JP2001235831A - Heat developable material, image forming method, heat developing method and sheet material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable material having uniformity of the film surface after coating and drying, having low fog and high sensitivity, excellent in preservability before and after processing, excellent also in conveyability in a heat processing machine and less liable to surface scuffing and stain, a heat developing method which ensures superior conveyability in a heat processing machine and suppresses stain and an image forming method which reduces unevenness in exposure and to provide a sheet material having improved conveyability, particularly a sheet material recording a printed image or a medical image and a sheet material having conveyability improved without adversely affecting its photographic performance and recording an image with light and heat or heat rays without passing through wet processing. SOLUTION: In the heat developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on the base, a specified fluorine-containing surfactant is contained in at least one layer or a compound of formula 1 is contained. Each of the sheet materials contains a compound of formula 2 in a layer on the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat developing material for forming an image by heat development, a heat developing method and an image forming method.
Excellent heat storage stability of photographic performance, improved heat resistance of the film surface of the heat-developable material, and less adhesion of dirt on the film surface.
In addition, the present invention relates to a heat development method that does not cause contamination in a processor that performs a heat development process, and further relates to an image forming method in which exposure unevenness is suppressed.

The present invention also relates to a sheet material having improved transportability, and more particularly, to a sheet material on which an image forming material is superimposed,
Or it relates to a superimposed sheet material. Further, the present invention relates to a material which does not adversely affect the photographic performance of the image forming material and has improved transportability until image formation.

[0003]

2. Description of the Related Art In recent years, in the fields of medical care and printing, there has been a strong demand for a heat-developable material which does not generate waste liquid due to wet processing of an image forming material in view of environmental protection and workability. There is a need for technology relating to photothermographic materials for photographic technology applications that can form high resolution, clear black images by thermal development.
Since these photosensitive materials are usually developed at a temperature of 80 ° C. or higher, they are called heat developing materials. The heat-developable material includes a photosensitive layer, a protective layer for the photosensitive layer, an anti-irradiation layer (AH layer) for the photosensitive layer, a backing layer (BC layer) opposite to the photosensitive layer with respect to the support, and a protective layer for the backing. Consists of layers. These layers need to be uniformly coated and dried so as not to cause unevenness.In handling, it is difficult to make scratches, stains, or when transporting on rollers in the manufacturing process of cutting and packaging. In order to prevent the occurrence of static electricity and prevent slippage during roller transport during processing by an automatic developing machine, a fluorine-based surfactant is often used in the uppermost protective layer. A fluorine-based surfactant (fluorine-based material) can be applied uniformly when used in a coating solution, but cissing unevenness is likely to occur in the finished product after drying due to the hydrophobic nature of the fluorocarbon group. In addition, the fluorine is oriented on the surface of the coating film surface, and is easily charged with static electricity. Therefore, fluorine surfactants are
This problem has been solved by introducing a part of a fluorine-containing aliphatic group and a part of a hydrophilic group such as a sulfonic acid group, a carboxyl group or an alkylene oxide group in a certain ratio. For example, JP-A-51-80219 and JP-A-61-20
No. 944, No. 62-135826, No. 63-3064
No. 37, JP-A Nos. 1-224245, 7-173225
No. 7-233268, No. 8-101480, No. 8-137045, No. 9-5925, No. 9-281
No. 636 discloses a technique using a fluorine-based surfactant by molecular design in which the ratio of a hydrophilic group to a hydrophobic group is changed. JP-A-7-233268 and JP-A-11-5
No. 05624 discloses a technique using an ion pair compound of a bisammonium cation of a polyalkylene oxide and a fluorine-containing aliphatic anion.

Contamination of the heat-developable material is caused by adhesion of dust mixed in from the surroundings other than the heat-developable material, and a substance that seeps out of the film surface of the heat-developable material onto the heat drum, or repeatedly adheres to the pressing roller. There are various routes, such as adhesion to the heat developing material and accumulation of dirt, and there are those that adhere with static electricity and those that adhere with adhesive force or cohesive force. The surface of the heat-developable material is added with a matting agent to the outermost layer in order to prevent fingerprints and to improve the vacuum suction property of feeding when transporting, in order to suppress adhesion between films at high humidity. Irregularities are formed. There is also dirt or the like in which minute dust is caught and accumulated on the uneven surface. Therefore, a method for preventing adhesion of dust focusing on static electricity is not sufficient, and it is necessary to prevent adhesion of dirt on a heat drum or a pressing roller. The heat drum and the pressing roller need to supply heat for heat development to the heat development material promptly and need to be a material having high thermal conductivity, but on the other hand, do not damage the heat development material, Characteristics such as uniform transmission of heat, difficulty in attaching dirt, and no failure in transport are required. These problems need to be improved by a combination of a heat development material and a heat development method, but they are still insufficient and are problems.

[0005] Non-uniformity and dirt on the film surface change the refraction of light and cause exposure unevenness. In recent image processing, laser exposure has become mainstream in order to cope with digital signals. The laser exposure has a defect called reflection unevenness or interference unevenness due to complicated characteristics of incident light and reflected light due to its coherent characteristics. In order to solve this drawback, an AH layer or a BC layer containing a dye or a dye for absorbing reflected light has been arranged, but the dye or the dye remains turbid after development, so that the residual color problem is caused. Get out. Therefore, as solutions other than pigments and dyes, designs that consider the thickness of each layer of the heat-developable material, the refractive index of the material to be used, and the wavelength of incident light due to exposure are being studied, but the matching is still insufficient, and the Met.

Examples of the sheet material include a packaging material for wrapping a product, a printing material for displaying tangible and intangible product information, a radiation recording material for displaying a medical image, and a material for overlaying a printing material and a radiation recording material. is there. Packaging materials include
In order to display the product information at the same time as the protection of the product, a process is added so that the ink or toner is easily superimposed. In order to increase the productivity by mechanically performing this processing, physicochemical properties of the surface suitable for the transport process are required. Printing materials and radiation recording materials also need to be transported mechanically and productively in processing equipment to print or record radiation or to make these materials. Suitable surface properties are required. Various physical properties are required for the surface physical properties suitable for transport according to the type of mechanism of the transport processing apparatus. For transport, a method in which the material to be mechanically transported by a roller or belt and the material to be transported come into contact with each other, and transport in a non-contact manner by controlling gas such as airflow and sound waves and using magnetic or electrostatic repulsion There is a way to do it. The method of contact and transport is widely used because the mechanism is simple and materials are easily available. However, regardless of whether the sheet material is in the form of a roll or a cut material cut to a certain length, cost-accuracy and accuracy are contradictory, while error-free conveyance accuracy is required. Not. The transportability factors include, for example, the accumulation and release characteristics of static electricity generated by rubbing of the same or different kinds of substances, the coefficient of friction relating to slipperiness, the scratch resistance to make the material less susceptible to mechanical damage, and the like. When the material is conveyed by contacting with a cup like a bowl and the inside of the cup is decompressed, the reduced material is difficult to stick and the cut material sticks to each other. Further, the cutting of the sheet is affected by the cutting blade, and if the blade is easily rusted, it is difficult to cut the sheet immediately, the cut cross section becomes uneven, the sheets are hardly loosened, and a conveyance failure easily occurs. In addition, a photothermal material that forms an image with light and heat is sensitive to pressure, so a mechanism that minimizes pressure during transport is desirable.However, to reduce transport failures and transport errors, a certain pressure It is required to have characteristics that can withstand the above. Improvement of materials to meet these demands is not enough and is a problem.

