JP2001013626A - Heat-developable photosensitive material, its production, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-developable photosensitive material which does not cause unevenness in an image and is excellent in image quality in continuous processing of a heat sensitive material of various sizes at the time of image forming by using an epoxy compound and an acid anhydride and specifying surface glossiness. SOLUTION: The heat-developable photosensitive material has a photosensitive layer containing an organic silver salt, a photocatalyst, a reducing agent and a binder, has at least one epoxy compound and at least one acid anhydride and has 1-6% surface glossiness. Preferably the photosensitive layer contains the epoxy compound, the epoxy compound is represented by formula I and the acid anhydride is represented by formula II. In the formula I, R is an alkylene which may have a substituent as a divalent combining group and X is a divalent combining group. In the formula II, Z is a group of atoms required to form a monocyclic or polycyclic system. The heat developable photosensitive material containing <=500 mg/m2 solvent is preferably developed by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, a method for producing the same, and an image forming method using the photothermographic material.

[0002]

2. Description of the Related Art Conventionally, in the printing plate making and medical fields, waste liquids caused by wet processing of image forming materials have been a problem in terms of workability. Weight loss is strongly desired. Therefore, there is a need for a technology relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter or laser imager and can form a high-resolution, clear black image.

As this technique, for example, US Pat.
No. 152,904, No. 3,487,075 and D.C.
"Dry Silver Photographi" by Morgan
c Materials) "(Handbook of
Imaging Materials, Marcel
Dekker, Inc. 48, 1991), a photothermographic material containing an organic silver salt, photosensitive silver halide grains, a reducing agent and a binder on a support is known.

However, when the photothermographic material described above is subjected to development processing of various sizes by an automatic developing machine capable of developing at a high temperature of 100 ° C. or higher, processing unevenness is generated on the surface of the photosensitive material, and the commercial value is remarkably high. Was lowered.

Therefore, even in high-temperature processing of 100 ° C. or more, a photothermographic material which does not cause processing unevenness on the surface of the photosensitive material,
There has been a demand for a manufacturing method and an image forming method.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable material which is free from image unevenness and has excellent image quality when heat-sensitive materials of various sizes are continuously processed during image formation. Method and an image forming method.

[0007]

The above objects of the present invention have been attained by the following items 1 to 7.

[0008] 1. A photothermographic material having a photosensitive layer containing at least an organic silver salt, a photocatalyst, a reducing agent and a binder on a support, comprising at least one epoxy compound and at least one acid anhydride, Is from 1% to 60%.

[0009] 2. 2. The photothermographic material according to the above item 1, wherein the photosensitive layer contains an epoxy compound.

[0010] 3. 3. The photothermographic material according to item 1 or 2, wherein the epoxy compound is represented by the following general formula (1), and the acid anhydride is represented by the following general formula (2).

[0011]

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[In the formula, R represents a divalent linking group which may have a substituent, and X represents a divalent linking group. ]

[0013]

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[In the formula, Z represents an atomic group necessary for forming a monocyclic or polycyclic ring system. ] 4. Using a laser scanning exposure machine in which the angle between the exposure surface and the scanning laser beam does not become substantially vertical,
4. An image recording method, comprising exposing the photothermographic material according to item 2 or 3.

[0015] 5. 5. The image recording method according to the above item 4, wherein a laser scanning exposure device that emits a scanning laser beam that is a vertical multi is used.

6. 4. An image forming method, wherein the photothermographic material according to any one of the above items 1, 2 and 3 is heat-developed in a state where the photothermographic material contains a solvent of 500 mg / m ² or less.

[7] The amount of water in the coating solution used for coating the photosensitive layer of the photothermographic material according to the above item 1, 2 or 3, is 5 to 1 mol of silver contained in the coating solution.
A method for producing a photothermographic material, wherein the weight is 50 g.

Hereinafter, the present invention will be described in more detail.

The epoxy compound used in the photothermographic material of the present invention may be any as long as it has at least one epoxy group, and there is no limitation on the number, molecular weight, etc. of the epoxy group.
The epoxy group is preferably contained in the molecule as a glycidyl group via an ether bond or an imino bond. The epoxy compound may be any of a monomer, oligomer, polymer and the like, and the number of epoxy groups present in the molecule is usually about 1 to 10, preferably 2 to 4.
When the epoxy compound is a polymer, it may be either a homopolymer or a copolymer, and a particularly preferable range of the number average molecular weight Mn is 2,000 to 20,000.
It is about 0.

The epoxy compound used in the present invention is preferably a compound represented by the above general formula (1).

In the general formula (1), the substituent of the alkylene group represented by R is preferably a group selected from a halogen atom, a hydroxyl group, a hydroxyalkyl group or an amino group. It is preferable that the linking group represented by R has an amide linking moiety, an ether linking moiety, and a thioether linking moiety. -SO ₂ As the divalent linking group represented by _{X -, - SO 2 NH -} , - S -, - O-, or the like are preferable -NR'-, R 'is a monovalent linking group ,
Preferably, it is an electron withdrawing group.

Hereinafter, specific examples of the epoxy compound used in the present invention will be shown, but the present invention is not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The epoxy compound used in the present invention comprises 1
Only one kind or two or more kinds may be used in combination, and the content is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / m ² ,
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² .

The epoxy compound used in the present invention can be added to any layer on the photosensitive layer side of the support such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer and an undercoat layer. Can be added to one or more layers. Also, it can be added to any layer on the opposite side of the support from the photosensitive layer. In the case of a photosensitive material having a photosensitive layer on both sides, any layer may be used.

The acid anhydride used in the photothermographic material of the present invention has at least one acid anhydride group represented by the following structural formula.
Compound.

[0031]

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The acid anhydride used in the present invention is not limited as long as it has at least one such acid anhydride group, and the number and molecular weight of the acid anhydride group are not limited. The compound represented by is preferred.

