JPH11338098A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat developable photosensitive material high in sharpness and good in transparency and low in fog and prevented from decoloration during storage by incorporating a pigment for preventing irradiation in a photosensitive layer and a dye for preventing irradiation in a nonphotosensitive layer. SOLUTION: The photosensitive layer contains the pigment for preventing irradiation and at least one nonphotosensitive layer on the same side of the photosensitive layer with respect to a support contains the dye for preventing irradiation. It is preferred that the total optical density obtained by preventing te irradiation is 0.05-1.0. The pigment to be used for the photosensitive layer can be embodied by azo pigments and polycyclic pigments, such as phthalocyanine type pigments and anthraquinone type pigments and the like, and inorganic pigments. The dyes to be used for the nonphotosensitive layers can be embodied by oxonole dyes having pyrazolone rings or barbituric acid rings, azo dyes, anthraquione dyes, and cyanine dyes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photothermographic material,
In particular, the present invention relates to a photothermographic material having good sharpness, high transparency, and little discoloration during storage.

[0002]

2. Description of the Related Art Photothermographic materials have been proposed for a long time, and are described in, for example, U.S. Pat. Nos. 3,152,904 and 3,457,757 and B. Shely, "Armally Processed Silver System (Thermally Processed). Processed Silver Syst
em) '' (Imaging Process and Materials, Neblette No. 8)
Edition, Sturge, V. Walworth,
A. Shepp, p. 2, 1996).

A photothermographic material generally comprises a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent, a reducible silver salt.
(Eg, organic silver salt), and has a photosensitive layer in which a color tone controlling silver tone is dispersed in a binder matrix.

A photothermographic material is heated to a high temperature (for example, 80 ° C. or higher) after image exposure, and a redox reaction between a silver halide or a reducible silver salt (functioning as an oxidizing agent) and a reducing agent is performed. As a result, a black silver image is formed. The oxidation-reduction reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, a black silver image is formed in the exposed area.

[0005] The heat development process has an advantage that a processing solution in the wet development process is not required, and the processing can be performed simply and quickly. However, in the field of photographic technology, an image forming method by wet development processing is still mainstream. This is because there remains an unsolved problem in the heat development processing that is not in the wet development processing.

[0006] It is known that the constituent layers of a photographic light-sensitive material are colored for the purpose of preventing irradiation. However, in a heat-developable photosensitive material, when a coloring agent is added to the photosensitive layer, the development fog is increased, the color is faded or discolored during storage, and the color is faded or discolored during storage. Even when there is no problem, there is a problem that transparency is low and absorbance is low.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photothermographic material having high sharpness, good transparency, low fog, and preventing fading during storage.

[0008]

The object of the present invention is to provide the following (1)
This was achieved by the photothermographic materials of (1) to (4). (1) A heat-sensitive material comprising a pigment for preventing irradiation in the photosensitive layer and a dye for preventing irradiation in at least one non-photosensitive layer on the same side of the support as the photosensitive layer. Developed photosensitive material. (2) The photothermographic material according to the above (1), wherein the photosensitive layer contains a polyhalogen compound. (3) The photothermographic material according to the above (1) or (2), wherein the layer on the photosensitive layer side with respect to the support has a total optical density for preventing irradiation of 0.05 to 1.0. (4) The photothermographic material according to any one of the above (1) to (3), wherein the photosensitive layer contains an organic silver salt, a reducing agent, and a photosensitive silver halide.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The photothermographic material of the present invention contains a pigment for preventing irradiation in the photosensitive layer, and further includes a non-irradiation preventing pigment in at least one non-photosensitive layer on the same side as the photosensitive layer and the support. Including dyes for The reason why the pigment is used for the photosensitive layer is that fogging can be reduced as compared with the dye, and discoloration and discoloration during storage can be suppressed.By adopting the above configuration, irradiation or halation is prevented. The resulting photothermographic material has excellent sharpness, low Dmin (minimum density), and excellent transparency. In contrast, when a pigment is used for the non-photosensitive layer, Dm
in rises. When the pigment is used only for the photosensitive layer and the non-photosensitive layer does not contain a dye or pigment for preventing irradiation, Dmin and fog increase. That is, good sharpness, low fog and low Dm
According to the present invention, it is necessary to use a pigment for preventing irradiation in the photosensitive layer and to use a dye for preventing irradiation in the non-photosensitive layer in order to achieve the compatibility of in.

In the present invention, as pigments used in the photosensitive layer, commercially available pigments and known pigments described in various documents can be used. For literature, see Color Index (The Society of Dyers and Colorists)
Ed.), “Revised New Edition Pigment Handbook”, edited by the Japan Pigment Technical Association (19)
1989), “Latest Pigment Application Technology,” CMC Publishing (198
6 years), Printing Ink Technology, CMC Publishing (1984), W. Herbst, K. Hunger, Industrial Orga
nic Pigments (VCH Verlagsgesellschaft, 1993) and the like. Specifically, organic pigments include azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments,
Indigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments,
Diketopyrrolopyrrole-based pigments, dyed lake pigments (lake pigments of acidic or basic dyes), azine pigments, and inorganic pigments can be used. Among them, in order to obtain a preferable bluish color tone, a phthalocyanine pigment,
Anthraquinone-based indanthrone pigments, dyed lake pigment-based triarylcarbonium pigments, indigo,
Ultramarine, navy blue and cobalt blue inorganic pigments are preferred. Further, in order to adjust the color tone, a red or purple pigment, for example, a dioxazine pigment, a quinacridone pigment, a diketopyrrolopyrrole pigment, or the like may be used in combination with the blue pigment.

Specific examples of preferred pigments will be listed below. Examples of blue pigments include phthalocyanine-based CI Pigment
Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6
(Copper phthalocyanine), monochloro or low chlorinated copper phthalocyanine, CI Pigment Blue 16 (metal-free phthalocyanine), phthalocyanine with a central metal of Zn, Al, Ti, indantron-based CI Pigment blue 60 also known as vat dyes, and the like. Halogen-substituted products, for example, CI Pigment Blue 64 and 21, azo type CI Pigment
Blue 25, indigo-based CI Pigment Blue 66 and lake pigment CI Pigment Blue 63, triarylcarbonium-type acidic dye or basic dye lake pigment CI Pigment Blue 1, 2, 3, 9, 9, 10 1
4, 18, 19, 24: 1, 24: x, 56, 61, and 62. Dioxazine based red or purple pigments
CIPigment Violet 23, 37, azo-based CIPigment Vi
olet 13, 25, 32, 44, 50, CIigment Red
23, 52: 1, 57: 1, 63: 2, 146, 150, 151,
175, 176, 185, 187, 245, quinacridone-based CIPigment Violet 19, 42, CIPigment Red 1
22, 192, 202, 207, 209, triarylcarbonium-based lake pigment CI Pigment Violet 1,
2, 3, 27, 39, CI Pigment Red 81: 1, Perylene-based CI Pigment Violet 29, Anthraquinone-based CIP
igment Violet 5: 1, 31 and 33, thioindigo C.
I. Pigment Red 38 and 88.

The pigment which can be used in the present invention may be the above-mentioned naked pigment or a pigment which has been subjected to a surface treatment. Examples of the surface treatment method include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. It is considered and is described in the following literature.

Properties and application of metal soap (Koshobo) Printing ink technology (CMC Publishing, 1984) Latest pigment application technology (CMC Publishing, 1986)

In the present invention, the pigment is used by being dispersed in a binder. Various dispersants can be used in accordance with the binder and pigment to be used, for example, a surfactant-type low-molecular-weight dispersant or a high-molecular-weight dispersant. It is more preferable to use a polymer type dispersant from the viewpoint of properties. Examples of dispersants include JP-A-3-69949 and EP 5494.
No. 86 and the like.

The average particle size of the pigment which can be used in the present invention is preferably in the range of 0.01 to 10 μm after dispersion, more preferably 0.05 to 1 μm.

As a method for dispersing the pigment in the binder, known dispersion techniques used in the production of inks and toners can be used. Examples of the dispersing machine include a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 19
86).

The coloring density (optical density for preventing irradiation) of the photosensitive layer is preferably 0.01 to 1.0 as an absorbance at the exposure wavelength in order to obtain a substantial effect on image quality such as sharpness. , Especially 0.03
~ 0.5 is preferred. When there are a plurality of photosensitive layers, the sum is the total value.