[0007] In recent years, photothermal materials as one field of sheet materials have been rapidly spreading in the fields of medical treatment and printing because no waste liquid is produced due to wet processing from the viewpoint of environmental protection and workability. The photothermal material includes a photosensitive layer, a protective layer for the photosensitive layer, an anti-irradiation layer (AH layer) for the photosensitive layer, a backing layer (BC layer) on the opposite side of the photosensitive layer with respect to the support, and a protective layer for the backing. Or a method in which a photosensitive layer is applied to both sides of a support. The simultaneous upper layer method of simultaneously applying each layer as a coating method is frequently used from the viewpoint of productivity, but the step of undercoating the support is often separated from the step of applying the photosensitive layer. The surface properties up to the undercoating and the surface properties in the case of coating up to the photosensitive layer and the photosensitive protective layer are different in design depending on whether there is a material to be finally applied or to be overlaid. In order to adjust the slipperiness during antistatic processing and roller transport when processing with an automatic developing machine, which is less likely to scratch during development processing, less dirt, and less likely to generate static electricity when transported by cutting or packaging. A fluorine-based surfactant is often used for the uppermost protective layer. The fluorine-based surfactant material has an effect of facilitating uniform application when used in a coating solution, but cissing unevenness is likely to occur in the finished product after drying due to the hydrophobic nature of the fluorocarbon group. In addition, the portion having a fluorine atom is oriented on the surface of the coating film surface, and is easily charged with static electricity. Then, the fluorine-based surfactant has solved this problem by introducing a fluorine-containing aliphatic group portion and a hydrophilic group such as a sulfonic acid group, a carboxyl group or an alkylene oxide group in a certain ratio. For example, JP-A-51-802196
No. 1, No. 61-20944, No. 62-135826
No. 63-306437, JP-A-1-24245
Nos. 7-173225, 7-233268, 8-101480, 8-137,045, 9-5
Nos. 925 and 9-281636 disclose a technique using a fluorine-based surfactant by molecular design in which the ratio of a hydrophilic group to a hydrophobic group is changed. JP-A-7-23326
No. 8 and JP-A-11-505624 disclose a technique using an ion pair compound of a bisammonium ion of a polyalkylene oxide and a fluorine-containing aliphatic anion. However, it cannot be sufficiently improved yet, and is a problem.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a coating film having a uniform and good surface after coating and drying, low fog, and high sensitivity. Another object of the present invention is to provide a heat-developable material which is excellent in preservability before and after processing, is hardly scratched on the surface, is hardly stained, is less likely to be charged with static electricity, and is free from dust. Another object of the present invention is to provide a developing method which does not cause stains in a processor for performing a heat development process.

A second object of the present invention is to provide a coating film having good uniformity after coating and drying, low fog, high sensitivity and excellent preservability before and after the treatment, less scratches on the surface, less contamination and less static electricity. Another object of the present invention is to provide a heat-developable material which is less likely to be stained and has no adhesion of dust. Another object of the present invention is to provide a developing method which does not cause stains in a processor for performing a heat development process. Another object of the present invention is to provide an image forming method in which uneven exposure is suppressed.

A third object of the present invention is to provide a sheet material having improved transportability, and more particularly, to supply a sheet material for recording a printed image or a medical image. It is to provide a sheet material for recording an image with light or heat without an improved wet treatment without adversely affecting the performance.

[0011]

Means for Solving the Problems The first object of the present invention is the following 1 to 8, the second object is 9 to 16 below, and the third object is the structure of the present invention described in 17 to 21 below. Achieved.

1. A heat-developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on a support, wherein at least one layer of the heat-developable material contains a fluorine-based surfactant; A surfactant having an average molecular weight of 1,800 or more and less than 15,000, and a group (i): an acrylate having a fluorine-containing aliphatic group (hereinafter abbreviated as an Rf group) or a methacrylate having an Rf group; Group (ii): a copolymer with poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate, and all monomer units of the acrylate having the Rf group or the methacrylate having the Rf group are the same as those of the copolymer. 2 to 24% by weight, and the Rf group has 1 to 26 carbon atoms, and the Rf group has a fluorine content of 18 to 83% by weight of the Rf group. Heat development material characterized by having an atomic. However, the fluorine-based surfactant, N- butyl perfluorooctane sulfonamide ethyl acrylate _{(C 8 F 17 SO 2 N} (C 4 H 9) CH 2
CH ₂ OOCCH = CH ₂₎ and (methyl - hepta - oxyethylene) acrylate _{(CH 3 (OC 2 H 4} ) 7 OOCC
H = CH ₂ ) and an average molecular weight of 15,000.

2. In a heat-developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on a support, at least one fluorine-containing surfactant is contained in at least one layer of the heat-developable material. A first type of the fluorine-based surfactant is a group (i): an acrylate having a fluorine-containing aliphatic group (Rf group) or a methacrylate having an Rf group; and a group (ii): poly (oxyalkylene) A copolymer with acrylate or poly (oxyalkylene) methacrylate, wherein all the monomer units of the acrylate having the Rf group or the methacrylate having the Rf group are 2 to 86% by mass of the copolymer, and the Rf group Has 1 to 26 carbon atoms, and the Rf group has 18 to 83% by mass or more of a fluorine atom of the Rf group,
The second type of the fluorine-based surfactant is an anionic surfactant having a fluorine-containing aliphatic group (Rf group), and the Rf
A heat-developable material, wherein the group has a fluorine atom in an amount of 18 to 83% by mass of the Rf group.