In the general formula (2), Z represents an atom group necessary for forming a monocyclic or polycyclic ring system. These ring systems may be unsubstituted or substituted. Examples of the substituent include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxy group, an aryloxy group (Eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group , A sulfonylamino group, an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group,
Includes sulfo groups and amino groups. As the substituent,
Those containing no halogen atom are preferred.

Hereinafter, specific examples of the acid anhydride will be shown, but the present invention is not limited thereto.

[0035]

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[0036]

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These acid anhydrides may be used alone or in combination of two or more, and the content thereof is 1 × 10 ^-6 to
1 × 10 ⁻² mol / m ² is preferable, and 1 × 10 ⁻² mol / m ² is more preferable.
10 ^- is a ⁵ to 1 × 10 ^-3 mol / m ^2.

In the present invention, the acid anhydride can be added to any layer on the photosensitive layer side of the support such as a photosensitive layer, a surface protective layer, an intermediate layer, an antihalation layer and an undercoat layer. It can be added to one or more layers. Especially, it is preferable to add to the same layer as the epoxy compound of the present invention. Further, it can be added to any layer on the opposite side of the support from the photosensitive layer. In the case of a photosensitive material having a photosensitive layer on both sides, any layer may be used.

In the method for producing a photothermographic material of the present invention, when the photosensitive layer is coated, the amount of water in the coating solution is from 5 to 50 g per mole of silver contained in the coating solution. ,
Preferably, it is 10 to 40 g, more preferably 1 to 40 g.
5 to 30 g.

In the method for producing a photothermographic material according to the present invention, by adjusting the amount of water in the coating solution for coating the photosensitive layer to the above-mentioned range, a high-sensitivity, low-fogging photothermographic material can be obtained. It was found that a material could be obtained, and that image unevenness during development was also improved.

As the photocatalyst used in the present invention, photosensitive silver halide is preferably used as a photosensor.

In the present invention, the average grain size of the photosensitive silver halide grains is preferably small in order to suppress white turbidity after image formation and to obtain good image quality.
The average particle size is 0.1 μm or less, more preferably 0.1 μm.
01 μm to 0.1 μm, especially 0.02 μm to 0.08 μ
m is preferred. Here, the particle size refers to the diameter (equivalent circle diameter) of a circle having the same area as an individual particle image observed with an electron microscope. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. The particle size is more preferably 30% or less, and particularly preferably 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Miller index [1
The ratio of the [00] plane is determined by utilizing the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tan
i. Imaging Sci. , 29, 165 (1
985).

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means that the square root of the projected area is defined as a particle size rμm, and the thickness in the vertical direction is defined as hμ.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958, and can easily obtain target tabular grains.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coatin by et al
g Photographic Emulsion (T
he Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and the formation of reacting a soluble silver salt and a soluble halide is performed using any one of a one-side mixing method, a double-mixing method, a combination thereof and the like. Is also good.

The silver halide used in the present invention preferably contains ions of metals belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe,
Co, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferable, and when used for a photosensitive material for printing plate making, it is preferably selected from Rh, Re, Ru, Ir, and Os.

The ions of these metals can be introduced into silver halide in the form of metal complexes or complex ions. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4 Represents-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand,
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re) and osmium (Os).

The following are specific examples of the transition metal complex ions used in the present invention, but the present invention is not limited to these.

[0051] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN ^2- 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir ( NO) Cl _5] ^2- these metal ions may be a metal complex or metal complex ions one type, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions, metal complexes or metal complex ions is generally from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, preferably from 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol. ^-8 to 1 × 10 ^-4 mol. The compound which provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into silver halide grains, and preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation. When adding,
It may be added in several portions and may be added uniformly in the silver halide grains.
29603, JP-A-2-306236, 3-16
No. 7545, No. 4-76534, No. 6-110146
As described in JP-A Nos. 5-273683 and 5-273683, they can be contained in the particles with distribution.

Preferably, a distribution can be provided inside the particles. These metal compounds can be added after being dissolved in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). A method in which an aqueous solution of the above or a metal compound and an aqueous solution in which NaCl and KCl are dissolved together are added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are simultaneously mixed. A method of preparing silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of mixing silver halides. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation is added and dissolved.

In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the surface of the particles, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

In the present invention, the photosensitive silver halide grains may or may not be desalted after grain formation. However, when desalting is performed, it is known in the art such as a noodle method and a flocculation method. Can be desalted by washing with water.

The photosensitive silver halide grains used 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. In addition, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, iridium compound or the like can be applied.

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 compounds described in JP-A-7-128768 and the like can be used. it can. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, and P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used.

Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate,
Potassium aurithiocyanate, gold sulfide, gold selenide, or compounds described in U.S. Pat. No. 2,448,060 and British Patent No. 618,061 can be preferably used.

Specific compounds used in the reduction sensitization method include, as well as ascorbic acid and thiourea dioxide, for example,
Stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

Next, the organic silver salt used in the present invention will be described.

The organic silver salt used in the present invention is such that tabular organic silver salt particles having an aspect ratio of 3 or more account for 60% of the total organic silver salt.
(Number) or more, more preferably 7 or more.
It is at least 0% (number), particularly preferably at least 80% (number).

In the organic silver salt used in the present invention, the number average of the acicular ratio of the tabular organic silver salt particles measured from the main plane direction is 1.1 or more and less than 5.0.

The tabular organic silver salt particles described above further include:
It is preferable that the average particle size is 1 μm or less and that the particles are monodispersed. The average particle size of the tabular organic silver salt particles is defined as the diameter of a sphere equivalent to the volume of the tabular organic silver salt particles. Average particle size is preferably 0.01 μm or more
0.8 μm, particularly preferably 0.05 μm to 0.5 μm. The monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.

In the present invention, the organic silver salt has an average particle size of 1
It is more preferable that the particles are monodisperse particles having a particle size of not more than μm.

