein the layer is formed from a coating solution containing water as a main component of a solvent. (5) heat-developable image recording material according to the support is conveyed by heat treatment at 0.04 kg / cm ² or more 6 kg / cm ² or less tension above (1) or (2). (6) The above (1) to (1), wherein at least one layer containing an organic silver salt is a photosensitive emulsion layer containing a photosensitive silver halide.
The heat-developable image recording material according to any one of (5).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The heat-developable image recording material of the present invention has a layer containing an organic silver salt, that is, at least one image forming layer, on a support, and such an image forming layer contains photosensitive silver halide. It is preferably a photosensitive emulsion layer, and such an image forming layer is formed by aqueous coating using a coating solution of a solvent (dispersion medium) containing water as a main component.

[0010] By such aqueous coating, the range of choice of the support can be expanded as compared with the solvent coating, and a support made of a material suitable for heat development can be selected. From this perspective,
In the present invention, the following supports are used.

1) Naphthalenedicarboxylic acid as a dicarboxylic acid component in an amount of at least 30 mol% or more, and
At a temperature of not lower than 220 ° C. and preferably 0.04 to 6 ° C.
Polyester transported at a tension of kg / cm ² and heat-treated,
Heat-treated at a temperature of preferably 50 ° C. or higher and lower than the glass transition temperature.

2) Polyethylene terephthalate (PET) heat-treated at a temperature of 80 ° C. or more and 220 ° C. or less, preferably one transported under a tension of 0.04 to 6 kg / cm ² and heat-treated.

3) Polyarylate polymer These supports are excellent in heat resistance, and in a heat-developable image recording material using them, the flatness of the image forming surface after heat development is maintained, and a high-quality image is obtained. can get.

The support used in the present invention will be described.

In the support of the present invention, the polyester is composed of dicarboxylic acid and diol. Preferred dicarboxylic acids are (2,6-, 1,5-, 1,4
-, 2,7-) naphthalenedicarboxylic acid (NDCA),
Examples include terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), paraphenylenedicarboxylic acid (PPDC), and ester-forms thereof. Among them, terephthalic acid (TPA),
2,6-naphthalenedicarboxylic acid (2,6-NDCA)
And their ester formers are preferred.

However, copolymerization of a hydrophilic monomer such as 3-sulfoisophthalate or sulfonaphthalenedicarboxylate undesirably causes a decrease in mechanical strength (particularly, bending elasticity) due to water absorption.

The diol is ethylene glycol (E
G), cyclohexane dimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (B
PA) and biphenol (BP) are preferred, and ethylene glycol is more preferred.

Polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol are not preferred because they cause a decrease in mechanical strength (particularly bending elasticity) due to water absorption.

Polyesters can be formed by using hydroxycarboxylic acids in addition to diols and dicarboxylic acids, and parahydroxybenzoic acid (PHBA), 6-hydroxy-2-
Naphthalene carboxylic acid (HNCA) may be used.

Of these, preferred are those comprising naphthalenedicarboxylic acid or its ester-forming product and ethylene glycol, wherein the content of naphthalenedicarboxylic acid in all dicarboxylic acid units is 30 mol% or more and 100 mol% or more. It is preferably at most 50 mol%, more preferably at most 50 mol% and at most 100 mol%, even more preferably at least 70 mol% and at most 100 mol%. this is,
It may be a copolymer or a polymer blend.

In the case of copolymerization, those obtained by copolymerizing units such as terephthalic acid, bisphenol A and cyclohexanedimethanol are also preferable. Among these, the most preferred is a copolymer of a terephthalic acid unit from the viewpoint of mechanical strength and cost.

Such a copolymer is prepared by subjecting the starting dicarboxylic acid and dialcohol to 180 to 280 ° C. under a pressure of 1 to ² kg / mm ² or atmospheric pressure, more preferably 230 to 270 ° C.
C. for 0.5 to 8 hours, more preferably 2 to 4 hours, and then transesterification, followed by heating at 240 to 290.degree. C. under a vacuum of 50 to 1 mmHg for 1 to 3 hours to polymerize. it can.

In the case of a polymer blend, a preferable partner to be blended with polyethylene naphthalate (PEN) which is a component for realizing the above-mentioned amount of naphthalenedicarboxylic acid is
From the viewpoint of compatibility, polyethylene terephthalate (PE
T), polyesters such as polyarylate (PAr), polycarbonate (PC), and polycyclohexanedimethanol terephthalate (PCT). Among them, preferred are mechanical strength and cost. It is a polymer blend with PET. The amount of PEN in such a polymer blend only needs to satisfy the above molar ratio, but is usually about 10 to 95% by weight.

In order to form such a polymer blend, 5 to 30 minutes, preferably 8 to 25 minutes, more preferably 10 to 2 minutes in an extruder.
It is preferable to knead the mixture for 0 minute or less. At this time, it is more preferable to use a twin screw extruder.

Preferred polyesters also include polyethylene terephthalate. In this case, after film formation, heat treatment is performed at a temperature of 80 ° C. or more and 220 ° C. or less as described later.

From the viewpoint of heat resistance, these polyesters preferably have a glass transition temperature (Tg) of 60 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 10 ° C. or higher.
0 ° C. or higher. The upper limit of Tg in this case is not particularly limited, but is about 200 ° C.

These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, an acid component may be directly esterified with a glycol component (direct weight method), or a dialkyl ester (for example, dimethyl ester or diethyl ester is preferable) as the acid component, and a transesterification reaction with the glycol component is performed. This may be heated under reduced pressure to remove excess glycol components (ester exchange method). Alternatively, an acid component may be used as an acid halide and reacted with glycol. Among them, the transesterification method is preferable,
This is the direct weight method.

In these polymerizations, a transesterification catalyst or a polymerization reaction catalyst may be used, if necessary, or a heat-resistant stabilizer (for example, phosphorous acid, phosphoric acid, trimethyl phosphate, triethyl phosphate, Tetraethylammonium).

Regarding these polyester synthesis methods,
For example, Polymer Science, Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980), pp. 103-136, “Synthetic Polymer V” (Asakura Shoten, 1971), 187-28.
Description on page 6, and JP-A-5-163337 and 3-179
No. 052, No. 2-3420, No. 1-275628,
Reference can be made to JP-A Nos. 62-290722 and 61-241316.

The polymer thus polymerized preferably has an intrinsic viscosity of 0.40 or more and 0.9 or less measured at 35 ° C. in an orthochlorophenol solvent.
Those having 0.45 to 0.70 are more preferable.

Preferred specific examples of the polyester compound used in the present invention are shown below, but the present invention is not limited thereto. In addition, Tg is shown.

Examples of polyester homopolymers (numbers in parentheses of starting monomers indicate molar ratios) HP-1: polyethylene naphthalate (PEN) [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol ( EG) (100/100)] (PEN) Tg = 119 ° C HP-2: Polyethylene terephthalate (PET) {terephthalic acid (TPA) / ethylene glycol (EG) (100/100)} (PET) Tg = 69 ° C

Polyester copolymer example (numbers in parentheses indicate molar ratio) CP-1: 2,6-NDCA / TPA / EG (70/30/100) Tg = 98 ° C. CP-2: 2,6- NDCA / TPA / EG (80/20/100) Tg = 105 ° C. CP-3: 2,6-NDCA / TPA / EG (90/10/100) Tg = 110 ° C. CP-4: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C CP-5: 2,6-NDCA / EG / BPA (100/25/75) Tg = 155 ° C CP-6: 2,6- NDCA / EG / CHDM / BPA (100/25/25/50) Tg = 150 ° C CP-7: 2,6-NDCA / NPG / EG (100/70/30) Tg = 145 ° C CP-8: 2 6-NDCA / E G / BP (100/20/80) Tg = 130 ° C

PB-1: PEN / PET (60/40) Tg = 95 ° C. PB-2: PEN / PET (80/20) Tg = 104 ° C PB-3: PEN / PET (90/10) Tg = 109 ° C PB-4: PAr / PEN (15/85) Tg = 138 ° C PB-5: PAr / PCT / PEN (10/10/80) Tg = 135 ° C PB-6: PAr / PC / PEN (10/10/80) Tg = 140 ° C PB-7: PEN / PET (20/80) Tg = 79 ° C

Another preferred support in the present invention is a polyarylate polymer.

The polyarylate (PAr) polymer is a polycondensate of bisphenol-A (2,2-bis (4-hydroxyphenyl) propane) as diol and terephthalic acid as dicarboxylic acid. It refers to those containing at least 50 mol% or more. Other dicarboxylic acid components include isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, and the like. Can be Examples of diols other than bisphenol-A include 4,4'-biphenol, bisphenol-S, bisphenol AF, and bisphenol-A.
Ru-Z, ethylene glycol and the like can be used.

These polymers can be polymerized by transesterification using the esters of these dicarboxylic acids as starting materials. These are polycondensed under vacuum at 150 ° C. to 350 ° C. using dibutyltin oxide, tetrabutyl titanate, disodium phenylphosphate or the like as a catalyst. At this time, it is also preferable to use a transesterification catalyst. Moreover, you may superpose | polymerize by a direct weight method. See J.Polym.Sc for details
i., 40, 399 (1959), J. Polym. Sci., 28, 179 (1958),
The method can be carried out with reference to methods such as 53-114895 and JP-A-5-331268. The molecular weight of the resulting polyarylate is from 5,000 to 100,000, preferably from 10,000 to 50,000.

Of these, those having bisphenol-A and terephthalic acid as constituent units are more preferred. These polymers may be used alone or as a mixture (polymer blend).

The Tg of these PAr polymers is 16
0-220 ° C.

It is also preferable to add a phosphoric acid ester to these polymers in order to impart stability. The added amount is preferably 0 ppm to 300 ppm in terms of phosphorus atom, more preferably 10 ppm to 100 ppm.

Further, an ultraviolet absorber may be added for the purpose of imparting stability over time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount of the ultraviolet absorber is usually about 0.5% to 20% by weight, preferably about 1% to 10% by weight based on the weight of the polymer film. It is.

Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2,2 '. Benzophenones such as 2,4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy3 ', 5'-di-t-
Benzotriazoles such as butylphenyl) benzotriazole and 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole; and salicylic acid-based ultraviolet absorbers such as phenyl salicylate and methyl salicylate. Can be

Further, in order to avoid the so-called light piping phenomenon, there are known a method of adding inert inorganic particles and the like to a film and a method of adding a dye. The method based on the addition of a dye is preferable because it does not significantly increase the film haze.

Regarding the dye used for film dyeing,
The color tone is preferably gray dyeing due to the general properties of the light-sensitive material, and preferably has excellent heat resistance in a film forming temperature range of the polyester film and excellent compatibility with the polyester.