3. In a heat-developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on a support, at least one fluorine-containing surfactant is contained in at least one layer of the heat-developable material. A first type of the fluorine-based surfactant is a group (i): an acrylate having a fluorine-containing aliphatic group (Rf group) or a methacrylate having an Rf group; and a group (ii): poly (oxyalkylene) Group (iii): All monomers of acrylate having glycidyl group or methacrylate having glycidyl group, and all monomers of acrylate having Rf group or methacrylate having Rf group. A glycidyl group-containing acrylate or glycidyl The total monomer units of methacrylate are 2 to 70% by weight of the copolymer, the Rf group has 1 to 26 carbon atoms and 18 to 83% by weight of the Rf group has fluorine atoms, The second type of fluorine-based surfactant is an anionic surfactant having a fluorine-containing aliphatic group (Rf group), and the Rf group has 18 to 83% by mass of fluorine atoms of the Rf group. Heat developing material.

4. 4. The heat-developable material as described in 1, 2, or 3, wherein lithium ion is contained in an amount of 1/1000 to 100 times the total amount of the fluorine-based surfactant.

5. 5. The heat of 1, 2, 3 or 4, wherein the acrylate having a fluorine-containing aliphatic group (Rf group) or the methacrylate having an Rf group has an alkylsulfonamide group having 1 to 4 carbon atoms in the molecule. Developing material.

6. The heat-developable material has a photosensitive layer and a protective layer, and contains latex as a binder in the photosensitive layer and the protective layer.
6. The heat-developable material as described in 1, 2, 3, 4 or 5, wherein the temperature is ℃.

[7] 7. The heat-developable material according to 6, wherein the latex contains a halogen atom in a molecule.

8. A metal oxide is applied to silicone rubber as a heat developing roller disposed opposite to a heat drum of a developing machine for processing a heat developing material described in 1, 2, 3, 4, 5, 6, or 7. A heat development method characterized in that processing is carried out using a containing pressing roller.

9. A heat-developable material containing a compound represented by the following general formula (1).

[0021]

Embedded image

In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a substituent to Q, and at least one of the substituents represents a group having a fluorine atom.
A ₁ and A ₂ each represent an anionic group, L ₁ and L ₂ each represent a divalent linking group, and Z represents a group having an alkylene oxide unit.

10. 10. The heat-developable material according to item 9, which contains an organic silver salt. 11. 11. The heat-developable material as described in 9 or 10, further comprising an organic silver salt and silver halide grains.

12. 9. containing an organic silver salt, silver halide particles, a reducing agent and a latex,
The heat-developable material according to 0 or 11.

13. Characterized in that latex is contained in an amount of 65 to 100% by mass based on the total mass of the binder;
13. The heat-developable material according to any one of the above items 12.

14. 14. The heat-developable material as described in 12 or 13, wherein the latex has a halogen atom.

(15) An image forming method, wherein a laser beam having a plurality of spectra is converged and bound on the heat-developable material according to any one of (1) to (14), and is exposed imagewise.

After exposing the heat-developable material according to any one of 16.9 to 14 to a laser beam, the temperature is 80 to 180.
A heat development method, wherein heat development is performed by a drum or a roller heated to ° C.

17. A sheet material comprising a layer on a support containing a compound represented by the following general formula (2).

[0030]

Embedded image

In the formula, P represents a phosphorus atom, Rt ₁ and Rt ₂ each represent an aliphatic group, an aromatic group or a heterocyclic group which may have a substituent, and A ₁ and A ₂ each represent an anionic group. Represent
R _{1 to} R ₆ each represent a hydrogen atom or a substituent of a hydrogen atom, L ₁ and L ₂ each represent a divalent linking group, and Z ₁ represents a group having an alkylene oxide unit.

18. 18. The sheet material according to 17, wherein the sheet material contains silver halide grains.

19. 19. The sheet material according to 17 or 18, further comprising an organic silver salt.

20. The sheet material according to 17, 18, or 19, wherein the total number of repeating alkylene oxide units of the group having an alkylene oxide unit represented by Z ₁ in formula (2) is 4 to 40.

21. Rt ₁ and Rt ₂ are each an aliphatic group containing a fluorine atom;
21. The sheet material according to 9 or 20.

Hereinafter, the present invention will be described in detail. << Explanation of the inventions of claims 1 to 8 and 9 to 16 of the present invention >> The heat-developable material is provided with at least one photosensitive layer on a support, and below the photosensitive layer (between the support and the photosensitive layer). A
A protective layer is provided on the H layer and the photosensitive layer. Further, a backing layer (BC layer) is provided on the side opposite to the side having the photosensitive layer with respect to the support, and a protective layer is provided thereon. The photosensitive layer contains silver halide, an organic silver salt, a reducing agent, and a binder (polymer binder). AH
In the layer and the BC layer, a dye having high absorption efficiency at the photosensitive wavelength and hardly remaining color is present in the binder to prevent deterioration of sharpness and interference fringes due to irregular reflection at the interface between constituent layers of the heat-developable material. I do. As the binder such as the AH layer, the BC layer, and the protective layer, the same or different material as the photosensitive layer can be used. When a dye is used for the BC layer, the AH layer may not be provided. In some cases, a dye capable of being decolorized by heat to reduce residual color derived from dyes in the AH layer and the BC layer, and a base-generating precursor to further promote thermal decoloration can be used. The curing of the binder, irrespective of only the protective layer, the photosensitive layer, the AH layer and the BC layer, etc. by appropriately selecting an epoxy crosslinking agent, a hydrazide compound, an acid anhydride compound and a base generating precursor, photographic performance and scratch resistance,
Residual color and storage stability can be improved.

<< Description of the Inventions of Claims 1 to 8 of the Present Invention >> Group (i) used as a monomer of the first component in the fluorosurfactant (copolymer) of the present invention: Fluorine-containing aliphatic An acrylate having a group (hereinafter abbreviated as an Rf group) or a methacrylate having an Rf group will be described.

The fluorinated surfactant (copolymer) of the present invention
Group (i): a fluorine-containing aliphatic group (Rf
The acrylate having an Rf group or the methacrylate monomer having an Rf group includes an Rf group,
The other branched terminal may contain a chlorine atom or a hydrogen atom, but is preferably a linear or branched perfluoroalkyl group, or a monomer having an Rf group as a terminal of a perfluoroether group. In particular, those in which the vinyl group and the Rf group are bonded by a sulfonamide group are particularly preferable.

Preferred specific examples of the monomer of the group (i) having a fluorine-containing aliphatic group (Rf group) used as a monomer of the first component in the fluorine-containing surfactant (copolymer) of the present invention are described below. Is shown.