In the present invention, the tabular grains having an aspect ratio of 3 or more are grains having an aspect ratio (abbreviated as AR) of 3 or more, which is represented by the ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) The aspect ratio of the tabular organic silver salt particles used in the present invention is more preferably 3 to 20. The reason is that if the aspect ratio is too low, the organic silver salt particles are likely to be densest, and if the aspect ratio is too high, the organic silver salt particles are likely to overlap each other and disperse in a state of sticking. The above-mentioned range is considered to be a preferable range, since light scattering or the like is likely to occur, and as a result, the transparency of the photosensitive material is likely to decrease.

In the present invention, the tabular organic silver salt particles having a smaller shape anisotropy of two substantially parallel surfaces (principal planes) having the largest area are more suitable for filling in the photosensitive layer. Specifically, the number average of the acicular ratio of the particles measured from the main plane direction is 1.1 or more and less than 5.0.

The number average of the acicular ratio of the tabular organic silver salt particles described above is determined by the following procedure.

First, the photosensitive layer containing the tabular organic silver salt particles was swollen with an organic solvent capable of dissolving the photosensitive layer binder, peeled off from the support, and subjected to ultrasonic washing, centrifugal separation using the above solvent, Repeat the supernatant removal 5 times. The above steps are performed under safelight. Subsequently, the mixture is diluted with MEK (methyl ethyl ketone) so that the organic silver solid content concentration becomes 0.01%, dispersed by ultrasonic waves, and then dropped and dried on a polyethylene terephthalate film hydrophilized by glow discharge.

The film on which the particles are mounted can be used for observation after obliquely vapor-depositing 3 nm thick Pt-C with an electron beam from a 30 ° angle to the film surface with a vacuum vapor deposition device. preferable.

For details of the electron microscopy technique and the sample preparation technique, see “Electronic Microscopy Society of Japan, Kanto Chapter / Medical and Biological Electron Microscopy” (Maruzen), “Japan Electron Microscopy Society of Kanto Chapter, Electronics”. Microscopic biological sample preparation method ”(Maruzen).

The produced sample was subjected to an acceleration voltage of 2 kV using a field emission scanning electron microscope (hereinafter referred to as FE-SEM).
The secondary electron image is observed at a magnification of 5,000 to 20,000 times at 4 to 4 kV, and the image is stored in an appropriate recording medium.

For the above processing, it is convenient to use an apparatus which can AD-convert an image signal from the electron microscope main body and record it directly as digital information on a memory, but an analog image recorded on a polaroid film or the like can also be used. It can be used by converting it into a digital image with a scanner or the like and performing shading correction, contrast / edge enhancement, etc. as necessary.

As for an image recorded on an appropriate medium, it is preferable that one image is decomposed into at least 1024 pixels × 1024 pixels, preferably 2048 pixels × 2048 pixels or more, and image processing is performed by a computer.

As a procedure of the above-described image processing, first, a histogram is prepared, and a portion corresponding to organic silver salt particles is extracted by a binarization process. The unavoidably agglomerated particles are cut by a suitable algorithm or manual operation to perform contour extraction. Then, the maximum length of each particle (MX
LNG) and the minimum width when sandwiched between two parallel lines, that is, the minimum Feret diameter width (WIDTH) is at least 100.
The measurement is performed for each of the 0 particles, and the acicular ratio is determined for each particle by the following formula.

Needle-like ratio = (WIDTH) ÷ (MX LNG) Thereafter, the number average of the needle-like ratio of all the measured particles is calculated. When the measurement is performed in the above procedure, it is preferable that the correction of the length per pixel (scale correction) and the correction of the two-dimensional distortion of the measurement system are sufficiently performed using a standard sample in advance. As a standard sample, Uniform Latex Particles (DULP) commercially available from Dow Chemical Co., USA is suitable, and polystyrene particles having a coefficient of variation of less than 10% with respect to a particle size of 0.1 to 0.3 μm are suitable. Preferably, specifically, the particle size is 0.2
Lots with 12 μm and standard deviation 0.0029 μm are available.

The details of the image processing technology can be referred to “Image processing application technology (Industrial Research Committee) edited by Hiroshi Tanaka”.
The image processing program or device is not particularly limited as long as the above operation can be performed, and an example is Luzex-III manufactured by Nireco.

The method for obtaining the organic silver salt particles having the above-mentioned shape is not particularly limited, but includes a mixed state when forming an organic acid alkali metal salt soap and / or a mixed state when adding silver nitrate to the soap. Optimization of various conditions is effective. It is preferable that the tabular organic silver salt particles used in the invention are preliminarily dispersed together with a binder, a surfactant and the like, if necessary, and then dispersed and pulverized with a media disperser or a high-pressure homogenizer. For the preliminary dispersion, a general stirrer such as an anchor type or a propeller type, a high-speed rotary centrifugal radiation type stirrer (dissolver), and a high-speed rotary shear type stirrer (homomixer) can be used.

Examples of the media dispersing machine include a rolling mill such as a ball mill, a planetary ball mill and a vibrating ball mill, a bead mill as a medium stirring mill, an attritor, and the like.
Other basket mills and the like can be used,
Various types can be used as the high-pressure homogenizer, such as a type that collides with a wall, a plug, or the like, a type in which liquids are divided into a plurality of pieces and then the liquids collide with each other at high speed, and a type in which a thin orifice passes.

In the apparatus used for dispersing the tabular organic silver salt particles used in the present invention, zirconia, alumina,
It is preferable to use ceramics such as silicon nitride and boron nitride or diamond, and particularly preferable to use zirconia.

Further, in the present invention, it is preferable to have a photosensitive layer containing 0.01 mg to 0.5 mg of Zr per 1 g of silver, and it is particularly preferable that the photosensitive layer is 0.01 mg to 0.3 mg of silver. This is the case where Zr is contained.