Dyes which can be used in the non-photosensitive layer on the photosensitive layer side in the present invention include, for example, British Patent Nos. 506,385 and 1,177,429.
Nos. 1,311,884, 1,338,799, 1,385,371,
No. 1,467,214, No. 1,433,102, No. 1,553,516, JP-A-48-85,130, No. 49-114,420, No. 52-117,123, No. 5
5-161,233, 59-111,640, JP-B-39-22,069,
Nos. 43-13,168 and 62-273527, U.S. Pat.
No. 3,469,985, oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus described in 4,078,933, etc., U.S. Pat.Nos. 2,533,472, 3,379,533, and other oxonol dyes described in British Patent 1,278,621 etc. , UK Patent Nos. 575,691, 680,631, 599,623
Nos. 786,907, 907,125, 1,045,609, U.S. Pat.No.4,255,326, Azo dyes described in JP-A-59-211,043, etc., 50-50,116, 54-118,247, 2, 01
Anthraquinone dyes described in 4,598, 750,031 and the like, U.S. Pat.Nos. 2,538,009, 2,688,541, 2,538,
No. 008, UK Patent Nos. 584,609 and 1,210,252, JP-A-5
0-40,625, 51-3,623, 51-10,927, 54-118,
No. 247, Japanese Patent Publication Nos. 48-3,286, 59-37,303, etc., arylidene dyes, Japanese Patent Publication Nos. 28-3,082, 44-16,594
Nos. 59-28,898, styryl dyes described in British Patent Nos. 446,583 and 1,335,422, and triarylmethane dyes described in JP-A-59-228,250, etc.
075,653, 1,153,341, 1,284,730, 1,475,2
And merocyanine dyes described in US Pat. Nos. 2,542,807 and 3,294,539, and the like. Also, so-called squarylium dyes and croconium dyes can be used.

Among these, the dyes which can be particularly preferably used in the present invention are represented by the following general formulas (I), (II) and
A dye represented by (III), (IV), (V) or (VI).

[0020]

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In the general formula (I), Z ₁ and Z ₂ may be the same or different and each represents a nonmetal group necessary for forming a heterocyclic ring, and L _{1 to} L ₅ each represent a methine group. And n ₁ , n ₂
Represents 0 or 1, and M ⁺ represents a hydrogen atom or other monovalent cation.

[0022]

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[0023] In the general formula _{(II), X 11, Y} 11 may be the same or different, represents an electron withdrawing group, X ₁₁ and Y
₁₁ may be linked to form a ring.

R ₄₁ and R ₄₂ may be the same or different and include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and a sulfo group. Represents a group.

R ₄₃ and R ₄₄ may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group or a sulfonyl group, and R ₄₃ and R ₄₄ are linked to form a ring. You may.

The above X ₁₁ , Y ₁₁ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ may have a sulfo group or a carboxyl group as a substituent.

L ₁₁ , L ₁₂ and L ₁₃ each represent methine. k is
Represents 0 or 1.

[0028]

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In the general formula (III), Ar ₁ and Ar ₂ may be the same or different and represent a substituted or unsubstituted aryl group or a substituted heterocyclic group.

[0030]

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In the general formula (IV), R ₅₁ , R ₅₄ , R ₅₅ and R ₅₈
May be the same or different from each other, and include a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group,
Represents an aryloxy group, a carbamoyl group, an amino group, and a substituted amino group.

R ₅₂ , R ₅₃ , R ₅₆ and R ₅₇ may be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, an amino group, a sulfo group or a carboxyl group.

[0033]

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In the general formula (V), L ₂₁ and L ₂₂ represent a substituted or unsubstituted methine group or a nitrogen atom, and m represents 0, 1, 2 or 3.

Z ₃ is a pyrazolone nucleus, a hydroxypyridone nucleus, a barbituric acid nucleus, a thiobarbituric acid nucleus, a dimedone nucleus, an indan-1,3-dione nucleus, a rhodanine nucleus, a thiohydantoin nucleus, and oxazolidin-4-one-2. -Thion nucleus, homophthalimide nucleus, pyrimidine-2,4-dione nucleus, 1,2,3,4-
Represents a group of nonmetallic atoms necessary to form a tetrahydroquinoline-2,4-dione nucleus.

Y ₃ is an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a pyridine nucleus, a quinoline nucleus, a benzimidazole nucleus,
Non-metal atoms necessary for forming a naphthoimidazole nucleus, an imidazoquinoxaline nucleus, an indolenine nucleus, an isoxazole nucleus, a benzoisoxazole nucleus, a naphthoisoxazole nucleus and an acridine nucleus, and Z ₃ and Y ₃ are further substituents May be provided.

[0037]

Embedded image

In the general formula (VI), R ₃₁ and R ₃₂ may be the same or different and represent a substituted or unsubstituted alkyl group.

L ₃₁ , L ₃₂ and L ₃₃ may be the same or different from each other and represent a substituted or unsubstituted methine group;
m ₁ represents 0, ₁ , 2 or 3.

Adjacent L _{31 to} L ₃₃ may form a 4-, 5- or 6-membered ring.

Z ₄ and Z ₅ may be the same or different from each other, and represent a group of non-metallic atoms necessary for forming a substituted or unsubstituted heterocyclic ring, and k ₁ and k ₂ are each 0 or 1
It is.

[0042] X ^- represents an anion. p represents 1 or 2, and p is 1 when the compound forms an inner salt.

As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, or a state in which the dye is used as a polymer mordant may be used.

The non-photosensitive layer on the photosensitive layer side with respect to the support includes a so-called undercoat layer, an antihalation layer, a protective layer (a layer farther from the support than the photosensitive layer), and a photosensitive layer and a protective layer. When there are a plurality of photosensitive layers, there is an intermediate layer between them.

The coloring density (optical density for preventing irradiation) of these non-photosensitive layers is preferably 0.01 to 1.0, and particularly preferably 0.0 to 1.0, as the absorbance at the exposure wavelength.
3 to 0.5 is preferred. When a plurality of non-photosensitive layers are colored, this is the total value.

The color density of all the layers on the photosensitive layer side with respect to the support is preferably 0.05 to 1.0, more preferably 0.1 to 1.0, as the absorbance at the exposure wavelength. It is as follows.

The coloring density can be determined, for example, by preparing a light-sensitive material sample containing a colorant in the target layer under the same conditions as the light-sensitive material, measuring the optical density (absorbance) at the exposure wavelength, and coloring the layer. It can be determined as a value obtained by subtracting the optical density (absorbance) of a light-sensitive material sample containing no agent.
Absorbance can be easily measured by well-known spectrophotometer methods.

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. (For these, see EHImmergut "Polymer Han
dbook "VI187-231, Intersciense Pub. New York
1966 and JP-A-50-39528 and 50-471.
96, 50-68881, 51-133526, 64-538, 63-174698, Japanese Patent Application No. 1-24
0965, JP-A-1-240965 and JP-A-2-18484
4, JP-A-48-89870 and JP-A-48-93672).

The second layer of the undercoat layer is formed by independently using the same polymers as those described in the first layer. If necessary, a crosslinking agent, inorganic particles,
Surfactants, thickeners, dyes, preservatives and the like may be added.

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.

The point is that the drying temperature in the single-layer method and the multi-layer method is from 50 ° C. to 150 ° C.

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, the required adhesiveness may be obtained only by the surface treatment, in which case it is not necessary to perform the undercoating.

The glow treatment is 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. Nos. 3,462,335, 3,475,307, 3,761,299, 4,072,769, British Patent 891,469, 997,093, etc. be able to.

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%. When the partial pressure of water vapor becomes small, it becomes 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 adhesion is improved in a short time, which is effective. The preheating temperature is preferably from 50 ° C. to Tg (glass transition temperature), more preferably from 60 ° C. to Tg, and even more preferably from 70 ° C. to Tg. Preheating at a high temperature exceeding Tg deteriorates the adhesiveness.

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. Discharge treatment intensity is 0.01KV · A · min / m ² -5KV · A
Min / m ² is preferred, more preferably 0.15 KV · A
The desired adhesive performance can be obtained at / m ^{2 to 1} KV · A · min / m ² .

The corona treatment is the most well-known method, and any of the methods 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 object, 0.001KV
・ A ・ min / m ² 〜5KV ・ A ・ min / m ² , preferably 0.01KV ・
A · min / m ² １1 KV · A · min / m ² is appropriate. 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, 365 nm
High-pressure mercury lamp whose main wavelength is
-10,000 (mJ / cm ² ), more preferably 50-2
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 (m
J / cm ² ), more preferably 200 to 1500 (mJ / cm 2
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 . It is more effective to set the distance between the tip of the internal flame of the burner and the support to 4 cm or less. 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.

For the intermediate layer and the protective layer in the present invention, a polymer compound or a polymer which is usually used as a binder is arbitrarily used, and a colorless transparent or translucent polymer is generally used.

A natural or semi-synthetic polymer (eg, gelatin, gum arabic, hydroxyethyl cellulose, cellulose ester, casein, starch) can be used, or the following synthetic polymers can be used.

Examples of synthetic polymers include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethyl methacrylate, polyvinyl chloride, polymethacrylic acid, styrene / maleic anhydride copolymer, styrene /
Includes acrylonitrile copolymer, styrene / butadiene copolymer, polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyester, polyurethane, phenoxy resin, polyvinylidene chloride, polyepoxide, polycarbonate, polyvinyl acetate, and polyamide. Hydrophobic polymers are preferred over hydrophilic polymers. Therefore, styrene / acrylonitrile copolymer, styrene / butadiene copolymer, polyvinyl acetal, polyester, polyurethane, cellulose acetate butyrate, polyacrylic acid, polymethyl methacrylate, polyvinyl chloride and polyurethane are preferred, and styrene / butadiene copolymer and polyvinyl acetal are more preferred. .