As the dye, from the above viewpoints, it is possible to achieve the object by mixing a dye commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Particularly, from the viewpoint of heat stability, anthraquinone dyes can be used. For example, those described in JP-A-7-168309 and Japanese Patent Application No. 6-265180 can be preferably used.

The polymer support according to the present invention can be imparted with lubricity depending on the application, and kneading of an inert inorganic compound or coating of a surfactant is used as a general method.

The inert inorganic particles include SiO 2
₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. In addition to the lubricity imparted by the external particle system in which inert particles are added to the polyester synthesis reaction system described above, a lubricity imparting method using an internal particle system in which a catalyst or the like to be added during the polymerization reaction of the polyester is precipitated can also be adopted. It is. As the external particle system, it is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester film, or an internal particle system capable of relatively reducing the particle diameter of precipitation.

The preferred addition amount is 5 ppm or more and 1000 p
pm or less, more preferably 10 ppm or more and 500 ppm
The content is more preferably 20 ppm or more and 200 ppm or less. The size of the particles to be added is preferably from 0.01 μm to 10 μm, more preferably from 0.05 μm to 5 μm, even more preferably from 0.1 μm to 2 μm.

Next, a method for forming a film of these polymer supports will be described.

The polymer polymerized by the method described above is pelletized and dried at 80 ° C. to 200 ° C. for 1 hour or more. Thereafter, the melting point temperature (Tm) of the polymer or more,
Melts below 330 ° C. Thereafter, it is preferable to previously filter the molten polymer using a filter. Examples of the filter include wire mesh, sintered wire mesh, sintered metal, sand, glass fiber, and the like. This is melt-extruded from a T-die to form an unstretched film.
When performing two or more polymer blends, it is preferable to use a usual multi-screw kneading extruder. Also, when forming a laminate, co-extrusion method, in-line laminating
Or the off-line laminating method.

The molten polymer extruded from the T-die is
It is extruded onto a casting drum having a Tg of -80 ° C to Tg (Tg: glass transition temperature of polyester), more preferably a Tg of -60 ° C to Tg-10 ° C. At this time, the flatness may be improved by improving the adhesion to the drum by an electrostatic application method or a liquid film formation method (a fluid such as water is applied on a casting drum to improve the adhesion between the melt and the drum). preferable.

In the unstretched film thus obtained, an amorphous polymer such as polyarylate is used in an unstretched state. For a crystalline polymer such as PET or PEN, the unstretched film is simultaneously or successively used. A biaxially stretched film is formed by axial stretching, heat setting, and thermal relaxation. Longitudinal direction·
Although the number of times of stretching in the transverse direction is not limited, a sequential biaxial stretching method in which transverse stretching after longitudinal stretching and heat setting are performed is preferred.

This is because the unstretched film is stretched in a uniaxial direction (longitudinal direction or transverse direction) from Tg−10 ° C. to Tg + 70 ° C., more preferably Tg−Tg + 50 ° C., and still more preferably
2.5 to 4.5 times, more preferably 2.7 to 4.0 times, and more preferably 2.8 to 3.0 times at + 5 ° C to Tg + 35 ° C.
Stretch 8 times. Such stretching is performed, for example, at the outlet row.
This can be achieved by making the roller speed faster than the roller speed at the entrance.

Next, in the direction perpendicular to the stretching direction (when the first-stage stretching is the longitudinal direction, the second-stage stretching is in the transverse direction) at a temperature of Tg ° C. to Tg + 70 ° C., from 2.5 to 4.5 times. Preferably, it is 2.7 to 4.0 times, more preferably 2.8.
Stretch to 3.8 times. When the stretching ratio is small in both the vertical and horizontal directions, the elastic modulus is lowered, which is not preferable in handling. On the other hand, when the draw ratio is large, the heat shrinkage tends to be large,
Not preferred.

After that, the biaxially stretched film is heated to Tg + 30 ° C.
~ Melting temperature (Tm), more preferably Tg + 40 ° C ~
Tm−10 ° C., more preferably Tg + 60 ° C. to Tm
Heat set at a temperature of -20 ° C. The preferred heat setting time is 1
0 seconds or more and 3 minutes or less, more preferably 15 seconds or more and 1 minute 30
Seconds, more preferably 20 seconds or more and 60 seconds or less. Further, it is also preferable to carry out thermal relaxation subsequent to heat setting. The temperature at this time is Tg + 30 ° C. to Tm, more preferably Tg + 40 ° C. to Tm−10 ° C., further preferably,
Tg + 60 ° C to Tm-20 ° C. The preferred amount of relaxation is 0% or more and 15% or less, more preferably 2% or more and 12% or less, and still more preferably 3% or more and 10% or less. Relaxation may be in either the longitudinal or lateral direction or both. After that, it is cooled and trimmed and wound up on a roll.

Both ends or one end of the polymer support may be used.
It is also preferable to apply embossing having a height of 1 μm to 100 μm at a position of 2 cm to 10 cm from the viewpoint of improving the handleability.

The base thickness of the polymer support is preferably 50 μm or more and 300 μm or less. More preferably 80 μm or more and 200 μm or less, more preferably 90 μm
It is 180 μm or less. When the base is thin, the stiffness of the base is weak. On the other hand, when the base is thick, the base is too strong, which is not preferable in handling.

In particular, in the case of a PEN support or the like, the support thus obtained can be subjected to a heat treatment of 50 ° C. or more and less than Tg (hereinafter sometimes referred to as BTA treatment). This can significantly reduce the curl of the support.

The Tg in the present invention can be determined by using a scanning differential thermal analyzer (DSC). That is, in a nitrogen stream, a sample amount of 10 mg was
/ Minute after heating to 300 ° C (1st run), quenching to room temperature, and then heating again at 20 ° C / minute (2nd ru
In n), it is obtained as the arithmetic mean of the temperature at which deviation starts from the base line and the temperature at which it returns to the new base line.

The BTA treatment is preferably carried out at 50 ° C. or more and less than Tg, more preferably at Tg-35 ° C. or more and less than Tg, and more preferably at Tg-20 ° C. or more and less than Tg. That is, the point is to perform at a temperature lower than Tg,
The upper limit of such a temperature is, for example, Tg-1 ° C. When performed at a low temperature, it takes a long time to obtain a sufficient curling effect, and industrial productivity is poor, which is not preferable. On the other hand, at a high temperature, it is difficult to form a winding habit.

The BTA treatment may be performed at a constant temperature within this temperature range, or may be performed while raising or cooling the temperature. In the heat treatment while raising or cooling the temperature, the temperature may be continuously changed or may be changed stepwise. Of these, heat treatment at a constant temperature or while cooling is preferable. The average cooling rate is -0.0.
01 to -150C / hour, more preferably -0.1 to-
100 ° C./hour, more preferably −0.2 to 80 ° C./hour
Time. In such a case, the cooling start temperature can be Tg. BTA processing time is 0.1 hours or more 1
500 hours or less, more preferably 0.2 hours or more and 500
Hours or less, more preferably 0.3 hours or more and 150 hours or less. In a short time, a sufficient effect cannot be obtained, and in a long time, the effect is saturated, while coloring or embrittlement of the support is likely to occur.

In order to further increase the effect of eliminating such curl, it is also preferable to carry out a heat treatment (hereinafter sometimes referred to as “pre-heat treatment”) at a temperature of Tg or more and less than Tm before the BTA treatment. .

The pre-heat treatment is preferably performed at a temperature of at least Tg and lower than the melting point, and more preferably at a temperature of Tg + 20 ° C. or higher and lower than the crystallization temperature.

The pre-heat treatment may be performed at a constant temperature within this temperature range, may be performed while lowering the temperature, or may be performed while raising the temperature. The pre-heating time is 0.1
Minutes to 1500 hours, more preferably 1 minute to 1 hour
Less than an hour. In a short time, a sufficient effect cannot be obtained, and in a long time, the support tends to be colored or embrittled.

After this pre-heat treatment, the post-heat treatment BTA
Although the treatment is performed, the temperature may be rapidly cooled from the pre-heat treatment end temperature to the BTA treatment temperature, or may be continuously cooled to the BTA treatment temperature. After cooling to room temperature, BTA treatment may be performed.

When the BTA-treated support is measured by DSC, an endothermic peak having a maximum value between Tg-20 ° C. and Tg + 80 ° C. appears. Area of this endothermic peak (endothermic amount)
The larger the is, the less likely the winding habit is. Endotherm is 10
It is preferably from 0 mcal / g to 1000 mcal / g. If the amount of heat absorbed is small, the curl cannot be sufficiently formed, and even if the amount of heat absorbed becomes large, the effect of making the curl difficult is saturated. More preferably, 150
It is from mcal / g to 500 mcal / g, more preferably from 200 mcal / g to 400 mcal / g. The amount of endotherm was 2 for 10 mg sample using DSC.
This is a value measured in a nitrogen stream while heating at a rate of 0 ° C./min.

As described above, in the case of the PET support, only the material corresponding to the above-mentioned pre-heat treatment may be used.
Subsequently, post-heat treatment can be performed at a temperature of about 30 to 60 ° C. for about 5 to 100 seconds. Such post heat treatment is performed by PE
N is also effective.

The heat treatment of such a support (BTA treatment,
The pre-heat treatment) can be carried out while being conveyed in a roll form or a web form.

In the case of heat treatment in a roll form, the roll is heat-treated in a constant temperature bath from room temperature (hereinafter referred to as a low-temperature winding method).
It may be carried out by any of a method of performing a heat treatment for winding into a round shape (hereinafter referred to as a high-temperature winding method). The former method requires time for raising and lowering the temperature, but has the advantage of reducing capital investment. On the other hand, the latter method requires an equipment for winding at a high temperature, but has the advantage that the time for raising the temperature can be omitted.

[0070] low-temperature winding method, with hot winding method, the winding tension per unit width is preferably from 0.1 to 20 kg / cm ^2, more preferably 0.2~18kg / cm ^2, more preferably 0.5~15kg
/ cm ² . When the winding tension is small, the roll is apt to be sagged due to its own weight during the heat treatment due to gentle winding. On the other hand, when the winding tension is large, wrinkles due to tightness of the winding are liable to occur.

The diameter of the core around which the support is wound is 50 mm or more and 2000 mm or less, more preferably 1 mm or less.
00 mm or more and 1000 mm or less, more preferably 15
0 mm or more and 600 mm or less. The material of the winding core is not particularly limited, but is preferably a material that does not cause a decrease in strength or deformation due to heat, and examples thereof include stainless steel, aluminum, and a resin containing glass fiber. Further, rubber or resin may be lined on these cores as necessary. Further, a heating heater may be provided inside for heating from the inside where heat transfer is slow, or may be hollow so that hot air or high-temperature liquid can flow.