(I) group (1) CF_Three(CF_Two)_FourCH_TwoOOCC (CH_Three) = CH_Two (2) CF_Three(CF_Two)₆(CH_Two)_TwoOOCC (CH_Three) =
CH_Two (3) CF_Three(CF_Two)₆OCOCH = CH_Two (4) CF_Three(CF_Two)₇(CH_Two)_TwoOOCCH = CH_Two (5) CF_Three(CF_Two)₇(CH_Two)_TwoOOCC (CH_Three) =
CH_Two (6) (CF_Three)_TwoCF (CF_Two)_Five(CH_Two)_TwoOOCCH
= CH_Two (7) CF_Three(CF_Two)₇(CH_Two)_FourOOCCH = CH_Two (8) (CF_Three)_TwoCF (CF_Two)₆(CH_Two)_ThreeOOCCH
= CH_Two (9) (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH (OOCC
H_Three) OOCC (CH_Three) = CH_Two (10) (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH (OH)
CH_TwoOOCCH = CH _Two (11) CF_Three(CF_Two)₈(CH_Two)_TwoOOCCH = CH_Two (12) CF_Three(CF_Two)₈(CH_Two)_TwoOOCC (CH_Three)
= CH_Two (13) CF_Three(CF_TwoCl) CF (CF_Two)₇CONHC
OCH = CH_Two (14) CH_Two= CHCOOC_TwoH_FourOOCCF (CF_Three)
(OC_ThreeF₆)_TwoOC_FourF ₉ (15) CH_Two= CHCONHC_TwoH_FourOOCCF (C
F_Three) OC_ThreeF₆OC_FourF₉ (16) CH_Two= C (CH_Three) CONHC_TwoH_FourOOCCF
(CF_Three) OC_FourF₉ (17) CF_Three(CF_Two)₇CONH (CH_Two)_TwoOOCC
H = CH_Two (18) CF_Three(CF_Two)₈CONH (CH_Two)_TwoOOCC
(CH_Three) = CH_Two (19) CF_Three(CF_Two)₇SO_TwoN (C_ThreeH₇) (CH_Two)_Two
OOCCH = CH_Two (20) CF_Three(CF_Two)₇SO_TwoN (CH_Three) (CH_Two)_Two
OOCC (CH_Three) = CH_Two (21) CF_Three(CF_Two)₇SO_TwoN (C_TwoH_Five) (CH_Two)_Two
OOCCH = CH_Two (22) CF_Three(CF_Two)₁₁SO_TwoN (C_FourH₉) (CH_Two)
_TwoOOCCH = CH_Two (23) CF_Three(CF_Two)₇SO_TwoN (C_FourH₉) (CH_Two)_Two
OOCCH = CH_Two No. (ii) used in the fluorosurfactant of the present invention.
Group: poly (oxyalkylene) acrylate or poly
(Oxyalkylene) methacrylate
You.

The fluorinated surfactant (copolymer) of the present invention
Group (ii) as a monomer of the second component which can be copolymerized with the monomer containing an Rf group used in the above: poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate monomer; The group having 1 to 8 carbon layers may have a substituent in the alkylene portion, and the number of repeating oxyalkylene units (number of units) in the poly (oxyalkylene) group is 1 to 50.
Is preferable, and 3 to 40 are particularly preferable. The oxyalkylene group is, for example, —CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH _{2
O -, - CH (CH 3} ) CH 2 O-, or -CH (CH
₃₎ CH (CH ₃₎ a O- is preferred. The oxyalkylene units in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), or two or more oxyalkylene units different from each other are irregularly distributed. It may be a linear or branched oxypropylene unit and an oxyethylene unit, or may be a linear or branched oxypropylene unit block and an oxyethylene unit block. . The poly (oxyalkylene) group can have various linkages (eg, -C
ONHC ₆ H ₄ NHCO—, —S—, etc.). When the chain bond has three or more valences, a branched oxyalkylene unit and the like can be mentioned. The number of repetitions of the oxyalkylene unit of the poly (oxyalkylene) group is related to the solubility in water or a solvent. When the number is large, the solubility is deteriorated or the charging characteristics are disadvantageous. .

In the following, the (i) used as a monomer of the second component in the fluorine-based surfactant (copolymer) of the present invention is described.
i) Group: Preferred specific examples of poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate monomer are shown. As in the following (13) and (14), a bis structure such as diacrylate or dimethacrylate may be used.

Group (ii) (1) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₁₀ H (2) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₁₀ CH ₃ (3) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₁₀ CH ₂ CH
₃ (4) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₂₀ CH ₃ (5) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₃₀ CH ₃ (6) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₃₀ H (7) CH ₂ ＣＨCHCOOCH ₂ CH ₂ O (CH ₂ CH ₂ C
_{H 2 O) 15 H (8} ) CH 2 = CHCOOCH 2 CH 2 O (CH (CH 3)
_{CH 2 O) 15 H (9} ) CH 2 = CHCOO (CH 2 CH 2 CH 2 O) 15 H (10) CH 2 = C (CH 3) COO (CH 2 CH 2 O) 30
CH ₃ (11) CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ O (CH
₂ CH ₂ CH ₂ O) ₁₅ CH ₃ (12) CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ O (CH
(CH ₃ ) CH ₂ O) ₃₀ H (13) CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) ₂₀
COCH = CH ₂ (14) CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ O (CH
(CH ₃ ) CH ₂ O) ₂₀ CO ＝ CH ₂ (15) CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₇ CH _{3 As a} third component monomer in the fluorine-based surfactant (copolymer) of the present invention Group (iii) used: As the acrylate having a glycidyl group or the methacrylate monomer having a glycidyl group, besides glycidyl acrylate or glycidyl methacrylate, a poly (oxyalkylene) acrylate or a poly (oxyalkylene) methacrylate having a glycidyl group terminated. May be introduced.

The following (ii) are used as the third component monomer in the fluorosurfactant (copolymer) of the present invention.
i) Group: Specific examples of the acrylate having a glycidyl group or the methacrylate having a glycidyl group are shown below. The symbol Gy represents a glycidyl group.

Group (iii) (1) CH ₂ ＣＨCHCOOGy (2) CH ₂ ＣＨCHCOOCH ₂ CH ₂ OGy (3) CH ₂ ＣC (CH ₃ ) COOGy (4) CH ₂ ＣC (CH ₃ ) COOCH _{2 CH 2 OGy (5) CH} 2 = CHCOO (CH 2 CH 2 O) 20 Gy (6) CH 2 = CHCOO (CH 2 CH 2 O) 30 Gy (7) CH 2 = C (CH 3) COO (CH ₂ CH ₂ O) ₂₀ G
y (8) CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH ₂ O) ₄₀ G
y As the monomer of the fourth component or more used as a monomer in the fluorine-based surfactant (copolymer) of the present invention, a wide range of monomers can be selected as long as the effects of the present invention are not deteriorated. , Vinyl chloride,
Vinyl fluoride, vinylidene halide, styrene, α-methylstyrene, p-methylstyrene, N-methylol (meth) acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, benzyl (meta A) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, maleic anhydride, aziridinyl (meth) acrylate, (meth) acrylate having polysiloxane, N-vinylcarbazole, and the like.