The binder is used after being dissolved or emulsified in a solvent (water or organic solvent) of the coating solution for the photosensitive layer or the non-photosensitive layer. When emulsifying the binder in the coating solution, the emulsion of the binder may be mixed with the coating solution.

The amount of the binder used in the layer containing the dye is preferably adjusted so that the amount of the dye applied is 0.01 to 60% by weight of the binder. The dye is
Preferably it is 0.05 to 40% by weight of the binder, most preferably 0.1 to 20% by weight.

The support for the photothermographic material is preferably a plastic film. Examples of the plastic used for the support include polyalkyl methacrylate (eg, polymethyl methacrylate), polyester (eg, polyethylene terephthalate: PET), polyvinyl acetal, polyamide (eg, nylon), and cellulose ester (eg, cellulose nitrate). , Cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate).

The support may be coated with a polymer. Examples of the polymer include polyvinylidene chloride, an acrylic acid-based polymer (eg, polyacrylonitrile, methyl acrylate), a polymer of unsaturated dicarboxylic acid (eg, itaconic acid, acrylic acid), carboxymethylcellulose, and polyacrylamide. Copolymers may be used. Instead of coating with a polymer, an undercoat layer containing a polymer may be provided.

The photothermographic material of the present invention is preferably of a monosheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material).

The photothermographic material is photosensitive silver halide,
It preferably contains an organic silver salt, a reducing agent and a binder, and has a photosensitive layer containing a photosensitive silver halide (a catalytically active amount of a photocatalyst) and a reducing agent, and a non-photosensitive layer. The photosensitive layer further comprises a binder (generally a synthetic polymer),
Contains an organic silver salt (reducible silver source). Further, it is preferable to include a hydrazine compound (a super-high contrast agent) and a color tone adjuster (which controls the color tone of silver). A plurality of photosensitive layers may be provided. For example, a high-sensitivity photosensitive layer and a low-sensitivity photosensitive layer can be provided on a photothermographic material for the purpose of adjusting the gradation. The order of arrangement of the high-sensitivity photosensitive layer and the low-sensitivity photosensitive layer may be such that the low-sensitivity photosensitive layer is disposed below (the support side) or the high-sensitivity photosensitive layer is disposed below.

As the silver halide, any of silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The particle size is preferably 0.01 μm or more and 0.08 μm or less in average sphere equivalent diameter, more preferably 0.01 μm or more and 0.05 μm or less.
m or less.

[0075] The addition amount of the silver halide, when expressed by the coating amount per photographic material 1 m ^2, is preferably 0.03~0.6g / m ^2, at 0.05 to 0.4 g / m ² More preferably, it is most preferably 0.1 to 0.4 g / m ² .

The silver halide is prepared as a silver halide emulsion by reacting silver nitrate with a soluble halide salt. However, it may be prepared by reacting silver soap with halogen ions and converting the soap portion of silver soap into halogen. Further, halogen ions may be added during the formation of the silver soap. In the present invention, the former silver halide emulsion is preferably a method prepared by reacting silver nitrate with a soluble halide salt.

In the present invention, the silver halide is preferably spectrally sensitized. Spectral sensitizing dyes are described in JP-A-60-140335, JP-A-63-159841,
Nos. 3-231437, 63-259651 and 63
-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 47.
No. 41966, No. 4751175, No. 48335096
No. is described in each specification.

As the reducing agent, phenidone, hydroquinones, catechol and hindered phenol are preferred. As for the reducing agent, US Pat. Nos. 3,770,448, 3,773,512, 3,593,863 and 44,606.
No. 81, and Research Disclosure Magazine Nos. 17029 and 2996
No. 3 describes it.

Examples of the reducing agent include aminohydroxycycloalkenones (eg, 2-hydroxy-piperidino-
2-cyclohexenone), N-hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea), hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone), phosphoramidophenols, phosphates Amidoanilines,
Polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone, 2,
5-dihydroxy-phenylmethylsulfone), sulfohydroxamic acids (eg, benzenesulfohydroxamic acid), sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline), 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone), tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydroquinoxaline), amidooxines, azines (eg, aryl aryl carboxylate) Hydrazides) and ascorbic acid, polyhydroxybenzene and hydroxylamine, reductone, hydrazine, hydroxamic acids, azines and sulfonamidephenols, α-cyanophenylacetic acid derivatives, bis-β- Naphtho , A combination of a 1,3-dihydroxybenzene derivative, 5-pyrazolones, sulfonamidophenols, and 2-phenylindane-1,3-
Dione, chroman, 1,4-dihydropyridines (eg,
2,6-dimethoxy-3,5-dicarbethoxy-1,
4-dihydropyridine), bisphenols (eg, bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy -3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-
Butyl-6-methyl) phenol), UV-sensitive ascorbic acid derivatives and 3-pyrazolidones.

An ester of an aminoreductone (eg, piperidinohexose reductone monoacetate) which functions as a precursor of the reducing agent may be used as the reducing agent.

Particularly preferred reducing agents are hindered phenols.

[0082] The addition amount of the reducing agent is preferably from 0.01~5.0g / m ^2, and more preferably 0.1 to 3.0 g / m ^2.

The photosensitive layer and the non-photosensitive layer have already been described for the intermediate layer and the protective layer, but preferably contain a binder. Generally, a colorless transparent or translucent polymer is used as the binder. Natural or semi-synthetic polymers (eg, gelatin, gum arabic, hydroxyethylcellulose, cellulose ester, casein, starch) can also be used, but considering heat resistance,
Synthetic polymers are preferred over natural or semi-synthetic polymers. However, even if a cellulose ester (eg, acetate, cellulose acetate butyrate) is a semi-synthetic polymer, it has relatively high heat resistance and is preferably used as a binder for a photothermographic material.

Examples of synthetic polymers include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethyl methacrylate, polyvinyl chloride, polymethacrylic acid, styrene / maleic anhydride copolymer, styrene /
Includes acrylonitrile copolymer, styrene / butadiene copolymer, polyvinyl acetal (eg, polyvinyl formal, polyvinyl butyral), polyester, polyurethane, phenoxy resin, polyvinylidene chloride, polyepoxide, polycarbonate, polyvinyl acetate, and polyamide.

The binder is used after being dissolved or emulsified in a solvent (water or organic solvent) of the coating solution for the photosensitive layer or the non-photosensitive layer. When emulsifying the binder in the coating solution, the emulsion of the binder may be mixed with the coating solution.

The amount of the binder used in the layer containing the pigment is such that the amount of the pigment is not less than 0.01% by weight and
It is preferable to adjust the coating amount so as to be not more than% by weight. Pigment is 0.05% to 40% by weight of binder
And more preferably 0.1% by weight or more and 20% by weight or more.
It is particularly preferred that the content is not more than weight%.

The photosensitive layer or the non-photosensitive layer preferably further contains an organic silver salt. Organic acids that form silver salts are
Long chain fatty acids are preferred. Fatty acids have 10 carbon atoms.
-30, more preferably 15-25. An organic silver salt complex may be used. The ligand of the complex has a total stability constant of 4.0 to 1 for silver ions.
It is preferable to have it in the range of 0.0. Regarding organic silver salts, please refer to Research Discl.
osure) magazines 17029 and 29963.

Examples of organic silver salts include silver salts of fatty acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid), carboxyalkylthioureas (eg, 1- (3-carboxypropyl) ) Thiourea, 1-
Silver salt of (3-carboxypropyl) -3,3-dimethylthiourea), silver complex of polymer reaction product of aldehyde (eg, formaldehyde, acetaldehyde, butyraldehyde) and hydroxy-substituted aromatic carboxylic acid, aromatic carboxylic acid Silver salts of (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), thioenes (e.g., 3- (2-carboxyethyl)-
Silver salt or silver complex of 4-hydroxymethyl-4-thiazoline-2-thioene, 3-carboxymethyl-4-thiazoline-2-thioene), nitrogen acid (eg, imidazole, pyrazole, urazole, 1,2,4- Thiazole, 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole, benzotriazole)
Or silver complexes of saccharin, silver salts of 5-chlorosalicylaldoxime and silver salts of mercaptides. Silver behenate is most preferred. Organic silver salts
Is preferably used in 0.05 g / m ² or more 3 g / m ² or less as the amount of silver, and more preferably used in 0.3 g / m ² or more 2 g / m ² or less.

The photosensitive layer or the non-photosensitive layer preferably further contains a super-high contrast agent. When a photothermographic material is used in the field of photographic printing, it is important to reproduce a continuous tone image or a line image using halftone dots. By using a super-high contrast agent, the reproducibility of halftone images and line images can be improved. As the super-high contrast agent, a hydrazine compound, a quaternary ammonium compound or an acrylonitrile compound (described in US Pat. No. 5,545,515) is used. Hydrazine compounds are particularly preferred ultrahigh contrast agents.