[0072] If the support prior to application of the photosensitive emulsion layer is subjected to heat treatment before a glass transition temperature or higher at web-like, conveyance tension is preferably 0.04 kg / cm ² or more 6 kg / cm ² or less, 0.2
kg / cm ² or more and 5.5 kg / cm ² or less, more preferably 1 kg / cm ²
It is more preferably at least 5 kg / cm ² . If the transport tension is reduced, the support flaps during transport, and scratches are likely to occur during transport. On the other hand, when the transporting tension is increased, the support is elongated by the tension, and the support becomes a tin plate-like shape, and the flatness is likely to deteriorate, which is not preferable.

This heat treatment may be performed at a constant temperature.
A plurality of heat treatment zones may be provided and the treatment may be performed while changing the treatment temperature.

The heat treatment (BTA treatment, pre-heat treatment) may be performed anywhere from the film formation to the application of the photosensitive layer.

Examples of preferred heat treatments (BTA treatment, pre-heat treatment) are shown below, but are not limited thereto. (→ in the following example indicates that the treatment was performed continuously, and → is not described.) During this period, it indicates a discontinuous treatment once cooled to room temperature).

Pre-heat treatment BTA treatment (roll method; high-temperature winding method) # 1 10 minutes at Tg + 50 ° C. → winding at Tg → 24 hours at Tg-5 ° C. constant # 2 5 minutes at Tg + 20 ° C. → Winding at Tg → Cooling from Tg to Tg-30 ° C at -1 ° C / hr # 3 None Winding at Tg-5 ° C → Holding at Tg-5 ° C constant for 24 hours, then -1 ° C / Tg to 30 ° C Cooling at hr # 4 30 min at Tg + 20 ℃ → Winding at Tg → Cooling from Tg to 50 ℃ at -2 ℃ / hr # 5 None Winding at Tg → Cooling from Tg to 90 ℃ at -1 ℃ / hr After cooling down to 50 ℃ at -2 ℃ Pre-heat treatment BTA treatment (roll method; low temperature winding method) # 6 Tg + 50 ℃ for 10 minutes Tg-5 ℃ constant for 24 hours # 7 Tg + 20 ℃ for 5 minutes Cooling from Tg to Tg-30 ℃ at -1 ℃ / hr # 8 None After holding at Tg-5 ℃ constant for 24 hours, cooling to Tg-30 ℃ at -1 ℃ / hr # 9 Tg at + 20 ℃ for 30 minutes From Tg Cooling down to 50 ℃ at -2 ℃ / hr # 10 None Tg-5 ℃ constant for 48 hours

Pre-heat treatment BTA treatment (web method) Heat treatment zone No.1 Heat treatment zone No.2 Heat treatment zone No.3 # 11 5 minutes at Tg + 20 ° C. → 10 minutes at Tg-5 ° C. → 10 minutes at Tg-5 ° C → 10 minutes at Tg-5 ° C # 12 3 minutes at Tg + 40 ° C → 5 minutes at Tg ° C → 10 minutes at Tg-5 ° C → 5 minutes at Tg-10 ° C # 13 Tg + 5 minutes at 50 ° C → 10 minutes at Tg-5 ° C → 10 minutes at Tg-15 ° C → 5 minutes at Tg-25 ° C # 14 None 10 minutes at Tg-5 ° C → 10 minutes at Tg-15 ° C → Tg- 5 minutes at 25 ° C # 15 5 minutes at Tg + 50 ° C → 20 minutes at Tg-5 ° C → 20 minutes at Tg-15 ° C → 15 minutes at Tg-25 ° C

The support of the present invention may have an undercoat layer.

The undercoat layer in the present invention refers to a layer other than the photosensitive layer, which is coated directly on the support, and can be provided on either the photosensitive layer side or the back layer side. In addition to adhesiveness, the undercoat layer can be provided with antistatic properties, antihalation properties, crossover cut properties, dyeing properties, ultraviolet cut properties, matte properties, scratch resistance, and the like.

As the undercoat layer provided with the adhesive property,
A layer that adheres well to the support (hereinafter abbreviated as first undercoat layer) is provided as a layer, and a layer that adheres the undercoat first layer and the photographic layer well as a second layer (hereinafter abbreviated as undercoat second layer) is provided thereon. )
And a single-layer method in which only a single layer of the support and the photographic layer is adhered to each other.

The undercoating first layer in the multilayer method is selected from, for example, vinyl chloride, vinylidene chloride, butadiene, vinyl acetate, styrene, acrylonitrile, methacrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like. Copolymer starting from the obtained monomer, epoxy resin, gelatin, nitrocellulose,
Polyvinyl acetate or the like is used. Also, if necessary,
Triazine-based, epoxy-based, melamine-based, isocyanate-based including blocked isocyanate-based, aziridine-based, oxazaline-based crosslinking agents, colloidal silica and other inorganic particles, surfactants, thickeners, dyes, preservatives, etc. Is also good. (For these, see EHImmergut "Polymer
Handbook "VI187-231, Intersciense Pub.New Y
ork 1966 and JP-A-50-39528, 50-4
No. 7196, No. 50-63881, No. 51-1335
No. 26, No. 64-538, No. 63-174698,
Japanese Patent Application No. 1-240965, JP-A-1-240965
No. 2-184844, JP-A-48-89870
No. 48-93672, etc.).

In the single-layer method, in many cases, a method of swelling a support and mixing it with an undercoat polymer at an interface to obtain good adhesion is often used. Examples of the undercoat polymer include gelatin, gelatin derivatives, casein,
Water-soluble polymers such as agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer and maleic anhydride copolymer, cellulose esters such as carboxymethylcellulose and hydroxyethylcellulose, vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers Latex polymers such as polymers, acrylate ester-containing copolymers, vinyl acetate-containing copolymers, and vinyl acetate-containing copolymers are used. As the gelatin, any of those generally used in the art, such as so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin, can be used.
Among these gelatins, lime-treated gelatin and acid-treated gelatin are most preferably used.

It is also possible to use only the first layer of the multilayer method.

It is important that the drying temperature in the single-layer method and the multi-layer method is set at 50 ° C. or more and 150 ° C. or less as described above.

It is also preferable to perform a surface treatment prior to the undercoating in order to improve the adhesiveness. Preferred surface treatments are glow discharge treatment, corona treatment, ultraviolet irradiation treatment,
Flame treatment. Depending on the formulation of the photosensitive emulsion layer or the backing layer (backing layer), the required adhesion may be obtained only by the surface treatment, in which case it is not always necessary to perform the undercoating.

The glow treatment can be performed by a conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-10336,
No. 45-22004, No. 45-22005, No. 45
Nos. 240040 and 46-43480,
No. 129262, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638, 3,309,299, 3,424,735. No. 3,462,335, No. 3,475,307, No. 3,761,299, No. 4,072,769, British Patent 891,469, No. 997,093, etc. Can be used.

In such a glow treatment, the most excellent bonding effect can be obtained particularly when steam is introduced into the atmosphere. The water vapor partial pressure is preferably from 10% to 100%, more preferably from 40% to 90%. If it is less than 10%, it will be difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like.

Further, if the glow treatment is performed in a state where the support to be surface-treated is heated, the adhesiveness is improved in a short time, which is effective. The preheating temperature is preferably from 50 ° C. to Tg, more preferably from 60 ° C. to Tg, and even more preferably from 70 ° C. to Tg. Preheating at a temperature above Tg deteriorates adhesion.

The degree of vacuum during the glow treatment is 0.005 to 20.
Torr is preferred. More preferably 0.02
~ 2 Torr. The voltage is 500-5000.
Preferably between V. More preferably 500-3000V
It is. The discharge frequency used is, as seen in the prior art, from DC to several 1000 MHz, preferably 50 Hz to
20 MHz, more preferably 1 KHz to 1 MHz. The discharge treatment intensity is 0.01 KV · A · min / m ² -5
KV · A · min / m ² is preferable, and 0.1 is more preferable.
Desired adhesive performance at 5 KV · A · min / m ² ~1KV · A · min / m ^2.

The corona treatment is the most well-known method, and any method known in the art, for example,
Nos. 5043 and 47-51905, JP-A-47-28
Nos. 067, 49-83767 and 51-41770
And JP-A-51-131576. Discharge frequency is 50Hz-500
0 kHz, preferably 5 kHz to several 100 kHz is appropriate. Regarding the processing strength of the processing object, 0.001K
V · A · min / m ² ~5KV · A · min / m ^2, preferably is 0.01 kV · A · min / m ² ~1KV · A · min / m ² suitably. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.

The ultraviolet treatment is described in JP-B-43-2603,
It is preferably carried out by the processing methods described in JP-B-43-2604 and JP-B-45-3828. The mercury lamp is a high-pressure mercury lamp or a low-pressure mercury lamp formed of a quartz tube, and preferably has a wavelength of ultraviolet light of 180 to 380 nm.

Regarding the method of irradiating ultraviolet rays, if the high-pressure mercury lamp has a main wavelength of 365 nm, the irradiation light amount is 20 to
10,000 (mJ / cm ² ) is preferable, and more preferably 50 to 2
000 (mJ / cm ² ). In the case of a low-pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 10,000.
(MJ / cm ² ), more preferably 200 to 1500.
(MJ / cm ² ).

The method of flame treatment may be natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, a preferable mixing ratio of propane gas / air is 1/14 to 1/22, preferably 1/16 to 1/19 by volume ratio. In the case of natural gas, the ratio is 1/6 to 1/10, preferably 1/7 to 1/9.

The flame treatment is preferably carried out at 1 to 50 Kcal / m ² , more preferably at 3 to 30 Kcal / m ² . Further, it is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. As the processing device, a frame processing device manufactured by Kasuga Electric Co., Ltd. can be used. The backup roll supporting the support during the flame treatment is a hollow roll, which is preferably cooled at a constant temperature by passing through cooling water.