The above-mentioned copolymer used in the present invention is, for example,
For example, fluoroaliphatic group-containing acrylate or fluoro
Aliphatic group-containing methacrylate and poly (oxyalkylene)
Acrylate) or poly (oxyalkylene) meth
Acrylates, such as monoacrylate or diacryle
By a free radical initiated copolymerization reaction with
Can be manufactured. Molecular weight of polyacrylate oligomer
Are the initiator concentration and activity, the monomer concentration and the polymerization reaction.
By adjusting the reaction temperature and chain transfer agents, eg
For example, by adding n-octyl mercaptan
Can be adjusted. As an example, fluoroaliphatic group-containing acrylic
Rate (Rf-R "-OCO-CH = CH _Two,here
R ″ is, for example, sulfonamidoalkylene, carboxyl,
It is a midalkylene or an alkylene. )
For example, C₈F₁₇SO_TwoN (C_FourH₉) CH_TwoCH_TwoOCOCH =
CH_TwoIs a poly (oxyalkylene) monoacrylate
And the copolymer described below is obtained.

In order to obtain the above-mentioned polymer having an Rf group, a method in which a raw material monomer is dissolved in an appropriate organic solvent and solution polymerization is carried out by the action of a polymerization initiator can be usually employed. Suitable solvents for solution polymerization include, for example, toluene, ethyl acetate, isopropanol, dichloropentafluoropropane, acetone, methyl ethyl ketone and the like.

In the present invention, not only one kind of polymer having Rf group or poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate but also a combination of two or more kinds can be used.

In the invention of claim 1 of the present invention, the total monomer unit of the acrylate or methacrylate containing Rf group in the copolymer is 2 to 24% by mass based on the mass of the copolymer, The group has from 1 to 26 carbon atoms and from 18 to 83% by weight of the Rf group of fluorine atoms.

In the above, the total monomer unit of the acrylate or methacrylate containing Rf group in the copolymer is from 2 to 24% by mass, but preferably from 8 to 22% by mass based on the mass of the copolymer. Is preferred, and 12 to 20
More preferably, it is mass%. When the amount is less than 2% by mass, it is difficult to obtain a uniform coating surface after coating and drying, and the effect of the present invention is difficult to be exerted, such as being easily charged with static electricity and the generation of dust and dirt. Since the aqueous property is excessively increased, repelling is generated, so that adhesion of dust and dirt are likely to occur.

In the above, the Rf group has from 1 to 26 carbon atoms, and more preferably the Rf group has from 4 to 16 carbon atoms. If it is 26 or more, it is difficult to dissolve in a solvent and it is difficult to obtain a uniform coating surface.

In the above, when the Rf group is 18 to 8 of the Rf group,
Contains 3% by mass of fluorine atoms, but 30 to 80% by mass
It is preferable to contain a fluorine atom of If it is less than 18% by mass, it is difficult to obtain a uniform coating surface after coating and drying, and it is difficult to exert the effects of the present invention such as being easily charged with static electricity and easily causing adhesion of dust and dirt. Since the aqueous property is excessively increased, repelling is generated, so that adhesion of dust and dirt are likely to occur.

On the other hand, a fluorine-containing aliphatic group (Rf
(Invention 2 or 3 of the present invention), lithium ion (invention 4 of the present invention) and latex of the present invention in combination. In the invention (claim 6 or 7 of the present invention) and the like, the total monomer unit of the Rf group-containing acrylate or Rf group-containing methacrylate in the copolymer is 2 to 86% by mass, preferably 2 to 86% by mass, based on the mass of the copolymer. Is 5 to 60% by mass, and the range can be broadened more than when the range is not used in combination (2 to 24% by mass). 2% by mass of a fluoroaliphatic group-containing monomer unit
When the amount is less than the above, the effect is not sufficient. On the other hand, when the amount is more than 86% by mass, the water repellency is excessively increased, so that repelling is generated, so that adhesion of dust and dirt easily occur, and the solubility in the solvent is too low. Is not preferred. The molecular weight of the copolymer used in the present invention is preferably from 1,800 to 14,999, and if it is smaller than 1,800, the effect is not sufficient,
If it is larger than 14,999, the solubility in a solvent is undesirably reduced. A particularly preferred range is from 2,000 to 12,
000.

The preferred range of use of the fluorosurfactant of the present invention is 100 μg to 10 g per 1 kg of the coating solution, and more preferably 1 mg to 1 g. If the amount is less than 100 μg, the effect is insufficient. If the amount is more than 10 μg, the coating film may not be sufficiently dried or the performance of the photosensitive material may be adversely affected.

It is preferable that the fluorinated surfactant of the present invention is added as an organic solvent solution. In particular, the boiling point of the organic solvent is preferably 40 to 200 ° C, and 60 to 1
60 ° C. is more preferred. The place of addition to the heat-developable material may be at any position in the constituent layer, but is preferably added to the protective layer. The protective layer can be added to one or both of the protective layer of the photosensitive layer and the BC layer. A particularly preferred layer is a protective layer which is an upper layer of the photosensitive layer. Photosensitive layer or B
When it is added to the C layer, it is preferable to add it in a range of one half to one hundredth, which is smaller than the amount added to the protective layer. The fluorinated surfactant is added in advance to the coating solution in a batch system (usually from 1 hour to 50 hours from application to application) or immediately before application (within 60 seconds).
May be applied while mixing with a coating solution using a static mixer, but the latter is preferred.

The fluorinated surfactant of the present invention (copolymer)
Preferred specific examples (copolymer examples) of (first type) are shown below.

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* F value: Fluorine content of Rf group Fluorine-containing aliphatic group which is a second kind of fluorine-based surfactant used in combination with the fluorine-based surfactant (copolymer) (first type) of the present invention The anionic surfactant having (Rf group) has a carboxyl group or a sulfonic acid group as an anion part, and contains 18 to 83% by mass of a fluorine atom based on the mass of the Rf group. A preferred anionic surfactant having a fluorine-containing aliphatic group (Rf group) has a carboxyl group or a sulfonic group as an anion part. These can be obtained from the market and can be synthesized by known techniques.

The anion having a fluorine-containing aliphatic group (Rf group) which is a second type of fluorine-based surfactant used in combination with the fluorine-based surfactant (copolymer) (first type) of the present invention is described below. Preferred specific examples of the surfactant are shown below.