The hydrazine compound is hydrazine (H ₂ N
—NH ₂ ) and a compound in which at least one of the hydrogen atoms has been substituted. As the substituent, an aliphatic group, an aromatic group or a heterocyclic group is directly bonded to a hydrazine nitrogen atom, or an aliphatic group, an aromatic group or a heterocyclic group is bonded to a hydrazine nitrogen atom via a linking group. . Examples of linking groups include -CO
-, - CS -, - SO 2 -, - POR- (R is an aliphatic group, an aromatic group or a heterocyclic group), - CNH- and combinations thereof.

The hydrazine compound is described in US Pat.
Nos. 464738, 5496695, 5551241
Nos. 1 and 5,536,622, JP-B-6-77
Nos. 138 and 6-93082, JP-A-6-23049
7, No. 6-289520, No. 6-313951,
No. 7-5610, No. 7-77783, No. 7-104
No. 426 is described in each publication.

The hydrazine compound can be dissolved in an appropriate organic solvent and added to the photosensitive layer coating solution. Examples of organic solvents include alcohols (eg, methanol, ethanol, propanol, fluorinated alcohols), ketones (eg, acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, and methyl cellosolve. In addition, hydrazine compound is oily (auxiliary)
A solution dissolved in a solvent may be emulsified in a coating solution. Examples of oily (auxiliary) solvents include dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, diethyl phthalate, ethyl acetate and cyclohexanone. Further, a solid dispersion of a hydrazine compound may be added to the coating solution. The dispersion of the hydrazine compound is
It can be carried out using a known dispersing machine such as a ball mill, a colloid mill, a Menton-Gauling, a microfluidizer and an ultrasonic dispersing machine.

The addition amount of the super-high contrast agent is preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, and from 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. Mole, more preferably 2 × 10 ^{−5 to} 5 × 10 ⁻³ mole.

In addition to the super-high contrast agent, a high-contrast accelerator may be used. Examples of the high contrast accelerator include amine compounds (described in US Pat. No. 5,545,505), hydroxamic acids (described in US Pat. No. 5,545,507), acrylonitriles (described in US Pat. No. 5,545,507), and hydrazine compounds (described in US Pat. No. 5,545,507). 5558983).

The photosensitive layer or the non-photosensitive layer preferably further contains a color tone adjuster. About color tone adjuster,
It is described in Research Disclosure Magazine No. 17029.

Examples of color tone adjusting agents include imides (eg, phthalimide), cyclic imides (eg, succinimide), pyrazolin-5-ones (eg, 3-phenyl-2-pyrazolin-5-one, -Phenylurazole), quinazolinones (eg, quinazoline, 2,4-thiazolidinedione), naphthalimides (eg, N-hydroxy-1,
8-naphthalimide), a cobalt complex (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole), N- (aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide), blocked pyrazoles (eg, N, N′hexamethylene-1-carbamoyl-3,5-dimethylpyrazole), isothiuronium derivatives (eg, 1,8- ( A combination of 3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and a photobleach (eg, 2- (tribromomethylsulfonyl) benzothiazole), a merocyanine dye (eg, 3-
Ethyl-5-((3-ethyl-2-benzothiazolinylidene) -1-methylethylidene) -2-thio-2,4-oxazolidinedione (oxaz
olazinedione)), phthalazinone compounds and metal salts thereof (eg, phthalazinone, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, 2,3-dihydro-1,4- Phthalazinedione, 8-methylphthalazinone), a combination of a phthalazinone compound with a sulfinic acid derivative (eg, sodium benzenesulfinate), a combination of a phthalazinone compound with a sulfonic acid derivative (eg, sodium p-toluenesulfonate), Phthalazine and its derivatives (eg, phthalazine, 6-isopropylphthalazine, 6-
Methylphthalazine), a combination of phthalazines and phthalic acid, phthalazine or a phthalazine adduct and a dicarboxylic acid (preferably o-phenylene acid) or an anhydride thereof (eg, maleic anhydride, phthalic acid, 2,3-naphthalene) Dicarboxylic acid, phthalic anhydride, 4-methylphthalic acid, 4-nitrophthalic acid, tetrachlorophthalic anhydride), quinazolinediones, benzoxazine, naloxazine derivatives, benzoxazine-
2,4-diones (eg, 1,3-benzoxazine-
2,4-dione), pyrimidines, asymmetric triazines (eg, 2,4-dihydroxypyrimidine), tetraazapentalene derivatives (eg, 3,6-dimerocapto-
1,4-diphenyl-1H, 4H-2,3a, 5,6a
-Tetraazapentalene). Phthalazine and its derivatives are particularly preferred.

The color adjusting agent is preferably contained on the surface of the image forming layer in an amount of 0.1 to 50 mol% per mol of silver.
More preferably, the content is 0.5 to 20 mol%.

An antifoggant may be added to the photosensitive layer or the non-photosensitive layer (preferably the photosensitive layer). As an antifoggant, a mercury compound (described in US Pat. No. 3,589,903) is more preferable than a non-mercury compound (US Pat.
No. 946, No. 4546075, No. 44452885,
Nos. 4,756,999 and 5,028,523, UK Patent Application Nos. 92221383.4 and 93001777.7.
Nos. 9311790.1 and JP-A-59-1790.1.
57234) is preferably used.

Particularly preferred antifoggants are polyhalogen compounds, particularly preferred are halogens (F,
Cl, Br, I) is a heterocyclic compound having a substituted methyl group.

Polyhalogen compounds are described in, for example,
-119624, 50-120328, 51-121332, 54-5802
No. 2, 56-70543, 56-99335, 59-90842, 6
No. 1-129642, No. 62-129845, JP-A-6-208191, No. 7-5
Nos. 621, 7-2781, 8-15809, U.S. Pat.
And compounds disclosed in JP-A Nos. 5369000/5464737. Particularly, a polyhalogen compound represented by the following general formula (1) is preferable.

[0101]

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In the general formula (1), Q represents an alkyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ each represent a halogen atom. Z represents a hydrogen atom or an electron-withdrawing group. Y is -C (= O)-, -SO- or -SO
Represents _2- . n represents 0 or 1.

The general formula (1) will be described in detail. Q
Represents an alkyl group, an aryl group or a heterocyclic group. Q
The aryl group represented by may be monocyclic or condensed, is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and is more preferably a phenyl group. , A naphthyl group, and more preferably a phenyl group.

The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of N, O and S atoms, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring.

The heterocyclic group is preferably a 5- or 6-membered unsaturated heterocyclic group which may have a condensed ring, and more preferably a 5- or 6-membered aromatic group which may have a condensed ring. Group heterocyclic group. More preferably, it is a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and particularly preferably, a 5- or 6-membered aromatic heterocyclic group containing 1 to 4 nitrogen atoms and optionally having a condensed ring. It is.

Specific examples of the heterocyclic ring in the heterocyclic group include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, Indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, benzoselenazole, india Renin, tetrazaindene and the like. Preferably as a heterocycle, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine,
Triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole,
Oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline , Quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, tetrazaindene, more preferably imidazole, pyridine, pyrimidine, pyrazine,
Pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole and benzthiazole, particularly preferably pyridine, thiadiazole, quinoline and benzthiazole.

The aryl group and the hetero ring represented by Q may have a substituent other than-(Y) _n -CZ (X ₁ ) (X ₂ ). Examples of the substituent include an alkyl group (Preferably 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms
2, particularly preferably having 1 to 8 carbon atoms, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, Cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 carbon atoms.
-8, for example, vinyl, allyl, 2-butenyl, 3
-Pentenyl and the like. ), Alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl,
Pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenyl,
p-Methylphenyl, naphthyl and the like. ),
An amino group (preferably having 0 to 20 carbon atoms, more preferably having 0 to 10 carbon atoms, particularly preferably having 0 to 6 carbon atoms,
For example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like can be mentioned. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy, etc.), and an aryloxy group ( Preferably 6 to 2 carbon atoms
It has 0, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl,
Benzoyl, formyl, pivaloyl and the like can be mentioned. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
-20, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms.
0, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino), and an alkoxycarbonylamino group. (Preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 to 20, more preferably 0 to 16, and particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl,
Dimethylsulfamoyl, phenylsulfamoyl and the like can be mentioned. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl). An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methylthio, ethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenylthio, etc.), and a sulfonyl group (preferably having 1 carbon atom). ~ 20, more preferably 1 carbon atom
To 16, particularly preferably 1 to 12 carbon atoms, for example, mesyl, tosyl, phenylsulfonyl and the like. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoramide and phenylphosphoramide. ), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) )). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent is preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, heterocyclic group, and more preferably Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, nitro group, heterocyclic group,
More preferred are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a halogen atom, a cyano group, a nitro group, and a heterocyclic group, and particularly preferred. An alkyl group, an aryl group, and a halogen atom.

The alkyl group represented by Q may be linear, branched or cyclic, and preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms. Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tertiary octyl group.