The organic silver salt which can be used in the present invention is
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, in particular silver salts of long-chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Also preferred are complexes of organic or inorganic silver salts wherein the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver donor material can preferably comprise about 5-70% by weight of the imaging layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate,
Silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, 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 3-mercapto-4
-Phenyl-1,2,4-triazole silver salt, 2-mercaptobenzimidazole silver salt, 2-mercapto-5-aminothiadiazole silver salt, 2- (ethylglycolamide) benzothiazole silver salt, S- Silver salts of thioglycolic acid such as silver salts of alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithiocarboxylic acids such as silver salts of dithioacetic acid, silver salts of thioamides, 5 -Carboxyl-1-methyl-2-phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, silver salts described in U.S. Pat.No.4,123,274, for example, 3-amino-5 Silver salts of 1,2,4-mercaptothiazole derivatives such as -benzylthio-1,2,4-thiazole silver salt, 3- (3-carboxyethyl) -4- described in U.S. Pat.No. 3,301,678
Includes silver salts of thione compounds such as silver salt of 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, U.S. Pat.
0,709 1,2,4-triazole or 1-H-
Includes silver salts of tetrazole, silver salts of imidazole and imidazole derivatives, and the like. For example, U.S. Pat.
Various silver acetylide compounds as described in No. 1 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 minor axis is 0.01 μm or more and 0.2 μm or more.
0 μm or less, major axis of 0.10 μm or more and 5.0 μm or less, minor axis of 0.01 μm or more and 0.15 μm or less, and major axis of 0.10 μm or more and 4.0 μm or less are more preferred. The particle size distribution of the organic silver salt is preferably monodispersed. Monodisperse and the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by each minor axis, major axis is preferably 100% or less, more preferably 80% or less,
More preferably, it is 50% or less. 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 of measuring the monodispersity, there is a method of determining the standard deviation of the volume-weighted average diameter of the organic silver salt, the percentage of the value divided by the volume-weighted average diameter (coefficient of variation) is preferably 100% or less, more Preferably 80% or less,
More preferably, it is 50% or less. As a measuring method, for example, the particle size (volume weighted average diameter) obtained by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light is obtained. Can be.

The organic silver salt that can be used in the present invention is
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, and 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 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 copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, and JP-A-52-92716 and WO88 / 04794. Anionic surfactant described, the compound described in Japanese Patent Application No. 7-350753, or known anionic, nonionic,
Cationic surfactants and other known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose, or naturally occurring polymer compounds such as gelatin can be appropriately 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 obtain an organic silver salt powder or a wet cake. The pH may be controlled by a suitable pH adjuster before, during or after dispersion.

Instead of mechanically dispersing, fine particles may be formed by coarsely dispersing in a solvent by controlling the pH and then 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 the completion of the fine particle formation.

The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of 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.

[0104] While the organic silver salt according to the invention can be used in a desired amount, preferably 0.1-5 g / m ² as silver amount, more preferably from 1 to 3 g / m ^2.

The method of forming the photosensitive silver halide in the present invention is well known in the art, and employs, for example, the methods described in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. be able to. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method of preparing a photosensitive silver halide grain by adding a silver supply compound and a halogen supply compound to another polymer solution and mixing the resultant with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The particle size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation to be low.
20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less,
More preferably, the thickness is 0.02 μm or more and 0.12 μm or less. 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 shapes of the silver halide grains are 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. 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 grain is not particularly limited, but the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high.
The proportion occupied by the {100} plane is preferably high. The ratio is preferably 50% or more, more preferably 65% or more,
80% or more is more preferable. The Miller index ratio of {100} plane was determined by T. Tani; J. Imaging Sci., 29, 165 (1985) using the dependence of adsorption of sensitizing dyes on {111} and {100} planes. It can be determined by the method described. The halogen composition of the photosensitive silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide. In the present invention, silver bromide,
Alternatively, silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodide content is 0.1%.
Mol% or more and 40 mol% or less are preferable, and 0.1 mol% or more and 20 mol
% Or less is more preferable. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously, but as a preferable example, the silver iodide content inside the grains is High silver iodobromide grains can be used. Preferably, silver halide grains having a core / shell structure can be used. The structure is preferably 2
Core / shell particles having a ５5-fold structure, more preferably a 2- to 4-fold structure, can be used.

The photosensitive silver halide grains of the present invention preferably contain at least one metal complex selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt, mercury or iron. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferable content is in the range of 1 nmol to 10 mmol, and more preferably in the range of 10 nmol to 100 μmol per 1 mol of silver. 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 compound of cobalt and iron, a hexacyano metal complex can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion, and the like, but are not limited thereto. The metal complex in the silver halide may be uniformly contained,
The core portion may be contained at a high concentration, or the shell portion may be contained at a high concentration, and there is no particular limitation.

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

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, P-Te
Compounds having a bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used for the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, or U.S. Pat.
Compounds described in 18,061 and the like can be preferably 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. . 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 amount of the photosensitive silver halide used in the present invention is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, more preferably 0.03 to 0.3 mol, per mol of the organic silver salt. It is particularly preferably at least 0.25 mol and not more than 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt are mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. There is a method of mixing, 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 the effects of the present invention are sufficiently exhibited.

As the method for preparing silver halide of the present invention, a so-called halation 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 herein may be any compound as long as it is a compound that reacts with an organic silver salt to generate a silver halide, and includes N-halogenimide (N-bromosuccinimide, etc.), quaternary nitrogen halide (e.g. Tetrabutylammonium bromide, etc.), 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 reacts with an organic silver salt to generate silver halide.
(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.) ), A metal complex having a halogen ligand (such as sodium bromide iridate and ammonium rhodate), a halogen molecule (bromine, chlorine,
Iodine). Further, a desired organic / inorganic halide may be used in combination.

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

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 preferably contained in an amount of 5 to 50% (mole), more preferably 10 to 40% (mole), based on 1 mol of silver on the surface having the image forming layer. The layer to which the reducing agent is added may be any layer on the side having the image forming layer. When it is added to a layer other than the image forming layer, it is preferable to use a relatively large amount of 10 to 50% (mol) with respect to 1 mol of silver. Further, the reducing agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In photothermographic materials utilizing organic silver salts, a wide range of reducing agents are disclosed in JP-A-46-6074 and JP-A-47-1238.
47-33621, 49-46427, 49-115540, 50-14
No. 334, No. 50-36110, No. 50-147711, No. 51-32632,
No. 51-1023721, No. 51-32324, No. 51-51933, No. 52-8
4727, 55-108654, 56-146133, 57-82828
No. 57-82829, JP-A-6-3793, U.S. Pat.
No. 86, No. 3,679,426, No. 3,751,252, No. 3,751,255
Nos. 3,761,270, 3,782,949, 3,839,048,
3,928,686, 5,464,738, German patent 2321328,
It is disclosed in European Patent No. 692732 and the like. For example, phenylamide oxime, 2-thienylamide oxime and
Amide oximes such as p-phenoxyphenylamide oxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; such as the combination of 2,2-bis (hydroxymethyl) propionyl-β-phenylhydrazine and ascorbic acid A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (for example, hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or Such as 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-2,2-dihydroxy-1,1 Bis-β-naphthol as exemplified by -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); 5-pyrazolone, such as 3-methyl-1-phenyl-5-pyrazolone; dimethylaminohexose Reductones as exemplified by ductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; sulfones such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol Amidophenol reducing agents; 2-phenylindan-1,3-dione and the like; chromans such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarbethoxy 1,4-dihydropyridines such as -1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-t-
Butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1- Bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like; ascorbic acid derivatives (for example,
And aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidones and certain indan-1,3-diones; chromanols (such as tocopherols). Particularly preferred reducing agents are bisphenol and chromanol.

The reducing agent of the present invention 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.

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% (mole) per mole of silver on the surface having the image forming layer, and more preferably 0.5 to 20% (mole).
Further, the toning agent may be a so-called precursor which is derivatized so as to have a function effectively only during development.

In a photothermographic material utilizing an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077 and JP-A-47-10282.
Nos. 49-5019, 49-5020, 49-91215, 49-9
No. 1215, No. 50-2524, No. 50-32927, No. 50-67132,
No. 50-67641, No. 50-114217, No. 51-3223, No. 51-279
No. 23, No. 52-14788, No. 52-99813, No. 53-1020, No. 5
3-76020, 54-156524, 54-156525, 61-1836
No. 42, JP-A-4-56848, JP-B-49-10727, 54-2033
No. 3, U.S. Pat.Nos. 3,080,254, 3,446,648, 3,782,9
No. 41, No. 4,123,282, No. 4,510,236, British Patent 138079
No. 5, Belgian Patent No. 841910 and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as; naphthalimides (eg, N
-Hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-
Mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole N- (aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide ); And blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N'-hexamethylenebis (1-
Carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); 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-dihydro-1,4-phthalazinedione A combination of phthalazinone and a phthalic acid derivative (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride, etc.); phthalazine,
Phthalazine derivatives or metal salts, or derivatives such as 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives (for example, phthalic acid) Acid, 4
-Methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinedione,
Benzoxazine or naphthoxazine derivatives; rhodium complexes that function not only as color tone regulators but also in-situ as sources of halide ions for silver halide formation, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate And potassium hexachlororhodate (III); inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-
1,3-benzoxazine-2,4-dione and 6-nitro-1,3-
Benzoxazines such as benzoxazine-2,4-dione
2,4-dione; pyrimidine and asymmetric-triazine (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto- 1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4
H-2,3a, 5,6a-tetraazapentalene).

The color-toning agent of the present invention 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.

At least one of the image forming layers of the heat-developable image recording material of the present invention is a photosensitive layer using the polymer latex described below in an amount of 50% by weight or more of the total binder (hereinafter referred to as "the image forming layer of the present invention"). The polymer latex used for the "image forming layer" and the binder is referred to as "the polymer latex of the present invention"). However, the "polymer latex" referred to here is a water-insoluble hydrophobic polymer dispersed as fine particles in a water-soluble dispersion medium. The dispersion state is such that the polymer is emulsified in a dispersion medium, emulsion-polymerized, micelle-dispersed, or partially dispersed in polymer molecules and molecular chains themselves are molecularly dispersed. Any of them may be used.

The polymer latex of the present invention is described in "Synthetic Resin Emulsion (Hiroshi Okuda, edited by Hiroshi Inagaki, published by Polymer Publishing Association (1978))" and "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Kasahara) Edited by Keiji, published by the Society of Polymer Publishing (1993)), "Synthesis of Synthetic Latex (Souichi Muroi, published by the Society of Polymer Publishing (1970))" and the like.

The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably in the range of about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and a material having a wide particle size distribution or a material having a monodispersed particle size distribution may be used.

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

The minimum film forming temperature (MFT) of the polymer latex of the present invention is 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. An organic compound that lowers the minimum film forming temperature of polymer latex, also called a plasticizer
(Usually an organic solvent) and described in, for example, the aforementioned "Synthesis of Synthetic Latex (Souichi Muroi, published by Kobunshi Kankokai (1970))".