(1) CF_Three(CF_Two)_FourCH_TwoOSO_ThreeNa (2) CF_Three(CF_Two)₆(CH_Two)_TwoOSO_ThreeNa (3) CF_Three(CF_Two)₆SO_ThreeNa (4) CF_Three(CF_Two)₇(CH_Two)_TwoOSO_ThreeNa (5) CF_Three(CF_Two)₇(CH_Two)_TwoCOONa (6) (CF_Three)_TwoCF (CF_Two)_Five(CH_Two)_TwoCOONa (7) CF_Three(CF_Two)₇(CH_TwoO)_{twenty four}SO_ThreeNa (8) (CF_Three)_TwoCF (CF_Two)₆(CH_Two)_ThreeOCOCH
_TwoCH_TwoSO_ThreeNa (9) (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH_TwoOCOCC
H_TwoCH_TwoSO_ThreeNa (10) (CF_Three)_TwoCF (CF_Two)₆CH_TwoCH (OH)
CH_TwoOCOCH_TwoCH_TwoSO_ThreeNa (11) CF_Three(CF_Two)₈(CH_Two)_TwoSO_ThreeNa (12) CF_Three(CF_Two)₈(CH_Two)_TwoCOONa (13) CF_Three(CF_TwoCl) CF (CF_Two)₇CONHC
OCH_TwoCH_TwoSO_ThreeNa (14) CH_Two= CHCOO (C_TwoH_FourO)₂₀COONa
(15) CH having a degree of polymerization of 4_Two= CHCONH (C_TwoH_FourO)₂₀SO_ThreeNa
(16) CH having a degree of polymerization of 5_Two= C (CH_Three) CONH (C_TwoH_FourO)_{twenty five}C
Polymer having a degree of polymerization of OOH of 7 (17) CF_Three(CF_Two)₇CONH (C_TwoH_FourO)₂₀CO
OH (18) CF_Three(CF_Two)₈CONH (C_ThreeH₆O)_{twenty two}OS
O_ThreeNa (19) C_13F27SO_TwoN (C_ThreeH₇) (CH_Two)_TwoOSO_Three
Na (20) CF_Three(CF_Two)₇SO_TwoN (CH_Three) (CH_Two)_Two
COOH (21) CF_Three(CF_Two)₇SO_TwoN (C_TwoH_Five) (CH_Two)_Two
SO_ThreeNa (22) CF_Three(CF_Two)₇SO_TwoN (C_FourH₉) (CH_Two)
_{twenty two}COONa (23) CF_Three(CF_Two)₉SO_TwoN (C_FourH₉) (CH_Two)_Two
O (C_TwoH_FourO)_FifteenSO _ThreeNa The method of adding the fluorosurfactant compound of the present invention is publicly available.
It can be added according to a known addition method. Methaneau
Alcohols such as toluene and ethanol, methyl ethyl ketone
Ketones such as acetone and acetone, dimethyl sulfoxide and
Dissolve in polar solvent such as methylformamide and add
be able to. In addition, sand mill dispersion and jet mill
1μ or less due to dispersion, ultrasonic dispersion or homogenizer dispersion
It can be added as fine particles dispersed in water or organic solvent.
Wear. Many technologies have been disclosed for fine particle dispersion technology.
However, according to these, the average particle size is 0.05 micron.
10 micron particle dispersion can be added from
Wear. To use fine particles, average the standard deviation of the particle size.
The monodispersity expressed by a value obtained by dividing by the particle diameter and multiplying by 100 is 1 to
Preferably it is 30%, and it is 1-20%
More preferred.

The heat-developable material of the present invention preferably contains 1/100 to 100 times, more preferably 1/100 to 100 times the total amount of the fluorine-containing surfactant.
The molar ratio is particularly preferably 1/10 mol to 1 mol. From the viewpoint of exhibiting an antistatic effect and an effect of preventing dust adhesion and dirt, the amount is preferably at least 1 / 1,000 times the mole. On the other hand, dust adhesion and dirt due to excessive hygroscopicity. It is preferable that the amount be 100 moles or less in view of the increase in the amount.

To incorporate lithium ions into the heat-developable material of the present invention, a method using a lithium halide such as lithium chloride or lithium bromide, a dye, a dye, an anionic surfactant, a counter of an inhibitor or an accelerator. There is a method in which lithium ions are used as the ions for inclusion. Preferred addition methods include a method of adding lithium to the counter ion of the anionic surfactant using lithium, lithium bromide,
Examples thereof include a method of adding as an organic or inorganic salt compound such as lithium nitrate, lithium chloride, lithium sulfate, lithium citrate, lithium oxalate, lithium itaconate, lithium gluconate, lithium sulfite, lithium carbonate, lithium hydrogen carbonate and the like.

<< Description of the Inventions of Claims 9 to 16 of the Present Invention >> The compounds represented by formula (1) used in the present invention will be described.

The compound represented by the general formula (1) is composed of an onium nitrogen compound or an onium phosphorus compound having a fluorinated chain, and a compound having a polyalkylene oxide chain at the center of the molecule and having anions at both ends. It is combined with

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a substituent to Q, and at least one of the substituents represents a group having a fluorine atom.
A ₁ and A ₂ each represent an anionic group, L ₁ and L ₂ each represent a divalent linking group, and Z represents a group having an alkylene oxide unit.

In the general formula (1), Q represents a nitrogen atom or an adjacent atom. R ₁ , R ₂ , R ₃ and R ₄ represent a substituent on Q, and include a hydrogen atom, an alkyl group which may be substituted (an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a butyl group). Group, pentyl group, heptyl group, octyl group, dodecyl group, etc.), alkenyl group (alkenyl group having 1 to 30 carbon atoms, such as propenyl group, butenyl group, petenyl group, octenyl group, nonenyl group, etc.), alkynyl group, aromatic And a heterocyclic group (eg, a pyridyl group, a furyl group, a thiophenyl group, a pyrimidyl group), and the like, and at least one of the substituents is a group containing a fluorine atom.

Z represents a group having an alkylene oxide unit. As the group having an alkylene oxide unit, a single type of alkylene oxide unit may be arranged, or a plurality of types of alkylene oxide units may be alternately arranged. They may be arranged in a block, or may be arranged randomly. As the alkylene oxide unit, an alkylene oxide unit having 1 to 8 carbon atoms is preferable, and examples thereof include an ethylene oxide group, a propylene oxide group, and a butylene oxide group. The number of repeating units of the alkylene oxide unit is 1 to
60 is preferred, and particularly preferably 2 to 40.

A ₁ and A ₂ each represent an anionic group, preferably a sulfonic acid group, a phosphonic acid group and a carboxylic acid group, particularly preferably a sulfonic acid group.

L ₁ and L ₂ represent a divalent linking group,
A divalent hydrocarbon group having 1 to 30 carbon atoms (butylene group, butenylene group, pentylene group, pentenylene group, octenylene group, etc.), divalent aromatic group (phenylene group, naphthalene group, etc.) or divalent heterocycle Groups (pyridinediyl group, furandiyl group, thiophendiyl group, etc.), and these groups further have a divalent amide group, sulfonamide group, ether group, thioether group, sulfine group, or the like as a linking group. May be. The linking group may be substituted with a halogen atom, an alkyl group, an alkenyl group, an aromatic group, a heterocyclic group, or the like.