It is very preferable to optimize the binder concentration, the preliminary dispersion method, the operating conditions of the disperser, the number of dispersions, and the like, when performing the above dispersion, as a method for obtaining the organic silver salt particles of the present invention.

The organic silver salt used in the present invention is a reducible silver source, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long chains (10 to 30, preferably 15 to 30). Aliphatic carboxylic acids having up to 25 carbon atoms) and heterocyclic carboxylic acids having a nitrogen-containing heterocyclic ring are preferably used. Further, an organic or inorganic silver salt complex in which the ligand has a total stability constant for silver ions of 4.0 to 10.0 is also useful.

Examples of suitable silver salts include Research D
No. 17029 and 29996, and include: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver (E.g., 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); a polymer reaction formed between an aldehyde and a hydroxy-substituted aromatic carboxylic acid Silver complex, for example, aldehydes (formaldehyde,
Acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thiones, for example, 3- (2- (Carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole Complex or salt of a nitrogen acid and silver selected from, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; silver salts such as saccharin, 5-chlorosalicylaldoxime; and mercaptides Silver salt.
Preferred silver sources are silver behenate, silver arachidate and / or silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, but a forward mixing method, a reverse mixing method, a simultaneous mixing method and the like are preferably used. Further, it is also possible to use a controlled double jet method as described in JP-A-9-127463.

Specifically, an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.) was prepared by adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid. later,
Silver nitrate is added to the soap to produce organic silver salt crystals. At that time, silver halide grains may be mixed,
The above series of reaction steps need to be performed while stirring sufficiently using a suitable stirring member so that the inside of the reaction tank becomes uniform.

The photothermographic material of the present invention contains a reducing agent. Examples of suitable reducing agents are described in U.S. Pat.
Nos. 770,448, 3,773,512, 3,593,863, and Research Diss.
Closure Nos. 17029 and 29996, and include: Aminohydroxycycloalkenones (for example, 2-hydroxypiperidino-2)
-Cyclohexenone); aminoreductone esters (e.g., piperidinohexose reductone monoacetate) as precursors of reducing agents; N-hydroxyurea derivatives (e.g., N-p-methylphenyl-N-hydroxy) Ureas) hydrazones of aldehydes or ketones (e.g., anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone, and (2) , 5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amidooxins; Azines (eg, a combination of an aliphatic carboxylic acid hydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone or hydrazine; Hydroxanoic acids; Azines and sulfonamidophenol Α-cyanophenylacetic acid derivatives; bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,3-dione; Chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-
Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t)
-Butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0087]

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In the formula, R is a hydrogen atom or a group having 1 to carbon atoms.
Represents an alkyl group having 10 carbon atoms (eg, butyl group, 2,4,4-trimethylpentyl group, etc.), and R ′ and R ″ are each an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group). , T-butyl group, etc.).

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

[0090]

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[0091]

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

The heat-developable photographic light-sensitive material of the present invention preferably contains an antifoggant. What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. However, the use of mercury compounds is environmentally unfriendly.

Non-mercury antifoggants include, for example, US Pat. Nos. 4,546,075 and 4,452,88.
No. 5 and JP-A-59-57234 are preferred.

Particularly preferred non-mercury antifoggants are disclosed in US Pat. Nos. 3,874,946 and 4,756,99.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include paragraphs [003] of JP-A-9-288328.
0] to [0036] are preferably used. As another example of the preferred antifoggant, JP-A-9-90550, paragraph [006]
2] to [0063]. Still other suitable antifoggants are described in U.S. Pat.
8,523 and European Patent Nos. 600,587, 6
Compounds disclosed in JP-A Nos. 05,981 and 631,176 and the like can be used.

It is preferred to add a toning agent to the photothermographic material of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are Research Disc
No. 17029, which includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Combinations of acids; phthalazine (including adducts of phthalazine) and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example,
Combination with at least one compound selected from phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; quinazolinediones, benzoxazine, naloxazine derivatives; benzoxazine-2,4-dione (Eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg,
3,6-dimercapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The heat-developable photographic light-sensitive material of the present invention includes, for example, JP-A-63-159814 and JP-A-60-140335.
No. 63-231437, No. 63-296551
No. 63-304242, No. 63-15245,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
No. 175 and No. 4,835,096.

Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
17643 IV-A (p. 23, December 1978), and Item 18431 (p. 437, August 1979), etc. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-806
The compounds described in No. 79 are preferably used.

In the present invention, a mercapto compound, a disulfide compound and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like. be able to. When a mercapto compound is used in the present invention, any structure may be used, but Ar-SM, Ar-SM
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy (eg, For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
-Mercaptoquinoline, 8-mercaptopurine, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like,
The present invention is not limited to these.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and a matting agent is preferably provided on the surface of the photosensitive material in order to prevent the image after thermal development from being damaged. It is preferable that the content of the agent is 0.5 to 30% by weight based on all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic substances, starch described in U.S. Pat. No. 2,322,037, etc.,
Belgian patent 625,451 and British patent 981,
No. 198, etc., JP-B-44-36
No. 43, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, etc., polyacrylonitrile described in US Pat. No. 3,079,257, 3,022,169.
Organic matting agents such as the polycarbonates described in Nos. 1 and 2 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 The matting agent used in the present invention can be contained in any constituent layer, but in order to achieve the object of the present invention, It is preferably a constituent layer other than the photosensitive layer, and more preferably the outermost layer as viewed from the support. The method for adding the matting agent used in the present invention may be a method in which the matting agent is dispersed in a coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after applying the coating solution. May be used. When a plurality of types of matting agents are added, both methods may be used in combination.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.
In the present invention, the conductive compounds described in U.S. Pat. No. 5,244,773, columns 14 to 20, are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other constituent layers. In the heat-developable photographic light-sensitive material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used in addition to the above. These additives and the other additives mentioned above are Research Discl.
osure Item 17029 (p. June 1978, p.
Compounds described in 9 to 15) can be preferably used.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) ), Li (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic.