Examples of the polymer used in the polymer latex of the present invention include acrylic resins, vinyl acetate resins, polyester resins, polyurethane resins, rubber resins, vinyl chloride resins, vinylidene chloride resins, polyolefin resins, and copolymers thereof. There is.

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, a random copolymer or a block copolymer may be used. The polymer has a number average molecular weight of 5000 to 100000, preferably 10,000 to 100,000.
The degree is preferred. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film-forming properties are poor, which is not preferable.

The polymer of the polymer latex used in the present invention preferably has an equilibrium water content at 25 ° C. and 60% RH of 2% by weight or less, more preferably 1% by weight or less. The lower limit of the equilibrium moisture content is not particularly limited, but is preferably 0.01 wt.
%, More preferably 0.03 wt%. For the definition and measurement method of the equilibrium moisture content, for example, `` Polymer Engineering Course 14,
Polymer Material Testing Method (edited by the Society of Polymer Science, Jinjinshokan) ”and the like.

Specific examples of the polymer latex used as a binder for the image forming layer of the heat-developable image recording material of the present invention are as follows. Latex of methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, latex of methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer, latex of styrene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer Latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like.

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.),
FINETEX E is a polyester resin such as Nipol Lx811, 814, 821, 820, 857 (all manufactured by Nippon Zeon Co., Ltd.)
S650, 611, 675, 850 (Dai Nippon Ink Chemical Co., Ltd.)
HYDRAN AP10, 20, 30, and 4 as polyurethane resins such as WD-size, WMS (all manufactured by Eastman Chemical)
LACSTAR 7310K, 3307B, 4700H, and 7132C (all manufactured by Dainippon Ink & Chemicals, Inc.), Nipol Lx416, 410, 438C, 25
07, (Nippon Zeon Co., Ltd.), etc., vinyl chloride resins such as G351 and G576 (Nippon Zeon Co., Ltd.), etc., and vinylidene chloride resins, L502, L513 (Nippon Zeon Co., Ltd.) etc. Chemipearl S12 as olefin resin
0, 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.

The image forming layer of the present invention comprises 50 wt.
% Or more of the above polymer latex, but 70 wt%
It is preferable to use the polymer latex described above.

In the image forming layer of the present invention, if necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose or the like is added in an amount of 50% by weight or less of the whole binder. Is also good. The addition amount of these hydrophilic polymers is preferably 30% by weight or less of the total binder in the image forming layer.

The image forming layer of the present invention is characterized in that it is formed by applying an aqueous coating solution and then drying it. However, the term "aqueous" as used herein means that 30% by weight or more of the solvent (dispersion medium) of the coating liquid is water. As a component other than water of the coating solution, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used.

Examples of specific solvent compositions include the following. Water / methanol = 90/10, water / methanol = 70
/ 30, water / ethanol = 90/10, water / isopropanol =
90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80/15/5, water / methanol / dimethylformamide = 90/5/5. (However, the number is wt
Represents%. )

The total amount of the binder in the image forming layer of the present invention is 0.1.
2 to 30 g / m ^2, more preferably in the range of 1~15m ^2.

The image forming layer of the present invention contains an organic silver salt. This layer is preferably coated with a photosensitive silver halide, and if necessary, a reducing agent, a color tone agent, an antifoggant, Etc. may be added. Further, a dye for adjusting color tone, a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like may be added to the image forming layer of the invention.

The heat-developable image recording material of the present invention may be provided with an image forming layer other than the "image forming layer of the present invention", that is, an image forming layer which does not satisfy the above conditions. In this case, the binder, the solvent of the coating solution, and the like are not limited.

As the sensitizing dye in the present invention, any dye can 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 the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17
Item 643IV-A (p.23, December 1978), Item 1831X (August 1979)
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-Ne
For lasers, so-called red light sources such as red semiconductor lasers and LEDs, I-1 to I-1 described in JP-A-54-18726.
-38, the compound of I-1 to I-35 described in JP-A-6-75322 and the compound of I-1 to I-34 described in JP-A-7-287338, JP-B-55-39818 Dyes 1 to 20 described, compounds of I-1 to I-37 described in JP-A-62-284343 and compounds of I-1 to I-34 described in JP-A-7-287338 are advantageously selected. Is done.

For a semiconductor laser light source in the wavelength range of 750 to 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, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Patent 3,761,279,
3,719,495 and 3,877,943, British Patent 1,466,201
No. 1,469,117, No. 1,422,057, Tokuhei 3-10391
No. 6-52387, JP-A-5-341432, 6-94781,
It may be appropriately selected from known dyes as described in JP-A-6-301141.

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, see JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
72661, 6-222491, 2-230506, 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-30114
No. 1, U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes
(JP 47-6329, JP 49-105524, JP 51-127719, JP
52-80829, 54-61517, 59-214846, 60-6750
No. 63-159841, JP-A-6-35109, JP-A-6-59381,
Nos. 7-146537, 7-46537, JP-T-55-50111, British Patent 1,467,638, and US Pat. No. 5,281,515).

Further, dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887 as dyes forming a J-band,
JP-A-2-96131 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. Combinations of sensitizing dyes are often used, especially 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 Volume 176, 17643 (December 1978) No. 23
Section IV of Page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. To add sensitizing dyes to a silver halide emulsion, they may be directly dispersed in the emulsion,
Or water, methanol, ethanol, propanol,
Acetone, methylcellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2- It may be added to the emulsion by dissolving it in a solvent such as propanol or N, N-dimethylformamide alone or in a mixed solvent.

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. Method of adding to Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and this solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or base. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion as disclosed in U.S. Patent Nos. 3,822,135 and 4,006,025, JP-A-51-746, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion as disclosed in JP-A-51-746.
As disclosed in JP-A No. 24, a method of dissolving a dye using a compound that causes a red shift and adding this solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Patents 2,735,766 and 3,628,960,
4,183,756, 4,225,666, JP-A-58-184142,
As disclosed in the specification of JP-A-60-196749 and the like, the timing before the step of forming silver halide grains and / or before desalting, during and / or after desalting and before the start of chemical ripening. As disclosed in the specification such as JP-A-58-113920, any time immediately before chemical ripening or during the process, after chemical ripening, and before coating the emulsion before coating It may be added at the time and in the process.
Further, as disclosed in the specification of U.S. Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step. The compound may be divided and added during the ripening step or after the completion of the chemical ripening, or may be added separately before or during the chemical ripening or after the completion of the chemical ripening. May be added.

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

The silver halide emulsion according to the invention or /
And the organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and can be stabilized against reduced sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716; U.S. Pat.Nos. 2,886,437 and 2,444,605. Azaindene, U.S. Pat.
8,663 mercury salt, U.S. Pat.No. 3,287,135 urazole, U.S. Pat.No. 3,235,652 sulfocatechol, British Patent 623,448 Oxime,
Nitrone, nitroindazole, U.S. Patent No. 2,839,405
No. 3,220,839, thiuronium salts, and U.S. Pat.Nos. 2,566,263 and 2,597,915, palladium, platinum and gold salts, U.S. Pat.Nos. 4,108,665 and 4,442,202 No. 4,128,557
Nos. 4,137,079 and 4,138,365 and 4,
No. 4,59,350 and U.S. Pat.
And the phosphorus compounds described in No. 1,985.

The antifoggant preferably used in the present invention is an organic halide, for example, as described in JP-A-50-119624.
No. 50-120328, No. 51-121332, No. 54-58022, No.
56-70543, 56-99335, 59-90842, 61-12964
No. 2, 62-129845, JP-A-6-208191, 7-5621,
Nos. 7-2781, 8-15809, U.S. Pat.
Compounds such as those disclosed in US Pat.

The antifoggant of the present invention may be added by any method such as a solution, a powder or 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.

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

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 acids of the present invention may be any benzoic acid derivative, but examples of preferred structures include those described in U.S. Pat.
No. 4,152,160, Japanese Patent Application No. 8-151242, No. 8-151241
And the compounds described in JP-A-8-98051 and the like. The benzoic acid of the present invention may be added to any part of the image recording material. However, it is preferable to add the benzoic acid to a layer having an image forming layer such as a photosensitive layer. More preferably, it is added to the salt-containing layer.
The benzoic acid of the present invention may be added at any time during the preparation of the coating solution, and when it is added to the organic silver salt-containing layer, it may be added at any time from the preparation of the organic silver salt to the preparation of the coating solution. It is preferable after salt preparation and immediately before application. The benzoic acid of the present invention 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 of the present invention may be added in any amount, but not less than 1 μmol
Mol or less, more preferably 1 mmol or more and 0.5 mol or less.

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

When a mercapto compound is used in the present invention, it may have any structure, but may be any of Ar-SM, Ar-SSA
Those represented by r are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring group or a condensed 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 includes, for example, halogens (e.g., Br and Cl), hydroxy, amino, carboxy,
Alkyl (e.g. one or more carbon atoms, preferably 1-4
Having one carbon atom) and alkoxy (e.g.,
One having at least one carbon atom, preferably having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
Mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5
-Diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-
4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4 -
Thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxysil-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methyl Pyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole,
Examples include 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto.

The amount of the mercapto compound to be added is 0.001 to 1.0 per mol of silver in the emulsion layer which is the image forming layer.
A range of 0 moles is preferred, more preferably 0.01 to 0.3 moles per mole of silver.

In the image forming layer such as the photosensitive layer in 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, and US Pat. No. 2,588,765 And fatty acids or esters described in US Pat. No. 3,121,060 and silicone resins described in British Patent No. 955,061.

In the present invention, a super-high contrast agent can be used for forming a super-high contrast image. For example, U.S. Patent No. 5,464,73
No. 8, No. 5,496,695, No. 6,512,411, No. 5,536,622,
Japanese Patent Application Nos. Hei 7-228627, Hei 8-215822, Hei 8-130842
Nos. 8-148113, 8-156378, 8-148111, 8-
The hydrazine derivative described in 148116, the compound having a quaternary nitrogen atom described in Japanese Patent Application No. 8-83566, and the acrylonitrile compound described in US Pat. No. 5,545,515 can be used. Specific examples of the compound include compounds 1 to 10 and 5,49 of the aforementioned U.S. Pat.
H-1 to H-28 of 6,695, I-1 to I-86 of Japanese Patent Application No. 8-215822,
No. 8-130842 H-1 to H-62, No. 8-148113 No. 1-1 to 1-21,
No. 8-148111 No. 1-50, No. 8-148116 No. 1-40, No. 8-8356
No. 6, P-1 to P-26, and T-1 to T-18, U.S. Pat.
No. 15, CN-1 to CN-13 and the like.