The alkyl group represented by Q is-(Y) _n -C
It may have a substituent other than Z (X ₁ ) (X ₂ ),
Examples of the substituent include those similar to the substituents that can be used when Q is a heterocyclic group or an aryl group. As the substituent, preferably, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, a ureido group, and phosphorus Acid amide group, hydroxy group, halogen atom, heterocyclic group, more preferably aryl group, alkoxy group, aryloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, ureido group, A phosphoric amide group, a halogen atom, more preferably an aryl group, an alkoxy group,
An aryloxy group, an acylamino group, a sulfonylamino group, a ureido group, and a phosphoric amide group.

These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

Y is -C (= O)-, -SO- or -S
O ₂ —, preferably —C (＝ O) —, —SO ₂ —
And more preferably —SO ₂ —.

N represents 0 or 1, and is preferably 1.

X ₁ and X _{2 each} have a halogen atom;
_The halogen atoms represented by ₁ and X ₂ may be the same or different from each other and are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom. And a bromine atom, particularly preferably a bromine atom.

Z represents a hydrogen atom or an electron-withdrawing group;
The electron-withdrawing group represented by Z is preferably a substituent having a σp value of 0.01 or more, more preferably a substituent of 0.1 or more. Regarding Hammett's substituent constant,
Journal of Medicinal Chemistry, 1973, Vo
l.16, No.11, 1207-1216 etc. can be referred to.
Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06) and a chlorine atom (σp value: 0.2
3), bromine atom (σp value: 0.23), iodine atom (σ
p value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), an aliphatic aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), an alkynyl group (eg, C≡
CH (σp value: 0.23)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.44)), carbamoyl group (σp value: 0.3
6), a sulfamoyl group (σp value: 0.57), and the like.

Z is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl. Group, carbamoyl group, sulfamoyl group,
Particularly preferred is a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

Among the compounds represented by the general formula (1), a compound represented by the following general formula (1-a) is preferable.

[0118]

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In the formula, Q has the same meaning as in formula (1), and the preferred range is also the same. The substituents that Q can take are the same as the substituents that Q can take in general formula (1). X ₁ , X ₂ , Y, and Z have the same meanings as those in formula (1), respectively, and their preferred ranges are also the same.

Among the compounds represented by the general formula (1), more preferred are the compounds represented by the general formula (1-b).

[0121]

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In the formula, Q has the same meaning as in formula (1), and the preferred range is also the same. The substituents that Q can take are the same as the substituents that Q can take in general formula (1). X ₁ , X ₂ and Z have the same meanings as those in formula (1), and the preferred ranges are also the same.

Specific examples of the compound represented by the formula (1) are shown below, but the invention is not limited thereto.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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When Y = —SO— or —SO ₂ —, the compound represented by the general formula (1) according to the present invention is (1) an aryl or heterocyclic mercaptan and an α-halogenoacetic acid derivative or α-halogenoacetic acid derivative. Α from halogenoacetic acid ester derivatives
-An arylthio or heterocyclic thioacetic acid derivative is synthesized, and (2) the corresponding acetic acid derivative can be synthesized by oxidation and bromination. Also, JP-A 2-3-3
No. 04059, etc., a method for oxidizing and brominating a corresponding sulfide derivative, and a method disclosed in JP-A-2-264.
A method of halogenating the corresponding sulfone derivative as described in 754 or the like can also be used.

Conversion to an α-arylthio or heterocyclic thioacetic acid derivative can be carried out by reacting the corresponding mercaptan compound with an α-halogenoacetic acid derivative or the like under basic conditions.

Oxidation and halogenation of α-arylthio or heterocyclic thioacetic acid derivatives are described, for example, in US Pat. No. 3,874,946 and EP-A-60598, etc. Oxidation and halogenation can be performed simultaneously by adding and reacting an α-arylthio or heterocyclic thioacetic acid derivative or a salt thereof to a neutral aqueous solution. Also, α
-It can also be synthesized by converting an arylthio or heterocyclic thioacetic acid derivative into a sulfoxide or a sulfonylacetic acid derivative in advance using an oxidizing agent such as hydrogen peroxide and then halogenating the derivative.

As a method for synthesizing alkyl, aryl or heterocyclic mercaptans used as raw materials, for example, alkyl and aryl mercaptans are described in New Experimental Chemistry Course (Maruzen) 14-III, Chapter 8, 8-1, ORGANIC FUNCTIO
NAL GROUP PREPARATIONS (Sandler, Karo, ACADEMIC
PRESS New York and Rondon) I-Chapt.18 or
THE CHEMISTRY OF FUNCTIONAL GROUPS (Patai, JO
NE WILLY & SONS) "The Chemistry of the thiol g
roup "Chapt4. Various methods are known, and for heterocyclic mercaptans, Comprehensiv
e Heterocyclic Chemistry, Pergamaon Press, 1984
And Heterocyclic Compounds, John Wiley and Sons, V
ol. 1-9, 1950-1967 and the like.

When Y = —C (＝ O) —, the compound can be synthesized by (1) synthesizing acetophenone or a carbonyl-substituted heterocyclic derivative, and (2) α-halogenating the carbonyl compound. For α-halogenation of a carbonyl compound, a method described in New Experimental Chemistry Course (Maruzen) 14-I, Chapter 2, etc. can be used.

When n = 0, the compound can be synthesized by methylation of a heterocyclic compound having a toluene, xylene or methyl group. As the halogenation method, a method described in Chapter 2 of New Experimental Chemistry Course (Maruzen) 14-I, etc. can be used in the same manner as described above.

The polyhalogen compound of the present invention may be added by a method of preparing a solid fine particle dispersion using a dispersant in order to obtain fine particles having a small particle size and no aggregation.
The method of dispersing the polyhalogen compound of the present invention in solid fine particles can be carried out by a known fine means (for example,
Ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill) can be used for mechanical dispersion.

When the polyhalogen compound of the present invention is formed into solid fine particles using a dispersant, for example, polyacrylic acid, a copolymer of acrylic acid, a maleic acid copolymer, or a maleic acid monoester copolymer may be used. , Anionic polymers such as acryloylmethylpropanesulfonic acid copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethylcellulose, anionic polymers such as alginic acid and pectic acid, and JP-A-52-92716.
Surfactants described in Japanese Patent Application Publication No. WO 88/04794, compounds described in Japanese Patent Application No. 7-350753, known anionic, nonionic and cationic surfactants, and other polyvinyl alcohols and polyvinyl pyrrolidone Known polymers such as 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 polyhalogen compound of the present invention or the polyhalogen compound of the present invention in the form of a wet cake before dispersion and then sent to a dispersing machine as a slurry. A heat treatment or a treatment with a solvent may be performed in a state of being mixed with the compound of the present invention in advance to obtain a powder or a wet cake. The pH may be controlled by a suitable pH adjuster before, during or after dispersion.

In addition to the mechanical dispersion, the particles may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersing aid. 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 (for example, in a jelly state using gelatin) with a hydrophilic colloid. You can also do.
Further, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

The addition position of the polyhalogen compound of the present invention is not limited, and it is added to the image forming layer (photosensitive layer), the protective layer, and other layers. It is particularly preferable that the same layer as the layer containing the organic silver salt or the same layer as the layer containing the silver halide is used.

The polyhalogen compounds of the present invention may be used alone or in combination of two or more.

The polyhalogen compound of the present invention is preferably contained in an amount of 1 × 10 ^{-6 to} 0.5 mol per mol of silver on the surface having the image forming layer, and preferably 1 × 10 ^-5 to 1 × 10 ^-1. More preferably, it is contained in moles.

The photothermographic material further comprises a surfactant,
Antioxidants, stabilizers, plasticizers, ultraviolet absorbers or coating aids may be added. Various additives are added to either the photosensitive layer or the non-photosensitive layer.

The photothermographic material forms an image by heating after image exposure. By this heat development, a black silver image is formed. The image exposure is preferably performed using a laser. The heating temperature for thermal development is 80 to 250.
C., more preferably 100 to 200C. The heating time is generally between 1 second and 2 minutes.

As a method of thermal development, a plate heater method is preferable. The heat development method using the plate heater method is a method described in Japanese Patent Application No. 9-229684, in which a visible image is obtained by bringing the heat-developable photosensitive material on which a latent image is formed into contact with heating means in a heat development section. A heat developing device, wherein the heating means comprises a plate heater, and a plurality of pressing rollers are disposed to face each other along one surface of the plate heater, and the pressing roller is disposed between the pressing roller and the plate heater. A heat developing apparatus for performing heat development by passing a heat-developable photosensitive material.

As a thermal developing section of a thermal developing apparatus which employs such a heating method, for example, a form as shown in FIG. 1 can be mentioned.

As shown in FIG. 1, the heat developing section 18 heats the exposed photothermographic material conveyed in the direction of the arrow in the drawing to perform heat development to make the latent image a visible image. The present invention is characterized in that the heat developing section 18 includes a plate heater 120 and a plurality of pressing rollers 122 arranged to face the plate heater 120.

The plate heater 120 is a plate-like heating member in which a heating element such as a nichrome wire is laid and accommodated in a plane, and is maintained at the developing temperature of the photothermographic material. Further, it is preferable that a fluororesin is coated on a surface of the plate heater 120 for the purpose of reducing frictional resistance or imparting abrasion resistance, or a sheet made of a fluororesin is attached.