Further, in order to protect the surface of the photosensitive material and prevent abrasion, a non-photosensitive layer may be provided outside the photosensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, in order to increase the speed of thermal development, the amount of the binder in the photosensitive layer is 1.5 to 10 g / m ^2.
It is preferable that More preferably, 1.7 to 8 g
/ M ² .

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, or the like) in order to prevent deformation of an image after development processing.
Polyimide, nylon, cellulose triacetate, polyethylene naphthalate) are preferred.

Among them, a preferable support is a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene polymer having a syndiotactic structure. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm. A heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more, preferably at a temperature higher by 35 ° C. or more, More preferably, heating is performed at a temperature higher than 40 ° C.

Next, the plastic used in the present invention will be described.

PET is composed of polyethylene terephthalate as the polyester component. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, and 5-sodium sulfo acid are used as acid components. A polyester containing a modified polyester component of isophthalic acid, adipic acid or the like and a glycol component such as ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol or the like in an amount of 10 mol% or less of the entire polyester may be used.

SPS is a polystyrene having steric regularity unlike ordinary polystyrene (atactic polystyrene). The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that there are more regular parts such as two, three, five or more. In the present invention, the racemo chain is 2 It is preferably 85% or more in the chain, 75% or more in the three chains, 50% or more in the five chains, and 30% or more in the further chains. The polymerization of SPS can be carried out according to the method described in JP-A-3-131843.

As the method of forming a film of a support and the method of producing an undercoat used in the present invention, known methods can be used. Preferably, the method described in paragraph [0030] of JP-A-9-50094 is used.
To [0070].

The heat-developable photographic light-sensitive material of the present invention forms a photographic image by heat-development, and comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, It is preferable that the photothermographic material is a heat-developable photographic material containing a color tone agent for suppressing the color tone of silver in a state of being dispersed in a usual (organic) binder matrix.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon 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. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. To control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or pigment may be included in the active layer. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range, and examples thereof include JP-A-59-6481 and JP-A-59-1.
No. 82436, U.S. Pat. Nos. 4,271,263 and 4,594,312, European Patent Publication 533,008.
No. 652,473, JP-A-2-216140,
4-348339, 7-191432, 7-
The compounds described in No. 301890 are preferably used.

These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a slip agent such as a polysiloxane compound, wax or liquid paraffin.

The light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

The details of the heat-developable photographic light-sensitive material are described in, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075, and D.C. Morgan (Dry Silver Photographic Materials)
Photographic Material) "and D.C.
Morgan and B.A. Shelley
y) "Heat treated silver system (The
rmally Processed SilverSy
stems) "(Imaging Processes and Materials)
s and Materials) Neblette
Eighth Edition, Sturge, V.S. Walworth, A .; Shepp
Editing, 2nd page, 1969). Among them, the present invention is characterized in that an image is formed by thermally developing a photosensitive material at 80 to 140 ° C., and no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, after the heat development,
The optical transmission density of the light-sensitive material containing the support at 400 nm is preferably 0.2 or less. A more preferable value of the optical transmission density is 0.02 or more and 0.2 or less.

Examples of the solvent used in the present invention include ketones such as acetone, isophorone, ethyl amyl ketone, methyl ethyl ketone and methyl isobutyl ketone. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, cyclohexanol, and benzyl alcohol. As glycols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Hexylene glycol and the like can be mentioned. Ethylene glycol monomethyl ether as ether alcohols,
And diethylene glycol monoethyl ether. Examples of ethers include ethyl ether, dioxane, and isopropyl ether. Examples of the esters include ethyl acetate, butyl acetate, amyl acetate, and isopropyl acetate. N-pentane, n as hydrocarbons
-Hexane, n-heptane, cyclohexane, benzene, toluene, xylene and the like. Examples of chlorides include methyl chloride, methylene chloride, chloroform, dichlorobenzene and the like. Examples of the amines include monomethylamine, dimethylamine, triethanolamine, ethylenediamine, and triethylamine. Other examples include water, formamide, dimethylformamide, nitromethane, pyridine, toluidine, tetrahydrofuran, acetic acid and the like. However, it is not limited to these. These solvents may be used alone or
Several types can be used in combination.

The content of the solvent in the photosensitive material can be adjusted by changing conditions such as temperature conditions in a drying step after the coating step. The content of the solvent can be measured by a method using gas chromatography as described below.

[0127] The amount of solvent contained in the photothermographic material of the present invention in a total amount, 500 mg / m ² but less preferred, more preferably from 5 to 400 mg / m ^2,
Particularly preferably, it is 10 to 300 mg / m ² . By adjusting the content of the solvent in the photothermographic material to be within the above range, after heat development, while having high sensitivity,
In addition, a photothermographic material having a low fog density can be obtained.

In the present invention, the exposure is preferably performed by laser scanning exposure, but it is preferable to use a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular. .

Here, "not substantially vertical" means that the angle is most vertical during laser scanning, preferably 55 to 88 degrees, more preferably 60 to 86 degrees, and still more preferably. Is 65 degrees or more and 84 degrees or less,
Most preferably, it is not less than 70 degrees and not more than 82 degrees.

The beam spot diameter on the exposed surface of the photosensitive material when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. This is preferable because the smaller the spot diameter is, the less the angle of deviation of the laser incident angle from the vertical can be reduced. In addition,
The lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of interference fringe-like unevenness.

The exposure used in the present invention is preferably performed by using a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi. Image quality deterioration such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode. To achieve vertical multiplication, a method such as combining, using return light, or superimposing a high frequency is preferable. Note that the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more. There is no particular upper limit on the distribution of the exposure wavelength,
Usually, it is about 60 nm.