The compound represented by the general formula (1) of the present invention includes an onium nitrogen compound or an onium phosphorus compound having a fluorinated chain, and a compound having a polyalkylene oxide chain at the center of the molecule and having anionic moieties at both ends. Can be easily prepared by ionically binding (salt forming), and can be used.

In the compound of the present invention represented by the general formula (1), a compound for supplying a cation moiety represented by Q ⁺ (R ₁ , R ₂ , R ₃ , R ₄ ) in the general formula (1) is used. As the member A,
For example, Q ⁺ (R ₁ , R ₂ , R ₃ , R ₄ ) and an anion of a halogen atom as a counter ion (chlorine ion, bromine ion, iodine ion, etc.), boron tetrafluoride ion, perchlorate ion, etc. And a salt from an anion. These can be obtained from the market, and can also be synthesized by known techniques.

Hereinafter, in the general formula (1), Q ⁺ (R ₁ ,
Preferred specific examples of the member A for supplying the cation portion represented by R ₂ , R ₃ , and R ₄ ) are shown below, but are not limited thereto.

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[0075]

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[0076]

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The compound of the present invention represented by the general formula (1)
In the general formula (1), A₁ ^--L₁-ZL_Two-A_Two ^-In table
Examples of the member B for supplying the anion portion to be used include:
For example, A₁ ^--L₁-ZL_Two-A_Two ^-And counter ion
H as⁺, Li⁺, Na ⁺, Ka⁺Acid or na
Alkali metal salts such as thorium, potassium or lithium salts
And the like. These are, for example, polyalkylene oxides.
The glycol or glycol ester on the side
A member (group) having a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group
Can be obtained by introduction by addition or condensation, etc.
You.

[0078] The following, in general formula ₍₁₎ A 1 ^- -L 1
Preferred specific examples of the member B for supplying the anion portion represented by —ZL ₂ —A ₂ ^— are shown below, but are not limited thereto.

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[0080]

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[0081]

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[0082]

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The method of preparing and using the compound represented by the general formula (1) of the present invention is as follows. (1) The members A and B are added to the same layer or different layers of the heat developing material and A method for forming a compound represented by the general formula (1) in a coating film, (2) a method in which a member A and a member B are added to water, an organic solvent, a mixed solvent thereof and mixed to form A precipitation method obtained by precipitating a compound represented by the formula, (3) gelatin,
Member A and member B in a hydrophilic medium such as a gelatin derivative
Is added and solidified to leave the compound represented by the general formula (1) in the hydrophilic medium, and unnecessary inorganic salts are washed and desalted with water. (4) Water and ethyl acetate, butanol ,
The members A and B are added to a mixed solvent with an organic solvent such as toluene, n-hexane, dioxolan, methyl ethyl ketone, and methyl isobutyl ketone, and the compound represented by the general formula (1) of the present invention is separated into an organic phase. An extraction method in which an unnecessary inorganic salt is collected and discarded in a water phase, and an organic solvent in a separated organic phase is removed by distillation.

Preferred specific examples of the compound represented by the general formula (1) of the present invention obtained from a preferable combination of the member A and the member B are shown below, but the invention is not limited thereto.

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The fluorination rate of the optionally substituted alkyl group, alkenyl group, aromatic group and heterocyclic group represented by R _{1 to} R _{4 in} the compound represented by formula (1) of the present invention is determined by Can be expressed as a percentage of the number of fluorinated fluorocarbons relative to the total number of hydrocarbon groups before fluorination. For example, in the case of a fluorinated octyl group: C ₈ F ₁₇ , C ₈ H ₁₇ before fluorination Since the total number of hydrocarbons is 17 and the fluorination is 17, (17/17) × 100 = 100%.
(10/17) × 100 = 59 in the case of C ₈ F ₁₀ H ₇ group
%, In the case of C ₈ F ₄ H ₁₃ groups, (4/17) × 100 = 24
%. The preferred range of the fluorination rate is related to the number of carbon atoms of the hydrocarbon group before fluorination, and is preferably 75% or more when the number of carbon atoms is 4 or less, and 6% when the number of carbon atoms exceeds 20.
0% or less is preferable. Particularly preferred is a fluorinated carbon number of 5 to 15, and a fluorination rate of 50%.
~ 100%.

The compound of the present invention represented by the general formula (1) can be added according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles having a particle size of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion and added. Many techniques have been disclosed for the fine particle dispersion technique. According to these techniques, a fine particle dispersion having an average particle diameter of 0.05 μm to 10 μm can be added. In order to use fine particles, the monodispersity, expressed as a value obtained by dividing the standard deviation of the particle size by the average particle size and multiplying by 100, is preferably 1 to 30%, more preferably 1 to 20%. The position of the layer when added to the heat development material of the present invention,
It is preferred to use the protective layer of the photosensitive layer and BC layer, the addition amount is preferably 0.01mg~10g / m ^2, particularly preferably 0.1mg~1g / m ^2. When it is added to a layer other than the protective layer, the amount is preferably 0.02 to 0.6 g / m ² .

<< Description of the Inventions of Claims 1 to 8 and 9 to 16 of the Present Invention >> The organic silver salt used in the heat developing material of the present invention is preferably a needle crystal. As is well known in photosensitive silver halide light-sensitive materials, since the inverse relationship between the size of silver salt crystal grains and their covering power is established in the heat developing material of the present invention, the organic silver salt grains are large. In addition, since the covering power is small and the image density is low, reducing the size of the organic silver salt gives a good result. In the present invention, the minor axis of the organic silver salt is preferably from 0.01 μm to 0.20 μm, the major axis is preferably from 0.10 μm to 5.0 μm, the minor axis is from 0.01 μm to 0.15 μm, and the major axis is 0 μm. More preferably, it is not less than 10 μm and not more than 4.0 μm. The particle size distribution of the organic silver salt is preferably monodispersed.
The monodispersity of the organic silver salt is expressed as a percentage of the standard deviation of the length of each of the minor axis and major axis divided by the minor axis and major axis, and is preferably 80% or less, more preferably 60% or less. %
Or less, more preferably 40% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of calculating the standard deviation of the volume-weighted average diameter of the organic silver salt.
The 0 fraction (coefficient of variation) is preferably 80% or less, more preferably 60% or less, and still more preferably 40% or less.
As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with laser light, mathematically calculated from the fluctuation of the scattered light, and can be obtained from the obtained particle size (volume weight average diameter). In the heat developing material of the present invention, the amount of the organic silver salt used is generally preferably from 0.1 to 5 g / m ² ,
More preferably, it is 1 to 3 g / m ² .