Further, the present invention provides a method for forming a super-high contrast image.
A high contrast accelerator can be used in combination with the above-mentioned super-high contrast agent. For example, amine compounds described in U.S. Pat.No. 5,545,505, specifically AM-1 to AM-5, hydroxamic acids described in 5,545,507, specifically HA-1 to HA-11, and the like.
Acrylonitrile described in 5,545,507, specifically C
Hydrazine compounds described in N-1 to CN-13 and 5,558,983, specifically CA-1 to CA-6, onium salts described in Japanese Patent Application No. 8-132836, specifically A-1 to A-42, B-1 to
B-27, C-1 to C-14 and the like can be used.

The synthesis method, addition method, addition amount and the like of these super-high contrast agents and high-contrast accelerators can be carried out as described in each of the cited patents.

In the heat-developable image recording material of the present invention, a surface protective layer can be provided for the purpose of preventing adhesion of the image forming layer. Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials include wax, silica particles, styrene-containing elastomeric block copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and the like. And mixtures.

In the present invention, the emulsion layer or the protective layer of the emulsion layer as the image forming layer is described in US Pat. No. 3,253,921.
No. 2,274,782, No. 2,527,583 and No. 2,95
Light absorbing materials and filter dyes as described in 6,879 can be used. Also, dyes can be mordanted, for example, as described in US Pat. No. 3,282,699. The amount of the filter dye used is preferably such that the absorbance at the exposure wavelength is 0.1 to 3, and particularly preferably 0.2 to 1.5.

The image-forming layer or the protective layer of the image-forming layer according to the present invention may comprise a matting agent such as starch, titanium dioxide, zinc oxide, silica, of the type described in US Pat. Nos. 2,992,101 and 2,701,245. Polymer beads, including beads, can be included. The matte degree of the image forming surface may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably from 200 seconds to 10,000 seconds, and particularly preferably from 300 seconds to 10,000 seconds.

In the present invention, not only the above-mentioned image forming layer but also a binder which can be preferably applied in an aqueous system is preferable. Gelatin, polyvinyl alcohol, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, Polyacrylamide, dextran, and the like can be used.

If necessary, a hardening agent can be used.

The photothermographic emulsion of the present invention is contained in one or more layers on a support. One layer construction must include optional additional materials such as organic silver salts, silver halides, developers and binders, and toning agents, coating aids and other auxiliaries. The two-layer configuration is
One must contain the organic silver salt and silver halide in one emulsion layer (usually the layer adjacent to the support) and some other components in the second or both layers. However, a two-layer construction comprising a single emulsion layer containing all components and a protective topcoat is also contemplated. The construction of a multicolor photothermographic material may include a combination of these two layers for each color, and may include all components in a single layer as described in U.S. Pat.No. 4,708,928. Is also good. In the case of a multi-dye, multi-color photothermographic material, each emulsion layer is generally, as described in U.S. Pat.No. 4,460,681,
By using a functional or non-functional barrier layer between each emulsion layer (photosensitive layer), it is kept distinct from each other.

Various dyes and pigments can be used in the photosensitive layer, which is the image forming layer of the present invention, from the viewpoint of improving color tone and preventing irradiation. Dyes and pigments used in the photosensitive layer of the present invention may be any, for example, pigments and dyes described in the Color Index, specifically, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, Examples thereof include carbocyanine dyes, styryl dyes, triphenylmethane dyes, indoaniline dyes, indophenol dyes, organic pigments including phthalocyanine, and inorganic pigments. Preferred dyes used in the present invention include anthraquinone dyes (e.g., compounds 1 to 9 described in JP-A-5-341441, compounds 3-6 to 18 and 3-23 to 38 described in JP-A-5-165147), azomethine Dye (compound 17 described in JP-A-5-341441)
To 47 etc.), indoaniline dyes (e.g. JP-A-5-289227)
Nos. 11 to 19 and compounds described in JP-A-5-341441
47, compounds 2-10 to 11 described in JP-A-5-165147) and azo dyes (compounds 10 to 16 described in JP-A-5-341441). As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, and a state in which the dye is mordanted with a polymer mordant may be used. The amount of these compounds is determined by absorption of the purpose, generally the photosensitive material 1 m ²
It is preferable to use in a range of 1 μg or more and 1 g or less.

In the present invention, the antihalation layer can be provided on the side farther from the light source than the photosensitive layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably an absorption of an exposure wavelength of 0.5 or more and 2 or less, and an absorption in a visible region after processing of 0.001 or more. It is preferably less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3.

When antihalation dyes are used in the present invention, these dyes have the desired absorption in the wavelength range, have a sufficiently low absorption in the visible region after treatment, and have the desired absorbance spectrum shape of the antihalation layer. Any compound can be used as long as it is possible. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye, JP-A-59-56458, JP-A-Hei 2-
216140, 7-13295, 711432, U.S. Patent 5,380,
No. 635, JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9, and JP-A-3-24539, page 14, lower left column, page 16, lower right column The dyes that can be decolorized by the treatment include JP-A-52-139136, JP-A-53-132334, and
56-501480, 57-16060, 57-68831, 57-1018
No. 35, 59-182436, JP-A-7-36145, 7-199409
No., JP-B-48-33692, JP-B-50-16648, JP-B2-41734
Nos., U.S. Pat.Nos. 4,088,497, 4,283,487, 4,548,89
No. 6 and 5,187,049.

The heat-developable image recording material of the invention has an image forming layer such as a photosensitive layer containing at least one silver halide emulsion on one side of a support, and a back layer ( It is preferably a so-called single-sided image recording material having a backing layer).

In the present invention, a matting agent may be added for improving transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Pat.
No. 213, No. 2,701,245, No. 2,322,037, No. 3,262,782
Nos. 3,539,344, 3,767,448, 3,767,448, etc., the organic matting agents described in the respective specifications, 1,260,772, 2,192,241, and 3,300
257,206, 3,370,951, 3,523,022, 3,769,0
Those well known in the art, such as an inorganic matting agent described in each specification such as No. 20, can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of water-dispersible vinyl polymers, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, and starch derivatives such as carboxy starch, carboxynitrophenyl Gelatin hardened with a known hardener such as starch, urea-formaldehyde-starch reactant, and hardened gelatin formed into microcapsule hollow granules by coacervate hardening are preferably used. Can be. Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. . The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the coating film and the surface gloss, the particle size, shape, and particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, the back layer has a matte degree of Beck smoothness of preferably 250 seconds or less and 10 seconds or more, more preferably 180 seconds or less and 50 seconds or more.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the image recording material, a layer functioning as the outermost surface layer, or a layer close to the outer surface, and a layer functioning as a so-called protective layer. Is preferably contained.

In the present invention, suitable binders for the back layer are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (vinyl). (Alcohol), hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinylacetal) s (e.g., poly (vinylformal) and poly (vinylformal))
(Vinyl butyral)), poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (vinylidene chloride)
(Epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the present invention, the back layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range.
More preferably absorption is 0.5 or more and 2 or less, and the absorption in the visible region after the treatment is preferably 0.001 or more and less than 0.5, and more preferably a layer having an optical density of 0.001 or more and less than 0.3. . Examples of the antihalation dye used in the back layer are the same as those of the antihalation layer described above.

US Pat. Nos. 4,460,681 and 4,374,9
Backside resistive heating layer as shown in No. 21
stive heating layer) can also be used in a photosensitive heat developed photographic image system.

The photothermographic material according to a preferred embodiment of the present invention may be developed by any method. Usually, the photothermographic material on which a latent image is formed imagewise is heated and developed. The preferred development temperature is 80 to 250C, more preferably 100 to 140C. The development time is preferably from 1 to 180 seconds, more preferably from 10 to 90 seconds.

The latent image of the photothermographic material of the present invention may be formed by any method, but when it contains photosensitive silver halide, it is preferable to use a laser beam as an exposure light source. As the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. Further, a semiconductor laser and a second harmonic generation element can be used.

When the heat-developable image recording material of the present invention does not contain a photosensitive silver halide, the heat-developable image recording material of the present invention can form a latent image by heating. As the latent image forming method, a method described in US Pat. No. 5,279,928 can be used. Heating can be performed by direct heating using a thermal head or the like. Alternatively, a material (dye or pigment) that absorbs light of a specific wavelength and converts it into heat is present in the image recording material, and heating is performed indirectly. You can also do it. The light source used at this time is preferably the laser beam described above. Further, when a latent image is formed by heating, a latent image may be formed by heating in a first stage, and an image may be formed in a second stage. It can be performed up to the formation.

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The present invention will be specifically described below with reference to examples. Example-1 (1) Preparation of support (1-1) Preparation of PET support (PET: Tg = 69 ° C) Using terephthalic acid and ethylene glycol, IV = 0.66 (phenol- Le / tetrachloroethane = 6
/ 4 (measured at 25 ° C. in a weight ratio). This was pelletized and dried at 130 ° C. for 4 hours.
After being melted at ℃, the mixture was extruded from a T-die and then rapidly cooled to prepare an unstretched film having a thickness of 100 μm after heat setting.

This is performed by using rolls having different peripheral speeds.
The film was stretched twice in the longitudinal direction, and then stretched in the transverse direction by 4.5 times using a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. After that, it was heat-set at 240 ° C. for 20 seconds and relaxed 4% in the horizontal direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling is performed on both ends,
It was wound up at kg / cm ² . Thus, a roll having a width of 2.4 m, a length of 5000 m, and a thickness of 100 μm was obtained.

A roll having a thickness of 175 μm was obtained in the same manner.

(1-2) Preparation of PEN support (PEN: Tg
= 119 ° C) Starting from 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol, 50 ppm of spherical silica particles having an average particle size of 0.3 µm were added, and polyethylene-2,6- was obtained by a transesterification method according to a conventional method. Naphthalate was polymerized according to a conventional method. IV = 0.56 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.).

The pellets were dried at 170 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled to prepare an unstretched film having a thickness of 100 μm after heat setting. .

The film was stretched longitudinally to 3.0 times, and then 3.3 times.
Lateral stretching was performed twice. The temperature at this time was 14
0 ° C and 130 ° C. Then, after heat-setting at 250 ° C. for 20 seconds, it was relaxed by 3% in the lateral direction. This is the above PET
The film was wound at 4 kg / cm ² in the same manner as described above. In this way,
A roll having a width of 2.4 m, a length of 5000 m, and a thickness of 100 μm was obtained.

Similarly, the roll base was obtained by adjusting the thickness to 175 μm.

(1-3) Preparation of Polymer Blend Support PET and PEN prepared by the above method were formed into a polymer blend using a twin screw kneading extruder at the following ratio.