[0132]

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

Example 1 (Preparation of Support) 0.175 (densitometer PDA-65 manufactured by Konica Corporation) was colored blue and had a thickness of 175.
A corona discharge treatment of 8 W / m ² · min was applied to both sides of a μm PET film.

(Preparation of Photosensitive Silver Halide Emulsion A) Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, an aqueous solution containing 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide (equimolar to the above-mentioned silver nitrate) in a molar ratio of (98/2) was used.
0 ml and iridium chloride at 1 × 10 ^-4 per mole of silver.
Mole was added over 10 minutes by a controlled double jet method, keeping the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the particle size was 1
Cubic silver iodobromide grains of 2% and [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
5.9 and a pAg of 7.5 to obtain a photosensitive silver halide emulsion A.

(Preparation of Powdered Organic Silver Salt A) In 9450 ml of pure water, 324 g of behenic acid, 99 g of arachidic acid and 56 g of stearic acid were dissolved at 80 ° C. Next, 980 ml of a 1.5 M aqueous sodium hydroxide solution was added while stirring at a high speed. Next, 9.3 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. and stirred for 30 minutes.
(Containing 0.9 mole of silver and 1400 g of water) for 5 seconds and stirred for 5 minutes, and then 1M silver nitrate solution 1
Add 470 ml over 2 minutes and stir for another 20 minutes
Water-soluble salts were removed by filtration. Thereafter, washing with deionized water and filtration are repeated until the conductivity of the filtrate becomes 2 μS / cm, centrifugal dehydration is performed, and then hot air drying is performed at 37 ° C. until the weight is no longer reduced. I got

(Preparation of photosensitive emulsion dispersions 1 to 4) Polyvinyl butyral powder (Butva manufactured by Monsanto)
r B-79) 14.57 g of methyl ethyl ketone 14
Then, 500 g of the powdered organic silver salt A was gradually added and mixed well while stirring with a dissolver-type homogenizer. Thereafter, a media type dispersing machine (gettzm) filled with 80% of 1 mm diameter Zr beads (manufactured by Toray)
The emulsion was dispersed at a peripheral speed of 13 m and a residence time in the mill of 0.5 minute at a peripheral speed of 13 m to prepare a photosensitive emulsion dispersion liquid 1.

A photosensitive emulsion dispersion 2 was obtained in exactly the same manner as in preparation of the photosensitive emulsion dispersion 1, except that the residence time in the mill was changed to 3 minutes. The preparation of the photosensitive emulsion dispersion liquid 1 was carried out in the same manner as in the preparation of the photosensitive emulsion dispersion liquid 1, except that the dispersion was carried out with a high-pressure homogenizer (manufactured by APV) at 560 kgf / cm ² in one pass instead of the media type disperser. A photosensitive emulsion dispersion 3 was prepared in exactly the same manner as described above. Photosensitive emulsion dispersion liquid 4 was obtained in exactly the same manner as in preparation of photosensitive emulsion dispersion liquid 3, except that dispersion was repeated five times.

<< Preparation of Infrared Sensitizing Dye Liquid >> 350 mg of infrared sensitizing dye 1, 13.96 g of 2-chloro-benzoic acid,
And 2.14 g of 5-methyl-2-mercaptobenzimidazole were dissolved in 73.4 ml of methanol in a dark place to prepare an infrared sensitizing dye solution.

<< Preparation of Stabilizer Liquid >> 1.0 g of stabilizer 1,
0.5 g of potassium acetate was dissolved in 8.5 g of methanol to prepare a stabilizer solution.

<< Preparation of Developer Solution >> 17.74 g of reducing agent A-3 was dissolved in methyl ethyl ketone (MEK),
Finished to 0 ml and used as developer solution.

<< Preparation of Antifoggant Solution >> 5.81 g of the antifoggant 2 was dissolved in MEK and finished to 100 ml.
An antifoggant solution was used.

<< Preparation of Coating Solution for Photosensitive Layer >> The above-mentioned photosensitive emulsion dispersion 1 (50 g) and 15.11 g of MEK were kept at 21 ° C. while stirring, and 390 μl of antifoggant 1 (10% methanol solution) was added. Stirred for hours. Further, 889 μl of calcium bromide (10% methanol solution) was added, and the mixture was stirred for 30 minutes. Next, an infrared sensitizing dye solution 1.41
After adding 6 ml and 667 μl of the stabilizer solution and stirring for 1 hour, the temperature was lowered to 13 ° C. and further stirred for 30 minutes. While keeping the temperature at 13 ° C, polyvinyl butyral (M
onsanto Butvar B-79) 13.3
After adding 1 g and stirring for 30 minutes, the following additives were added at intervals of 15 minutes while stirring was continued.

Phthalazine 305 mg Tetrachlorophthalic acid 102 mg 4-Methylphthalic acid 137 mg Infrared dye 1 37 mg After adding the above and stirring for 15 minutes, antifoggant solution 5.47 ml developer solution 14.06 ml 10% MEK solution of epoxy compound A 10% MEK solution of an acid anhydride shown in Table 1 The additives described above shown in Table 1 were sequentially added and stirred to obtain a photosensitive layer coating solution 1.

Photosensitive emulsions 2 to 4 were prepared in the same manner as coating solutions 2 to 4 for photosensitive layers.

The following layers were sequentially formed on a support to produce photosensitive materials 1 to 4. In addition, each drying was performed at 75 ° C. for 5 minutes.

[0146]

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[0147]

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<< Coating on Back Side >> Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² Matting agent: Monodispersity 15% Average particle size 10 μm Monodispersed silica 30 mg / m ² << Coating on photosensitive layer side >> Photosensitive layer 1 4: The liquid having the above composition was applied so that the applied silver amount was 2 g / m ² .

Surface protective layer: A solution having the following composition was applied on the photosensitive layer.

Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Matting agent: Monodispersity 10% Average particle size 4 μm Monodisperse silica 70 mg / m ² << Preparation of photosensitive materials 5-8 >> Photosensitive material 1 described above In each of the surface protective layers of Nos. 1 to 4, light-sensitive materials 5 to 8 were prepared in the same manner as in the light-sensitive materials 1 to 4, except that a liquid having the following composition was applied.
Were each produced.

<< Surface protective layer composition of photosensitive materials 5-8 >> Methyl ethyl ketone (MEK) 17 ml / m ² Cellulose acetate 2.3 g / m ² Phthalazine 250 mg / m ² Paraloid A21 (Rohm and Haas Company, PMMA) 100 mg / m ² hardener (HD-1) 10% of 35 mg / m ² Desmodur N3300 methyl ethyl ketone solution 3.2 ml / m ² SuperPflex (Mintekku, calcium carbonate) 20 mg / m ²

[0152]

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<< Measurement of Solvent Content in Film >> A film area of 46.3 cm ² was cut out, finely chopped to about 5 mm, stored in a dedicated vial, sealed with a septum and an aluminum cap, and then manufactured by Hewlett-Packard Company. It was set on a headspace sampler HP7694. Gas chromatography connected to a headspace sampler (GC: Hewlett-Packard 5
Model 971) has a flame ionization detector (F
ID). The measurement conditions are shown below.

Headspace sampler heating condition: 120 ° C, 20 minutes GC introduction temperature: 150 ° C Column: DB-624 manufactured by J & W Increasing temperature: 45 ° C, hold for 3 minutes → 100 ° C (8 ° C / min) Measurement described above Under the conditions, a gas chromatogram was obtained.
The solvent to be measured was MEK and methanol, and a predetermined amount diluted with each of butanol in the solvent on the left was stored in a dedicated vial, and then prepared using the peak area of the chromatogram obtained by measuring in the same manner as above. The solvent content in the film was calculated using the calibration curve.

<< Exposure and Development Processing >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam. (Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.) Thereafter, the photosensitive material was processed using an automatic developing machine having a heat drum. 11 so that the protective layer and the drum surface are in contact with each other.
The film was thermally developed at 0 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

<< Glossiness >> Digital Variable Angle Specular Gloss Meter UGV
Using -5D (manufactured by Suga Test Instruments Co., Ltd.), the glossiness of the surface protective layer (light reflection preventing layer side) was measured at an incident angle of 20 ° with respect to the glass surface.

<< Evaluation of Image Unevenness >> The sample subjected to the exposure and development processing described above was visually evaluated for image unevenness. The evaluation was performed according to the following sensory evaluation criteria.

：: No image unevenness at all Δ: Slight image unevenness is generated, but practically acceptable X: Clearly image unevenness occurs, making it impractical

[0159]

[Table 1]

From Table 1, it is clear that the sample of the present invention has significantly less image unevenness than the comparative sample.

Example 2 A photographic support and a photosensitive silver halide emulsion A were prepared in the same manner as in Example 1.

(Preparation of Powdered Organic Silver Salt) In 4720 ml of pure water, 111.4 g of behenic acid, 83.8 g of arachidic acid,
54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, a 1.5 M aqueous sodium hydroxide solution 54 was added.
After adding 0.2 ml of concentrated nitric acid and 6.9 ml of concentrated nitric acid,
Upon cooling to ° C., a fatty acid sodium solution was obtained. While maintaining the temperature of the above-mentioned fatty acid sodium solution at 55 ° C., the above-mentioned photosensitive silver halide emulsion A and 450 ml of pure water were added, and the mixture was stirred for 5 minutes. Next, a 1M silver nitrate solution 760.6
ml was added over 2 minutes, stirred for another 20 minutes, and the water-soluble salts were removed by filtration. Thereafter, water washing with deionized water and filtration were repeated until the conductivity of the filtrate became 2 μS / cm, centrifugal dehydration was performed, and then hot-air drying was performed at 37 ° C. until weight loss was eliminated.

(Preparation of photosensitive emulsion dispersion) Polyvinyl butyral powder (Butvar B manufactured by Monsanto)
-79) 14.57 g of methyl ethyl ketone (MEK)
The mixture was dissolved in 1457 g, and 500 g of the powdered organic silver salt A was gradually added and mixed well while stirring with a dissolver type homogenizer. Thereafter, a media-type dispersing machine (gettz) filled with 80% of Zr beads (manufactured by Toray) having a diameter of 1 mm.
13m, residence time in the mill 0.5
For 1 minute to prepare a photosensitive emulsion dispersion.

(Preparation of infrared sensitizing dye liquid) 350 mg of infrared sensitizing dye 1, 13.96 g of 2-chloro-benzoic acid and 2.14 g of 5-methyl-2-mercaptobenzimidazole were added to methanol 73. The solution was dissolved in 4 ml in the dark to prepare an infrared sensitizing dye solution.

(Preparation of Photosensitive Layer Coating Solution) The above photosensitive emulsion dispersion (500 g) and 100 g of MEK were kept at 21 ° C. while stirring. Next, bis (dimethylacetamide) dibromobromate (0.20 g) was added, and the mixture was stirred for 1 hour. Further, calcium bromide (3.25 ml of a 10% methanol solution) was added, and the mixture was stirred for 30 minutes.

Next, 1.5 ml of the above-mentioned infrared sensitizing dye solution was added, and the mixture was stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C., 48 g of polyvinyl butyral is added and dissolved sufficiently, and then the following additives are added.

Phthalazine 1.5 g Tetrachlorophthalic acid 0.5 g 4-Methylphthalic acid 0.5 g 2- (tribromomethyl-sulfonyl) -pyridine 1.9 g Reducing agent A-3 15 g Epoxy compound (10% MEK solution) Table Acid anhydride (10% MEK solution) shown in Table 2 The coating liquid preparation step shown in Table 2 was carried out at 80% RH, 5%
Performed at 0% RH and 35% RH, and at 35% RH for 30%, 50%, and 100% of the total process time from the start of preparation, with nitrogen replacement, and under a total of six types of conditions, Coating solutions 1 to 24 were prepared.