Further, the heat development photosensitive material evaporates volatile components by heating during the heat development, and accordingly, the heat development photosensitive material floats up from the plate heater 120, and the contact between the heat development photosensitive material and the plate heater 120 becomes uneven. May be. Therefore, it is preferable to form minute irregularities on the surface of the plate heater 120 in order to release the vapor.

Further, in order to compensate for a temperature decrease due to heat radiation at both ends of the plate heater 120, it is preferable to provide a temperature gradient so that the temperature at both ends is higher than the other portions.

The holding roller 122 is a plate heater.
0, or at a predetermined pitch over the entire length of the plate heater 120 in the transport direction with an interval equal to or less than the thickness of the photothermographic material.
The plate 22 and the plate heater 120 form a path for transporting the photothermographic material. By arranging the photothermographic material conveying path at an interval equal to or less than the thickness of the photothermographic material, buckling of the photothermographic material can be prevented. A supply roller pair 126 for supplying the photothermographic material to the thermal developing section 18 in the direction indicated by an arrow in FIG. A pair 128 is provided.

Further, it is preferable to dispose a heat retaining cover 125 for keeping heat as shown in the drawing, on the opposite side of the pressing roller 122 from the plate heater 120.

When the photothermographic material is transported,
When the leading end of the photothermographic material strikes the pressing roller 122, the photothermographic material stops momentarily. At this time, if the pressing rollers 122 are separated at a constant pitch, the same portion of the photothermographic material stops for each pressing roller 122 and that portion is pressed by the plate heater 120 for a long time. As a result, in the photothermographic material, streak-like development unevenness extending in the width direction occurs. Therefore, it is preferable to make the pitch of each pressing roller 122 non-uniform.

Further, as shown in FIG.
Alternatively, a configuration may be adopted in which a driving roller 130 having the envelope surface of each pressing roller 122 as a peripheral surface is installed in contact with each pressing roller 122, and each pressing roller 122 is rotated by the rotation of the driving roller 130.

In the above description, the plate heater 120 also includes a plate member made of a heat conductor and a heat source disposed on the side of the plate member opposite to the heating surface of the photothermographic material.

[0156]

The present invention will be specifically described below with reference to examples. Example 1 << Preparation of PET support >> Terephthalic acid and ethylene glycol
And PET having an intrinsic viscosity IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) using a conventional method. This is pelletized and dried at 130 ° C. for 4 hours.
After melting at ℃, it was extruded from a T-die and quenched to prepare an unstretched film having a thickness of 175 μm after heat fixing.

This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then transversely stretched 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 lateral direction at the same temperature. Then, after slitting the chuck portion of the tenter, knurling was performed on both ends and wound at 4 kg / cm ² to obtain a roll having a thickness of 175 μm.

<< Surface 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, it was found that 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.

<< Preparation of Undercoat Support >> (Preparation of Undercoat Coating Solution A) Polystyrene fine particles (average particle size: 0.2 μm) in 200 ml of polyester copolymer water dispersion Pesresin A-515GB (30 wt%, manufactured by Takamatsu Oil & Fats Co., Ltd.) ) 1 g, the following surfactant (A) (1 wt%) 20 ml, and the pigment CIpiment shown below
A required amount of the optical density shown in Table 1 was added to a 20 wt% dispersion of Blue60, and distilled water was added to make 1000 ml to give an undercoating coating liquid A.

[0160]

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(Preparation of Undercoating Coating Solution B) 200 ml of an aqueous dispersion of a styrene-butadiene copolymer (styrene / butadiene / itaconic acid = 47/50/3 (weight ratio), concentration 30 wt%) in 680 ml of distilled water,
Add 0.1 g of polystyrene fine particles (average particle size 2.5 μm),
Further, distilled water was added to make 1000 ml, thereby obtaining an undercoating coating solution B.

(Preparation of Undercoating Coating Solution C) Inert Gelatin 1
0 g was dissolved in 500 ml of distilled water, and 40 g of an aqueous dispersion (40 wt%) of tin oxide-antimony oxide composite fine particles described in JP-A-61-20033 was added thereto, and distilled water was added thereto. Ten
Undercoating solution C was made up to 00 ml.

(Preparation of Undercoat Support) After the above-mentioned corona discharge treatment, the undercoat coating solution A was applied using a bar coater so that the wet coating amount was 5 ml / m ² , and dried at 180 ° C. for 5 minutes. The dry film thickness was about 0.3 μm. Then this back
After applying the corona discharge treatment to the (back side), the undercoat coating liquid
B is applied with a bar coater so that the wet coating amount is 5 ml / m ² , and the dried film thickness is about 0.3 μm, dried at 180 ° C. for 5 minutes, and further, the undercoat coating solution C is wet-coated with the bar coater. An undercoating support was prepared by applying the solution in an amount of 3 ml / m ² and a dry film thickness of about 0.03 μm and drying at 180 ° C. for 5 minutes.

(Preparation of Emulsion Dispersion of Dye) 8 g of the dye compound (a) shown below and 16 g of polymethyl methacrylate
And dissolved in 250 ml of methyl acetate to prepare a dispersion mother liquor,
1 g of the following surfactant (B) was added, and the temperature was maintained at 40 ° C.
wt% gelatin solution and mixed with a homogenizer (HF93, manufactured by SMT Co., Ltd.) according to a conventional method.
The mixture was stirred at a high speed of 000 rpm for 5 minutes to prepare an emulsified dispersion.

This emulsified dispersion was dispersed in an evaporator at 6
After slowly evaporating the ethyl acetate solvent at 5 ° C. for 2 hours to remove the ethyl acetate, distilled water was replenished to a final weight of 400 g to prepare a 2 wt% emulsified dispersion (a) of the dye compound.

[0166]

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Similarly, 2 wt% emulsified dispersions (b), (c) and (d) of each dye were prepared using the dye compounds (b), (c) and (d).

[0168]

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[0169]

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[0170]

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<< Preparation of 20 wt% Dispersion of Pigment >>
To 64 g of Blue 60 and 6.4 g of Demol N manufactured by Kao Corporation, 250 g of water was added and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm were 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 25 hours to obtain a pigment dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.

<< Preparation of Organic Acid Silver Dispersion >> 43.8 g of behenic acid (product name: Edenor C22-85R) manufactured by Henkel, 730 ml of distilled water,
While stirring tert-butanol (60 ml) at 79 ° C., 1N-NaOH aqueous solution (117 ml) was added over 55 minutes and reacted for 240 minutes. Then
112.5 ml of an aqueous solution of 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and cooled to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content of the filtrate had a conductivity of 30 μS / cm.
And washed with water. The solid content thus obtained is handled as a wet cake without drying, and
To a wet cake equivalent to 100 g, 7.4 g of polyvinyl alcohol (trade name: PVA-205) and water were added to make a total amount of 385 g, and the mixture was preliminarily dispersed with a homomixer.

Next, the pre-dispersed undiluted solution is dispersed in a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using G10Z interaction chamber).
The pressure was adjusted to 1750 kg / cm ² and the mixture was treated three times to obtain a silver behenate dispersion B. The silver behenate particles contained in the silver behenate dispersion thus obtained were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%. For particle size measurement, use MasterSizerX manufactured by Malvern Instruments Ltd.
I went in. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to a desired dispersion temperature.

<< Preparation of 25 wt% Dispersion of Reducing Agent >> 1,1-bis
176 g of water was added to 80 g of (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 70 g of a 20 wt% aqueous solution of modified polyvinyl alcohol Poval MP203 manufactured by Kuraray Co., Ltd. did. 700 g of zirconia beads having an average diameter of 0.5 mm was prepared, placed in a vessel together with the slurry, and dispersed with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 5 hours to obtain a reducing agent dispersion.
The reducing agent particles contained in the thus obtained reducing agent dispersion had an average particle size of 0.8 μm.

<< Preparation of 20 wt% Dispersion of Mercapto Compound >> 32 g of a 20 wt% aqueous solution of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole 64 g and modified polyvinyl alcohol poval MP203 manufactured by Kuraray Co., Ltd. 224 g of water was added thereto and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm were prepared, placed in a vessel together with the slurry, and dispersed with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 10 hours to obtain a mercapto dispersion. The mercapto compound particles contained in the thus obtained dispersion of the mercapto compound had an average particle size of 0.67 μm.

<< Preparation of 30 wt% dispersion of organic polyhalogen compound >> 48 g of tribromomethylphenylsulfone and 3-tribromomethylsulfonyl-4-phenyl-5-tridecyl-
224 g of water was added to 48 g of 1,2,4-triazole and 48 g of a 20 wt% aqueous solution of modified polyvinyl alcohol poval MP203 manufactured by Kuraray Co., Ltd., and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm are 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 an organic polyhalogen compound dispersion. Was. The polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had an average particle size of 0.74 μm.

<< Preparation of methanol solution of phthalazine compound >> 26 g of 6-isopropylphthalazine was dissolved in 100 ml of methanol and used.