PB-7: PEN / PET (20/80: weight ratio) Tg = 79 ° C.

This was dried under the same conditions as the PET support, and then dried.
After stretching 3.4 times vertically at 20 ° C, it was stretched 4.2 times horizontally at 140 ° C. After this, heat setting was performed at 245 ° C. for 20 seconds.
Relaxed 5% in the lateral direction. This was wound up at 4 kg / cm ² in the same manner as in PET. Thus, the width 2.4
m, a length of 5000 m, and a thickness of 100 μm were obtained.

(1-4) Preparation of Polyarylate (PAr) Support An unstretched film of 100 μm was used by a melt extrusion method.

On the above support, a surface treatment selected from the following and a primer coating were performed in combination to prepare a support as shown in Table 1.

[0192]

[Table 1]

(2) Surface treatment (2-1) Corona treatment Using a solid state corona treatment machine 6KVA model manufactured by Pillar Co., both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, the support was treated at 0.375 kV · A · min / m ² . At this time, the processing frequency was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.

(2-2) Glow discharge treatment The glow discharge treatment is described in "Invention Association Open Techniques, Official Technique No. 94-6.
No. 023 "in Example 1.

(3) Undercoat application (3-1) Undercoat layer formulation Formulation (first layer) An undercoat solution having the following composition was applied using a wire bar at 6 ml / m ^{2 and} dried at 120 ° C. for 2 minutes. Butadiene-styrene copolymer latex 13 ml (solid content 43%, butadiene / styrene weight ratio = 32/68) 2,4-dichloro-6-hydroxy-S-triazine sodium 7 ml salt 8% aqueous solution sodium laurylbenzenesulfonate 1% Aqueous solution 1.6ml distilled water 80ml

Formulation (Second Layer) An undercoat solution having the following composition was applied at 9 ml / m ² using a wire bar, and dried at 185 ° C. for 5 minutes. Gelatin 0.9 g Methyl cellulose (Metroose SM15 substitution degree 1.79 to 1.83) 0.1 g Acetic acid (99% concentration) 0.02 ml Distilled water 99 ml

Formulation (First Layer) An undercoat solution having the following composition was applied using a wire bar at 6 ml / m ^{2 and} dried at 120 ° C. for 2 minutes. Butadiene-styrene copolymer latex 13 ml (solid content 43%, butadiene / styrene weight ratio = 32/68) 1% aqueous solution of sodium laurylbenzenesulfonate 1.6 ml distilled water 87 ml

Formulation (Conductive Layer) An undercoat solution having the following composition was applied using a wire bar, and then dried at 185 ° C. for 5 minutes. SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 100 mg / m ² Gelatin 77 mg / m ² Sodium dodecylbenzenesulfonate 1 mg / m ² Dihexyl-α-sulfosuccinate sodium 4 mg / m ²

(4) Heat treatment According to the procedure shown in Table 1, a heat treatment was selected from the following methods.

(4-1) Heat treatment for transfer Heat treatment The support after surface treatment and, if necessary, undercoating was transferred through a heat treatment zone having a total length of 200 m set at the temperature and tension shown in Table 1 at a transfer speed of 20 m / min. .

Post heat treatment After the heat treatment, post heat treatment was performed at the temperature and time shown in Table 1 and the film was wound. The winding tension at this time is 1
It was 0 kg / mm ² .

(4-2) Post-roll heat treatment The support wound up with a tension of 4 kg / cm ² was kept at 115 ° C. for 48 hours while rotating at 0.2 revolutions / hour, and then cooled to room temperature while rotating. did.

(5) Preparation of photosensitive material A photosensitive layer and a back layer were coated on the support described above to prepare the photosensitive materials shown in Table 2.

Formulation 1 << Preparation of silver halide particles A >> After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjusting the pH to 5.0 at a temperature of 40 ° C., an aqueous solution containing 18.6 g of silver nitrate in 159 m
l and an aqueous potassium bromide solution were added over 10 minutes by a controlled double jet method while maintaining pAg of 7.7. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate, 8 μmol / l of dipotassium hexachloride iridate and 1 part of potassium bromide
An aqueous solution containing mol / liter was added over 30 minutes by a controlled double jet method while maintaining the pAg at 7.7.
Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, and 0.1 g of phenoxyethanol was added to adjust to pH 5.9 and pAg 8.0. The obtained particles were cubic particles having an average particle size of 0.07 μm, a variation coefficient of the projected area diameter of 8%, and a (100) plane ratio of 86%.

The temperature was adjusted to 6 with respect to the prepared silver halide grains A.
Raise the temperature to 0 ° C and use sodium thiosulfate 85μ per mole of silver.
Mol and 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide in 11 μmol, 2 μmol of tellurium compound, 3.3 μmol of chloroauric acid, 230 μ of thiocyanic acid
Mole was added and aged for 120 minutes. Thereafter, the temperature was changed to 40 ° C., and sensitizing dye A was changed to 3.5 × 10 ^{−4 with} respect to silver halide.
Mole, 2-mercapto-5-methylbenzimidazole, 4.
Add 6 × 10 ^-3 mol with stirring and stir for 10 minutes, then 2
Quenched to 5 ° C to finish preparation of silver halide grains 30 ° C
And the preparation of silver halide grains A was completed.

<< Preparation of Silver Halide Grains B >> Grain formation and desalting were carried out in exactly the same manner as for silver halide grains A, and 0.1 g of phenoxyethanol was added.
Adjusted to 8.0. The resulting particles have an average particle size of 0.07μ
m, cubic grains having a projected area diameter variation coefficient of 8% and a (100) face ratio of 86%.

Without chemically sensitizing the obtained emulsion,
After the temperature was raised to 40 ° C. in the same manner as for silver halide grains A, sensitizing dye A was 3.5 × 10 ^-4 mol based on silver halide, and 2-mercapto-5-methyl-benzimidazole was 4.6 × 10 ^-3 mol.
The mixture was added with molar stirring and stirred for 10 minutes, and then rapidly cooled to 25 ° C. and rapidly cooled to 30 ° C. to complete the preparation of silver halide grains B.

<< Preparation of Organic Acid Silver Dispersion >> Stearic acid 8
g, behenic acid 39 g, and distilled water 850 ml were vigorously stirred at 90 ° C. while adding 1N-NaOH aqueous solution 187 ml and reacting for 120 minutes. After adding 1N-nitric acid 65 ml, the temperature was lowered to 50 ° C. Next, 125 g of an aqueous solution of 21 g of silver nitrate was added over 100 seconds while stirring more vigorously, and the mixture was left as it was for 20 minutes. 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. 100 g of a 10 wt% aqueous solution of hydroxypropylmethylcellulose was added to the solid content thus obtained, and water was further added so as to have a total weight of 270 g, followed by elementary dispersion in an automatic mortar to obtain a coarse dispersion of silver organic acid. The organic acid silver dispersion was subjected to pressure of 56 using a Menton-Gaulin homogenizer.
The mixture was dispersed five times at 0 kg / cm ³ to obtain a silver salt of an organic acid. The organic acid silver particles contained in the organic acid silver dispersion thus obtained have an average minor axis of 0.
Acicular particles having a particle diameter of 04 μm, an average major axis of 0.9 μm, and a variation coefficient of 30% were obtained.

<< Preparation of Reducing Agent Dispersion >> 850 g of water was added to 100 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 50 g of hydroxypropyl cellulose.
Was added and mixed well to obtain a slurry. Average diameter 0.5mm
840 g of zirconia beads was prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 5 hours to obtain a reducing agent dispersion.

<< Preparation of Organic Polyhalide Dispersion >> 940 g of water was added to 50 g of tribromomethylphenylsulfone and 10 g of hydroxypropylcellulose and mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, and use a disperser (1/4
The mixture was dispersed for 5 hours using a G sand grinder mill (manufactured by Imex Co., Ltd.) to obtain an organic polyhalide dispersion.

<< Preparation of Emulsion Layer Coating Solution >> 100 g of the organic acid silver dispersion obtained above, 50 g of a reducing agent dispersion, 15 g of an organic polyhalide dispersion, LACSTAR 3307B
(Dainippon Ink and Chemicals, Inc .; SBR latex 49%)
40 g, silver halide emulsion A 15 g, silver halide emulsion B
Was mixed well with 5 g of water to prepare a coating solution for an emulsion layer. The average particle size of the dispersed particles of Luckstar 3307B, which is a latex of a styrene-butadiene copolymer, is about 0.1 to 0.15 μm.
The equilibrium water content under 0% RH condition was 0.6 wt%.

<< Preparation of Coating Solution for Emulsion Surface Protective Layer >> For 100 g of inert gelatin, 4 g of potassium salt of N-perfluorooctylsulfonyl-N-propylalanine, 1.3 g of sodium dodecylbenzenesulfonate, fine particles of polymethyl methacrylate (average particle size) 2 g of phthalazine (2.5 μm in diameter), 6 g of phthalazine, 11 g of 4-methylphthalic acid, 5 g of aluminum sulfate and sulfuric acid in such an amount that the pH of the film surface was 4.0 were added, and water was added so that the total amount became 160 cc to prepare a coating solution for the surface protective layer.

<< Back Layer Coating Solution >> A solid base such as N, N, N,
N-tetraethylguanidine and 4-carboxysulfonyl
-Phenylsulfone molar ratio 1: 2 salt 10g, polyvinyl alcohol 10g, water 88g and 1 / 16G sand grinder mill
(Imex Corporation) to obtain a base solution.

An organic solvent phase obtained by mixing and dissolving 2.1 g of a basic dye precursor, 7.9 g of an acidic substance, 0.1 g of a dye and 10 g of ethyl acetate was mixed with an aqueous phase composed of 10 g of polyvinyl alcohol and 80 g of water, and emulsified and dispersed at room temperature. A dye solution was obtained (average particle size 2.5
μm).

39 g of the base solution thus obtained, 26 g of the dye solution, and 36 g of a 10 wt% aqueous solution of polyvinyl alcohol were mixed to obtain a back surface coating solution.

<< Coating Solution for Back Surface Protective Layer >> Gelatin 20 g,
0.6 g of polymethyl methacrylate (average particle size 7 μm), 0.4 g of sodium dodecylbenzenesulfonate, X-22-2809
(Shin-Etsu Silicone Co., Ltd. silicone compound) 1g water 480g
To obtain a back surface protective layer coating solution.