The following layers were sequentially formed on a support, and
Samples 1 to 24 were prepared. In addition, each drying is 75
C. for 5 minutes.

About each coating solution, MK manufactured by Kyoto Electronics Co., Ltd.
The water content was measured by the Karl Fischer method using A-210. As Karl Fischer reagent SS, Mitsubishi Chemical No. E98062, and as a dehydrated solvent CM, Mitsubishi Chemical No. L97988 was used.

Table 2 shows the preparation conditions and the water content of each coating solution.

(Coating on Back Side) A coating solution having the following composition was applied to a wet thickness of 80 μm.

Polyvinyl butyral (10% MEK solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0173]

Embedded image

(Coating of photosensitive layer side) The photosensitive layer coating solution was coated such that the coating amount of the photosensitive layer was 2.0 g / m ² and polyvinyl butyral as a binder was 8.5 g / m ² . .

(Surface Protective Layer) A solution having the following composition was applied onto each photosensitive layer so as to have a wet thickness of 100 μm.

Acetone 175 ml Methanol 15 ml Cellulose acetate butyrate 8.0 g Phthalazine 1.0 g 4-methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g Monodisperse silica binder with an average particle size of 4 μm <Measurement of solvent content in film> The measurement of the solvent content in the film was performed in the same manner as in Example 1.

[0177]

[Table 2]

The following performance evaluation was performed on the sample obtained as described above.

<< Exposure and development treatment >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam. (Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared with the case where the angle was set to 90 degrees.) Thereafter, the protective layer of the photosensitive material was formed using an automatic developing machine having a heat drum. And the drum surface are brought into contact with each other.
C. for 15 seconds. At that time, exposure and development are 2
The test was performed in a room conditioned at 3 ° C. and 50% RH. Evaluation of the obtained image was performed using a digital densitometer PDA-65 (Konica Corporation)
Manufactured). The result of the measurement was evaluated by sensitivity (reciprocal of the ratio of the exposure amount giving a density higher than that of the unexposed portion by 1.0) and fog, and the sensitivity of photosensitive material 1 (N = 1) was evaluated as 100.
Table 3 shows the relative values.

<< Evaluation of Production Stability >> A coating solution for the photosensitive layer was prepared under each condition at N = 3, and sensitometric evaluation was similarly performed.

<< Evaluation of Sensitometry >> The coated sample was cut into 3.5 cm × 15 cm and exposed with a laser sensitometer equipped with an 810 nm diode.
After processing (developing) at 15 ° C. for 15 seconds, the obtained image was evaluated using a densitometer. The result of the measurement is Dmin, sensitivity (D
(Reciprocal of the ratio of the exposure amount giving a density 1.0 higher than min)
And the sample No. was evaluated. The relative sensitivity was shown with the sensitivity of 1 as 100.

Table 3 shows the obtained results.

[0183]

[Table 3]

<< Exposure and Development Processing >> From the emulsion side of the photosensitive material prepared as described above, a wavelength of 800
Exposure was performed by laser scanning using an exposing machine using a semiconductor laser having a vertical multi-mode of nm to 820 nm as an exposure source. At this time, an image was formed at an angle of 75 degrees between the exposure surface of the photosensitive material and the exposure laser beam. (Note that an image having less unevenness and unexpectedly good sharpness and the like was obtained compared to the case where the angle was set to 90 degrees.) Thereafter, protection of the photosensitive material was performed using an automatic developing machine having a heat drum. 11 so that the layer and the drum surface are in contact with each other.
The film was thermally developed at 0 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

<< Glossiness >> The glossiness was evaluated in the same manner as in Example 1.

<< Evaluation of Image Unevenness >> Evaluation of image unevenness was performed in the same manner as in Example 1.

Table 4 shows the obtained results.

[0188]

[Table 4]

As can be seen from Tables 3 and 4, the samples having a water content of 5 to 50 g per mol of silver in the coating solution had high sensitivity, low fog, and had very little image unevenness during development, and were excellent. It is clear that the characteristics are exhibited.

[0190]

According to the present invention, a high-sensitivity, low-fogging photothermographic material and an image forming method using the same can be provided.

Claims (7)

[Claims] 1. A photothermographic material comprising a support having thereon a photosensitive layer containing at least an organic silver salt, a photocatalyst, a reducing agent and a binder, comprising at least one epoxy compound and at least one acid anhydride. And a photothermographic material having a surface glossiness of 1% to 60%. 2. The photothermographic material according to claim 1, wherein the photosensitive layer contains an epoxy compound. 3. The photothermographic material according to claim 1, wherein the epoxy compound is represented by the following general formula (1), and the acid anhydride is represented by the following general formula (2). material. Embedded image [In the formula, R represents a divalent linking group which may have a substituent, and X represents a divalent linking group. [Chemical formula 2] [In the formula, Z represents an atomic group necessary for forming a monocyclic or polycyclic system. ] 4. The photothermographic material according to claim 1, 2 or 3, wherein an angle between an exposure surface and the scanning laser beam does not become substantially vertical. An image recording method, comprising: 5. The image recording method according to claim 4, wherein a laser scanning exposure device that emits a scanning laser beam that is a vertical multi is used. 6. An image forming method, wherein the photothermographic material according to any one of claims 1, 2 and 3 is heated and developed in a state in which the solvent contains 500 mg / m ² or less. . 7. The amount of water in a coating solution used for coating the photosensitive layer of the photothermographic material according to claim 1, 2 or 3, relative to 1 mol of silver contained in the coating solution. 5
A method for producing a photothermographic material, wherein the weight is 50 g.