<< Preparation of Silver Halide Grain 1 >> Distilled water 1421c
Add 1wt% potassium bromide solution 6.7cc to c and add 1N nitric acid
While stirring the liquid containing 8.2 cc and 21.8 g of phthalated gelatin in a titanium-coated stainless steel reaction vessel, the liquid temperature was maintained at 35 ° C, and a solution obtained by adding distilled water to 37.04 g of silver nitrate to 159 cc and diluting the solution a1 with odor was added. A solution b1 prepared by diluting 32.6 g of potassium iodide to a volume of 200 cc with distilled water was prepared, and the entire amount of the solution a1 was added over 1 minute at a constant flow rate while maintaining the pAg at 8.1 by the control double jet method. (Solution b1 was added by the controlled double jet method.) Then, 30 cc of a 3.5 wt% aqueous hydrogen peroxide solution was added, and 3 wt% of benzimidazole was further added.
33.6 cc of a 10% aqueous solution was added. Then, the solution a1 was again diluted with distilled water to 317.5 cc, and the solution a1 was dissolved with dipotassium hexachloride iridate to a final concentration of 1 × 10 ^-4 mol per mol of silver with respect to the solution b1. 400cc twice the amount of solution b1
Using the solution b2 diluted with distilled water until, again by the controlled double jet method, while maintaining pAg at 8.1,
The solution a2 was added at a constant flow rate over 10 minutes. (Solution b
2 added by controlled double jet method)
50 cc of a 0.5 wt% methanol solution of -mercapto-5-methylbenzimidazole was added, the pAg was further raised to 7.5 with silver nitrate, the pH was adjusted to 3.8 with 1N sulfuric acid, and stirring was stopped.
A precipitation / desalting / washing step was performed, 3.5 g of deionized gelatin was added, and 1N sodium hydroxide was added to adjust to pH 6.0 and pAg 8.2 to prepare a silver halide dispersion.

The grains in the completed silver halide emulsion are pure silver bromide grains having an average sphere equivalent diameter of 0.031 μm and a variation coefficient of the equivalent sphere diameter of 11%. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The {100} plane ratio of these particles was determined to be 85% using the Kubelka-Munk method.

The above emulsion was heated to 50 ° C. while stirring, and N,
5 ml of a 0.5 wt% methanol solution of N'-dihydroxy-N '', N ''-diethylmelamine and 5 cc of a 3.5 wt% methanol solution of phenoxyethanol were added, and after 1 minute, sodium benzenethiosulfonate was added to 1 mol of silver. 3 × 10 ^-5 mol was added. After a further 2 minutes, a solid dispersion of the spectral sensitizing dye (1) (aqueous gelatin solution) was added at 5 × 10 ^-3 mol per mol of silver, and after a further 2 minutes, a tellurium sensitizer (2) was added at 5 mol / mol of silver. × 10 ^-5 mol was added and the mixture was aged for 50 minutes. Immediately before the completion of the ripening, the temperature was lowered by adding 1 × 10 ⁻³ mol of 2-mercapto-5-methylbenzimidazole per 1 mol of silver, and the chemical sensitization was terminated to prepare silver halide grains 1.

<< Preparation of Silver Halide Grains 2 >> After dissolving 22 g of phthalated gelatin and 30 mg of potassium bromide in 700 ml of water, adjusting the pH to 5.0 at a temperature of 35 ° C., containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate An aqueous solution containing 159 ml of an aqueous solution and a 92: 8 molar ratio of potassium bromide and potassium iodide was pA
While maintaining the g at 7.7, it was added over 10 minutes by the control double jet method. Then, 1 ml in 476 ml and 1 liter of an aqueous solution containing 55.4 g of silver nitrate and 2 g of ammonium nitrate
X 10 ^-5 mol of an aqueous solution containing dipotassium hexachloride iridate and 1 mol of potassium bromide was added over 30 minutes by a control double jet method while keeping the pAg at 7.7, and then 4-hydroxy-6-methyl-1 was added. , 3,3a, 7-Tetrazaindene (1 g) was added, and the pH was further lowered to cause coagulation and sedimentation for desalination.
Then, 0.1 g of phenoxyethanol was added, pH 5.9, pAg
Adjusted to 8.2 silver iodobromide grains (iodine content core 8 mol%, average 2
Mol%, average size 0.05 μm, projected area variation coefficient 8%, {10
Preparation of (cubic particles having a {0} face ratio of 88%) was completed.

The silver halide grains thus obtained were heated to 60 ° C., and 85 μmol of sodium thiosulfate and 2,
1.1 × 10 ⁻⁵ mol of 3,4,5,6-pentafluorophenyldiphenylphosphine selenide, 1.5 × 10 ⁻⁵ mol of tellurium sensitizer (2), 3.5 × 10 ⁻⁸ mol of chloroauric acid, thiocyanate Acid 2.7 × 1
After ^0--4 mol was added and the mixture was aged for 120 minutes and rapidly cooled to 40 ° C, 1 × 10 ⁻⁴ mol of the spectral sensitizing dye (1) and 5 × 10 ⁻⁴ mol of 2-
Add mercapto-5-methylbenzimidazole and add 30 ° C
Then, silver halide emulsion 2 was obtained.

<< Preparation of Coating Solution for Emulsion Layer >> (Coating Solution for Emulsion Layer) 103 g of the organic acid silver dispersion obtained above and 5 g of a 20 wt% aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.)
Into a mixture maintained at 40 ° C., and the above 25 wt% reducing agent dispersion 23.
2 g, an aqueous dispersion of the pigment CI Pigment Blue 60 in an amount of 20 wt%, an amount required to obtain the optical density shown in Table 1, an organic polyhalogen compound 15 wt% dispersion, and a mercapto compound 20 wt% dispersion 4 g were added. Then, after adding 106 g of 40 wt% of ultrafiltration purified SBR latex kept at 40 ° C. and sufficiently stirring, 6 ml of a methanol solution of a phthalazine compound was added to obtain a liquid containing an organic silver salt. In addition, 4 g of silver halide grains 1
And 5 g of silver halide particles 2 were mixed well in advance and mixed with a solution containing an organic acid silver with a static mixer immediately before coating to prepare a coating solution for the emulsion layer, and the silver amount applied to the coating die as it was 1.
The solution was sent to 4 g / m ² .

The viscosity of the obtained emulsion layer coating solution was measured by Tokyo Keiki Co., Ltd.
Measured with a B-type viscometer, 85 [mPa] at 40 ° C (No. 1 rotor)
[S]. 25 ° C using an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd.
The viscosity of the coating solution at the shear rate of 0.1, 1, 10, 100, 1000
1500/220/70/40/20 [mPa ・
s].

The SBR latex purified by ultrafiltration was obtained as follows.

The following SBR latex diluted 10-fold with distilled water was used for ultrafiltration and purification, FS03-FC-FUY0
The product was diluted and purified using 3A1 (Daisen Membrane System Co., Ltd.) until the ionic conductivity became 1.5 mS / cm. At this time, the latex concentration was 40% by weight.

(SBR latex: -St (68) -Bu (29) -AA (3)-
Latex) Average particle size 0.1 μm, equilibrium water content 0.6 wt% under 25 ° C 60% RH condition, concentration 45 wt%, ionic conductivity 4.2 mS / cm (Ion conductivity is measured by Toa Denpa Kogyo Co., Ltd. Latex stock solution (40%) was measured at 25 ° C using CM-30S meter), pH 8.2

<< Preparation of Emulsion Surface Intermediate Layer Coating Solution >> (Intermediate Layer Coating Solution) Polyvinyl alcohol PVA-205 (Kuraray)
772 g of a 10 wt% aqueous solution of methyl methacrylate / styrene / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 59
/ 9/26/5/1) Aerosol OT in 27.5wt% latex liquid 226g
2 ml of a 5 wt% aqueous solution (manufactured by American Cyanamid Co., Ltd.), 4 g of benzyl alcohol, 1 g of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 10 mg of benzoisothiazolinone, and the above pigment CI Pigment 20wt% of Blue 60
The aqueous dispersion was added in an amount necessary to obtain the optical density shown in Table 1 to prepare a coating liquid for the intermediate layer, and the solution was fed to a coating die at a concentration of 5 ml / m ² . The viscosity of the coating solution was measured using a B-type viscometer at 40 ° C (No.
(1 rotor) and 21 [mPa · s].

<< Preparation of Emulsion Surface Protective Layer First Layer Coating Solution >> (Protective Layer First Layer Coating Solution) 80 g of inert gelatin was dissolved in water, 138 ml of a 10 wt% methanol solution of phthalic acid, and 28 ml of 1N sulfuric acid. Aerosol OT (American Cyanamid)
5 ml of a 5 wt% aqueous solution of 1 g of phenoxyethanol and 20 wt% of the above-mentioned pigment CI Pigment Blue 60 were added in an amount required to obtain the optical density described in Table 1, and water was added so that the total amount became 1000 g. It was used as a first layer coating solution and sent to a coating die so as to have a concentration of 10 ml / m ² . The viscosity of the coating solution is
It was 17 [mPa · s] at 40 ° C. (No. 1 rotor) with a B-type viscometer.