<< Preparation of Photothermographic Material >> A coating solution for the back layer was applied to a support selected from the supports shown in Table 1 prepared as described above in such an amount that the optical density at 647 nm was 0.7. after the coated 50 g / m ² simultaneous multilayer coating emulsion layer coating liquid coated silver amount 2 g / m ² on the surface opposite the back surface, the emulsion surface protective layer coating solution so that the amount of gelatin 1.5 g / m ² did. The smoothness of the photosensitive material thus obtained (J. TAPPI paper pulp test method N
oeck type smoothness measurement described in O.5 was used to determine the Beck smoothness) was 1000 seconds for the emulsion surface and 80 seconds for the back surface.

The structural formula of the compound used in the above is as follows.

[0219]

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Formulation 2 (Preparation of silver halide particles C) After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water and adjusting the pH to 5.0 at a temperature of 40 ° C., a 159-m aqueous solution containing 18.6 g of silver nitrate was prepared.
l and an aqueous solution containing potassium bromide were added over 10 minutes by the control double jet method while maintaining the pAg at 7.7.
An aqueous solution containing 8 × 10 ⁻⁶ mol / L of K ₃ [IrCl ₆ ] ^3- and 1 mol / L of potassium bromide was added over 30 minutes by the control double jet method while maintaining the pAg at 7.7.
Thereafter, the pH was adjusted to 5.9 and pAg 8.0.

The obtained particles had an average particle size of 0.07 μm
The cubic grains had a variation coefficient of projected area diameter of 8% and an (100) area ratio of 86%.

The above silver halide grains C were heated to a temperature of 60 ° C., and 8.5 × 10 ⁻⁵ mol of sodium thiosulfate and 1.1 × 10 ⁻⁵ mol of 2,3,4,5, 6-pentafluorophenyldiphenylsulfine selenide, 2 × 10 ⁻⁶ mol of the following tellurium compound-1, 3.3 × 10 ⁻⁶ mol of chloroauric acid, 2.3 ×
10 ^-4 mol of thiocyanic acid was added and aged for 120 minutes. Thereafter, at a temperature of 50 ° C., 8 × 10 ^-4 mol of the following sensitizing dye-B was added with stirring, and 3.5 × 10 ^-2 mol of potassium iodide was further added, followed by stirring for 30 minutes. The mixture was rapidly cooled to ℃ to complete the preparation of silver halide grains.

[0223]

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(Preparation of Silver Crystalline Dispersion of Organic Acid) Behenic Acid
40 g, stearic acid 7.3 g and distilled water 500 ml were mixed at 90 ° C. for 15 minutes, and 1N-NaOH aqueous solution 187 ml was added over 15 minutes with vigorous stirring, 1N-nitric acid aqueous solution 61 ml was added, and the temperature was lowered to 50 ° C. . Next, add 124 ml of 1N silver nitrate aqueous solution and leave
Stir for 30 minutes. Then, the solid content was filtered by suction filtration,
The solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. The solid content thus obtained was handled as a wet cake without drying, and 12 g of polyvinyl alcohol and 150 ml of water were added to a wet cake having a dry solid content of 34.8 g and mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, disperse them in a disperser (1 / 4G-sand grinder mill: manufactured by Imex Co., Ltd.) for 5 hours, and obtain a volume-weighted average of 1.5 μm. Of organic acid silver microcrystal dispersion was obtained. Particle size measurements are available from Malvern Instruments Ltd.
It was performed with MasterSaizerX manufactured by the company.

(Preparation of Material Solid Fine Particle Dispersion) Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
Solid fine particle dispersions were prepared for 5-trimethylhexane, phthalazine, and tribromomethylphenylsulfone.

To tetrachlorophthalic acid, 0.81 g of hydroxypropylcellulose and 94.2 ml of water were added, stirred well, and left as a slurry for 10 hours. Thereafter, 100 ml of zirconia beads having an average diameter of 0.5 mm and a slurry were put together in a vessel and dispersed for 5 hours using a dispersing machine of the same type as that used for the preparation of the silver salt of organic acid microcrystals. Was obtained. As for the particle size of the solid fine particles, 70 wt% was 1.0 μm or less.

With respect to the other materials, the amount of the dispersant used and the dispersion time were appropriately changed in order to obtain a desired average particle size to obtain a solid fine particle dispersion.

(Preparation of Emulsion Layer Coating Solution) The following compositions were added to the previously prepared organic acid silver microcrystal dispersion to prepare emulsion coating solutions.

Organic acid silver microcrystal dispersion 1 mol Silver halide emulsion C 0.05 mol Binder: SBR latex (LACSTAR 3307B, manufactured by Dainippon Ink and Chemicals, Inc.) 430 g Material for development: tetrachlorophthalic acid 5 g 1, 1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 98 g phthalazine 9.2 g tribromomethylphenylsulfone 12 g 4-methylphthalic acid 7 g hydrazine derivative-1 (described below) 4.2 × 10 ^-3 mol / mol Ag Additive B (described below) 1.7 × 10 ^-2 mol / mol Ag

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(Preparation of Emulsion Protective Layer Coating Solution) The following compositions were added to inert gelatin to prepare an emulsion protective layer coating solution. Inert gelatin 10 g Surfactant A (described below) 0.26 g Surfactant B (described below) 0.09 g Fine silica particles (average particle size 2.5 μm) 0.9 g 1,2- (bisvinylsulfone acetamide) ethane 0.3 g water 64g

(Preparation of Coloring Agent Dispersion A) Ethyl acetate 35
2.5 g each of the following compounds 1 and 2,
7.5 g was added and dissolved by stirring. To this solution was added 50 g of a 10% by weight solution of polyvinyl alcohol previously dissolved, and the mixture was dispersed with a homogenizer for 5 minutes. Thereafter, ethyl acetate was removed by removing the solvent, and then diluted with water to prepare a color former dispersion.

[0233]

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(Preparation of Back Surface Coating Solution) The following compositions were added to polyvinyl alcohol to prepare a back surface coating solution. Polyvinyl alcohol 30 g Color former dispersion A 50 g Additive-A (described below) 20 g Water 250 g Sildex H121 (Doukai Chemical's true spherical silica average size 12 μm) 1.8 g

[0235]

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(Preparation of Photothermographic Material) The coating solution of the emulsion layer prepared as described above was coated on a support shown in Table 1 with silver.
It was applied so as to be 6 g / m ² . On top of this, an emulsion layer protective layer coating solution was applied so that the coating amount of gelatin was 1.8 g / m ² . After drying, a coating solution for the back surface was applied on the surface opposite to the emulsion layer so that the optical density at 660 nm was 0.7, thereby preparing a sample.

Formulation 3 A photosensitive material coated with a photosensitive layer and a back layer described in Example 2 of JP-A-8-328197 was prepared. Here, the coating solvent for the photosensitive layer is a mixture of acetone, 2-propanol, methanol, and dimethylformamide (DMF).

(6) Evaluation of photosensitive material (Evaluation of surface condition) A photosensitive material prepared by applying a photosensitive layer was cut into half-cut sizes, left one by one, and visually observed for flatness. evaluated.

Further, this sample was processed with a heat roller at 125 ° C. so that the heat development time was adjusted to 15 seconds. The developed samples were similarly left one by one, and the flatness was visually observed and evaluated.

(Evaluation of photographic performance) The photosensitive materials of the photosensitive layer formulations 1 and 3 were exposed with a 647 nm Kr laser sensitometer (maximum output: 500 mW) at an inclination of 30 degrees with respect to the normal line. The photosensitive material was processed (developed) at 120 ° C. for 15 seconds, and the obtained image was evaluated with a densitometer. The result of the measurement is
It was evaluated by Dmin and Dmax.

For the photosensitive material of photosensitive layer formulation 2, 656 nm
Through a step wedge through an interference filter having a peak at a light emission time of 10 ^-4 sec, and heat-developed by a heat drum at 115 ° C. for 25 seconds.
Measure the gradation G033 at Dmin and density 0.3 to 3.0
0 was rated.

Table 2 also shows the results of the above-described evaluations performed on each photosensitive material. As for the photographic performance, only necessary data is shown.

[0243]

[Table 2]

(7) Evaluation Results As for the photosensitive material after the thermal development, the 100 μm PET base which was not subjected to the high-temperature heat treatment of No. 1 was not preferable because streak-like irregularities were observed. Irregularities were observed. On the other hand, all of the photosensitive materials using the support of the present invention showed good flatness.

All of the photosensitive materials of Formula 1 according to the present invention have low Dmin and sufficient Dmax, and have a photographic performance equal to or higher than that of the photosensitive material of Formula 3 prepared by applying an organic solvent using a heat-treated PET support. Thus, a photosensitive material having excellent flatness and little influence on the environment was obtained.

Also, the photosensitive material of the present invention of Formula 2 provided a low Dmin and a sufficiently large gradation, and also obtained a photosensitive material having excellent flatness and little influence on the environment.

[0247]

According to the present invention, a high-quality heat-developable image recording material can be obtained which has a wider range of choices of supports by water-based coating, is advantageous in terms of cost and environment, is excellent in thermal stability, and is excellent. Can be

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Claims (6)

[Claims] 1. A heat-developable image recording material having at least one layer containing at least one organic silver salt on a support, wherein the support contains at least 30 mol% of naphthalenedicarboxylic acid as a dicarboxylic acid component, and 80 ° C or higher 22
A heat-developed image using a polyester heat-treated at a temperature of 0 ° C. or lower, wherein the layer containing the organic silver salt is formed from a coating solution containing water as a main component of a solvent. Recording material. 2. A heat-developable image recording material having at least one layer containing at least one kind of organic silver salt on a support, wherein the support is made of polyethylene terephthalate heat-treated at 80 ° C. to 220 ° C. Wherein the layer containing an organic silver salt is formed from a coating solution containing water as a main component of a solvent. 3. A heat-developable image recording material having at least one layer containing at least one organic silver salt on a support, wherein the support contains at least 30 mol% of naphthalenedicarboxylic acid as a dicarboxylic acid component, and A polyester which has been heat-treated at a temperature of 50 ° C. or higher and lower than the glass transition temperature, wherein the layer containing the organic silver salt is formed from a coating solution containing water as a main component of a solvent. Developed image recording material. 4. A heat-developable image recording material having at least one layer containing at least one kind of organic silver salt on a support, wherein the support comprises a polyarylate-based polymer; A heat-developable image recording material, characterized in that the layer containing is formed from a coating solution containing water as a main component of a solvent. 5. The support is 0.04 kg / cm ² or more 6 kg / cm ² or less of the heat-developable image recording material according to claim 1 or 2 is transported heat treated at a tension. 6. The photosensitive emulsion layer containing a photosensitive silver halide, wherein at least one layer containing an organic silver salt is a photosensitive emulsion layer containing a photosensitive silver halide.
5. The heat-developable image-recording material according to any one of 5.