<< Preparation of Coating Solution for Emulsion Surface Protective Layer Second Layer >> (Protective Layer Second Layer Coating Solution) Inert gelatin (100 g) was dissolved in water, and N-perfluorooctylsulfonyl-N-propylalanine potassium salt was 5 wt%. 20 ml of solution, aerosol
16 ml of a 5 wt% solution of OT (manufactured by American Cyanamid Co.), polymethyl methacrylate fine particles (average particle size 4.0 μm) 25
g, 44 ml of 1N sulfuric acid, water to 10 mg of benzoisothiazolinone to a total amount of 1555 g, and 445 ml of an aqueous solution containing 4 wt% chrome alum and 0.67 wt% phthalic acid with a static mixer immediately before application. The mixture was used as a coating liquid for the second layer of the protective layer, and was fed to a coating die so as to have a concentration of 10 ml / m ² . The viscosity of the coating solution was 9 [mPa · s] with a B-type viscometer at 40 ° C. (No. 1 rotor).

<< Preparation of Back Surface Coating Solution >> (Preparation of Solid Precursor Dispersion of Base Precursor) 64 g of base precursor compound (3), diphenyl sulfone compound
(4) 14 g and 10 g of Kao Corporation's surfactant Demol N were mixed with 224 ml of distilled water, and the mixture was sand-milled (1/4 Gallon
The beads were dispersed using a sand grinder mill (manufactured by Amimex Co., Ltd.) to obtain a base precursor solid fine particle dispersion having an average particle diameter of 0.2 μm.

(Preparation of Dye Solid Fine Particle Dispersion) 9.6 g of the following cyanine dye compound (5) and 5.8 g of sodium p-alkylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixture was sand-milled (1/4 Gallon sand grinder mill). ,
Beads were dispersed using an Amimex Corporation to obtain a dye solid fine particle dispersion having an average particle diameter of 0.2 μm.

(Preparation of anti-halation layer coating solution) Gelatin 17 g, polyacrylamide 9.6 g, solid fine particle dispersion of the above base precursor 70 g, solid fine particle dispersion of the above dye 56 g, polymethyl methacrylate fine particles (average particle size 6.5 μm) 1.5 g, 2.2 g of sodium polyethylene sulfonate, 0.2 g of the coloring dye compound (6) and 844 ml of H ₂ O were mixed to prepare a coating solution for an antihalation layer.

(Preparation of Coating Solution for Protective Layer) The container was kept warm at 40 ° C., and 50 g of gelatin and sodium polystyrene sulfonate were prepared.
0.2 g, N, N'-ethylenebis (vinylsulfoneacetamide) 2.4 g, t-octylphenoxyethoxyethaneethanesulfonate 1 g, benzoisothiazolinone 30 mg,
32 mg of C ₈ F ₁₇ SO ₃ K, C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -S
64 mg of O ₃ Na and 950 ml of H ₂ O were mixed to prepare a coating solution for a protective layer.

[0195]

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<< Preparation of Photothermographic Material >> On the undercoated support, the coating amount of the antihalation layer was 0.04 g / m ² , and the coating amount of the protective layer was gelatin. simultaneous multilayer coated to a 1 g / m ^2, dried and after creating the antihalation back layer, the emulsion layer from the undercoat surface opposite the surface and the back surface, the intermediate layer, a protective layer first
The layers and the protective layer were coated simultaneously in the order of the second layer by a slide bead coating method to prepare Samples 2 and 3 of the photothermographic material. The emulsion surface was applied without winding after coating the back surface.

The coating was performed at a speed of 160 m / min, the distance between the tip of the coating die and the support was set to 0.18 mm, and the pressure in the decompression chamber was set 392 Pa lower than the atmospheric pressure. In the subsequent chilling zone, the dry bulb temperature is 18 ° C and the wet bulb temperature is 12 ° C
After blowing the wind at an average wind speed of 7 m / sec for 30 seconds to cool the coating solution,
A dry air having a dry-bulb temperature of 30 ° C. and a wet-bulb temperature of 18 ° C. was blown out of the hole at an air velocity of 20 m / sec for 200 seconds to volatilize the solvent in the coating solution.

Similarly, Sample No. 1 was prepared in the same manner as Sample Nos. 2 and 3, except that the undercoating coating solution (A) and the dispersion of the pigment CI Pigment Blue 60 in the intermediate layer and the first layer of the protective layer were removed. did. Instead of the undercoating coating solution A and the dispersion of the pigment CIigment Blue 60 in the intermediate layer and the first layer of the protective layer, emulsions (a), (b), (c) and (d) of the above dyes were used. Sample Nos. 4 to 11 were prepared in the same manner as Sample Nos. 2 and 3.

The optical density in Table 1 is 660 for the film sample containing no appropriate amount of the coloring dye or pigment in the corresponding layer, without adding any coloring dye or pigment.
The increase in optical density at nm is represented by absorbance. The absorbance was measured by using a spectrophotometer U-3500 manufactured by Hitachi and placing the sample at the entrance of an integrating sphere having an inner diameter of 200 mm.

(Developing fog increase value) Samples Nos. 1 to 11 of the prepared photothermographic materials were prepared by using the method shown in FIG. 1 described in Japanese Patent Application No. 9-229684.
The heat development was performed at 123 ° C. for 20 seconds in a dark place using a heat developing machine equipped with a plate heater type heat developing unit as shown in (1) above, and the fog increase value of the developed sample relative to the undeveloped sample was measured.

Measurement of Sharpness (MTF) After exposure using a semiconductor laser of 660 nm, heat development was carried out at 123 ° C. for 20 seconds with the above-mentioned heat developing machine, and MTF was measured. 30
μm × 500μm aperture, spatial frequency is 2.5
The evaluation was performed at an optical density of 1.0 using an MTF value of cycles / mm.

Measurement of Dmin (Minimum Concentration) The back surface of the prepared sample was removed as it was, and it was measured in a visual mode using a Macbeth densitometer TD-904, and the value of the base alone was subtracted to obtain a Dmin value. Table 1 shows the results.

[0203]

[Table 1]

It can be seen that the sample of the present invention has little Dmin and development fog and is excellent in sharpness. That is, when compared with the comparative sample, the sample of the present invention can reduce the Dmin and the development fog to obtain a good sharpness. In addition, since a pigment is used for the photosensitive layer, discoloration during storage is prevented.

[0205]

According to the present invention, Dmi is excellent in sharpness.
A photothermographic material having low n, good transparency and low fog can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of a thermal developing section of a thermal developing apparatus used in the present invention.

FIG. 2 is a schematic configuration diagram illustrating another example of a heat developing unit of the heat developing device used in the present invention.

[Explanation of symbols]

 Thermal developing unit 18 Plate heater 120 Holding roller 122 Drive roller 130

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[Procedure amendment]

[Submission date] May 27, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

[0037]

Embedded image

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

<< Preparation of Photothermographic Material >> On the undercoated support, the coating amount of the antihalation layer was 0.04 g / m ² , and the coating amount of the protective layer was gelatin. simultaneous multilayer coated to a 1 g / m ^2, dried and after creating the antihalation back layer, the emulsion layer from the undercoat surface opposite the surface and the back surface, the intermediate layer, a protective layer first
The layer and the protective layer were coated simultaneously in the order of the second layer by the slide bead coating method to prepare Sample No. 2 of the photothermographic material. The emulsion surface was applied without winding after coating the back surface.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

A sample No. 1 was prepared in the same manner as the sample No. 2 except that the undercoating coating solution (A) and the dispersion of the pigment CI Pigment Blue 60 in the intermediate layer and the first layer of the protective layer were removed. Instead of the undercoating coating solution A and the dispersion of the pigment CIigment Blue 60 in the intermediate layer and the first layer of the protective layer,
Sample N using emulsions (a), (b), (c) and (d) of the above dyes
Sample Nos. 3 to 10 were prepared in the same manner as in o.2.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0200

[Correction method] Change

[Correction contents]

(Development fog increase value) Samples Nos. 1 to 10 of the prepared photothermographic materials were prepared as shown in FIG. 1 described in Japanese Patent Application No. 9-229684.
The heat development was performed at 123 ° C. for 20 seconds in a dark place using a heat developing machine equipped with a plate heater type heat developing unit as shown in (1) above, and the fog increase value of the developed sample relative to the undeveloped sample was measured.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0203

[Correction method] Change

[Correction contents]

[0203]

[Table 1]

Claims (4)

[Claims] 1. A photosensitive layer comprising a pigment for preventing irradiation, and at least one non-photosensitive layer on the same side of the support as the photosensitive layer contains a dye for preventing irradiation. Photothermographic material. 2. The photothermographic material according to claim 1, wherein the photosensitive layer contains a polyhalogen compound. 3. The photothermographic material according to claim 1, wherein the layer on the photosensitive layer side with respect to the support has a total optical density for preventing irradiation of 0.05 to 1.0. 4. The photothermographic material according to claim 1, wherein the photosensitive layer contains an organic silver salt, a reducing agent, and a photosensitive silver halide.