The reducing agent used in the heat developing material of the present invention is
Any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The amount of the reducing agent used is preferably 1 to 10% by mass of the image forming layer.
In multilayer constructions, if the reducing agent is added to a layer other than the emulsion layer, a slightly higher proportion, about 2 to 15% by weight, tends to be more desirable. As a reducing agent for a heat developing material using an organic silver salt, a general reducing agent can be used. For example, bisphenol derivatives (2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1-bis (2-hydroxy-3,
5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like, ascorbic acid derivatives (for example, 1-ascorbyl palmitate, stearic acid) Aldehydes and ketones such as benzyl and biacetyl, 3-pyrazolidone and indane-1,3-dione, and tocopherol. Particularly preferred reducing agents are bisphenol derivatives. The amount of the reducing agent of the present invention is generally 0.1 to 15 g.
/ M ² is preferred, and more preferably 0.5 to 10 g /
m ² .

As a binder for the heat developing material of the present invention, a material which is preferable as a place where silver halide, an organic silver salt and a reducing agent react, and a reaction in which a thermal decoloring dye is decolorized by heat of 80 ° C. to 200 ° C. Materials that are preferable for the above, and materials in which the base generation precursor quickly generates a base by heat are preferable. For example, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, cellulose derivatives such as ethylcellulose, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, styrene-
Maleic anhydride copolymer, polyacrylamide, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene- Butadiene-acrylic copolymer and the like. After drying and forming a film, the coating film preferably has a low equilibrium moisture content. As for the composition of the polymer preferable as the binder, the glass transition point is more preferably from -60 ° C to 80 ° C, particularly -50 ° C.
To 70 ° C. This is because if the glass transition point is high, the temperature for thermal development becomes high, and if the glass transition point is low, fogging is liable to occur, resulting in a decrease in sensitivity and softness.

The water-dispersed hydrophobic polymer is called a latex and is preferably dispersed as fine particles having an average particle diameter of 1 nm to several μm, and is widely used as a binder for aqueous coating. Latex for improving the property is preferred, and latex having a halogen atom in the molecule is particularly preferred. Examples of the latex containing a halogen atom in the molecule that are preferable in the present invention include polyvinylidene fluoride, a homopolymer of polyvinylidene chloride, vinylidene fluoride, and a copolymer of vinylidene chloride with an acrylic or olefinic compound. Polyvinylidene fluoride or polyvinylidene chloride has the general formula (CX ₂
—CH ₂ ) _n , wherein X is a fluorine atom or a chlorine atom,
n is a positive integer), and is a fluorine compound having an average fluorine content in one molecule of preferably 50% to 60%, preferably a form in which methylene groups and methylene fluoride groups are alternately stable. Are combined.

The amount of the latex used for the purpose of obtaining water resistance as a binder is determined in consideration of coatability, but is preferably as large as possible from the viewpoint of moisture resistance, and is preferably from 50% to 100% with respect to the total mass of the binder. , 65% or more and 100% or less, particularly preferably 80% or more and 100% or less.

Preferred specific examples of the water-dispersed hydrophobic polymer (latex) are shown below, but are not limited thereto.

Here, styrene is St, methyl acrylate is MA, methyl methacrylate is MMA, ethyl acrylate is EA, butyl acrylate is BA, isononyl acrylate is INA, cyclohexyl methacrylate is CA, hydroxyethyl acrylate is HEA,
Hydroxyethyl methacrylate is HEMA, acrylic acid is AA, itaconic acid is IA, maleic acid is MAA, acrylamide AAm, styrene sulfonic acid is St-S,
Acrylamide-2-methylpropanesulfonic acid amide is AMPS, isoprenesulfonic acid is IP-S, 2-propenyl-4-nonylphenoxyethylene oxide (n = 10) sulfonic acid ester is PF-S, vinylidene chloride is CVD and fluorinated. Vinylidene is abbreviated as FVD. The accompanying small letters represent composition mass composition ratio.

[0095] Monomer compositions molecular weight _{(Thousands) Tg (1) EA 97 AA} 3 1 -26 (2) EA 100 2 -29 (3) EA 40 BA 57 AA 3 10 -46 (4) EA 97 MMA 3 13 -23 _{(5) St 20 MMA 30 EA} 40 BA 8 AA 2 20 38 (6) St 10 IP-S 10 MMA 30 EA 50 2 46 (7) EA 90 AMPS 10 5 -16 (8) MMA 10 EA 88 AMPS 2 0 _{.2 -15 (9) St 30 MMA} 20 EA 40 BA 5 AA 5 0.8 33 (10) CA 60 INA 30 IP-S 10 3 -46 (11) MMA 50 EA 40 AMPS 10 4 10 (12) MMA ₅₀ EA ₄₀ St-S ₁₀ 10 15 (13) EA ₉₀ PF-S ₁₀ 50 -20 (14) MMA ₅₀ EA ₄₀ AAm ₁₀ 20 22 (15) St ₂₀ MMA ₃₀ EA ₅₀ HEA ₁₀ 10 23 (16) St ₁₀ MMA ₃₀ E _{50 HEMA 10 10 18 (17)} BA 40 St 20 EA 30 AA 10 10 11 (18) CA 60 INA 30 MA 10 20 -38 (19) CA 60 INA 30 AMPS 10 4 -34 (20) CA 50 INA 30 EA _{10 AMPS 10 3 -32 (21)} EA 95 AA 5 10 -25 (22) EA 97 BA 3 13 -26 (23) EA 50 BA 47 AA 3 20 -36 (24) EA 95 MMA 5 2 -24 (25 _{) St 20 MMA 30 EA 39 BA} 8 AA 3 5 32 (26) St 15 IP-S 5 MMA 30 EA 50 0.2 33 (27) EA 80 AMPS 20 0.8 23 (28) MMA 2 EA 88 AMPS 10 _{3 27 (29) St 32 MMA} 20 EA 40 BA 5 AA 3 4 30 (30) CA 50 INA 30 IP-S 20 10 5 (31) MMA 40 EA 50 AMPS 10 50 33 (32) MMA 25 _{A 40 St-S 30 20 26} (33) EA 80 PF-S 20 10 -16 (34) MMA 50 EA 45 AAm 5 10 24 (35) St 15 MMA 30 EA 50 HEA 5 10 23 (36) St 10 MMA _{35 EA 50 HEMA 5 20 33 (} 37) BA 44 St 20 EA 30 AA 6 4 -33 (38) CA 64 INA 33 MAA 3 3 -36 (39) CA 40 INA 40 AMPS 20 10 -40 (40) CA 53 INA ₃₀ EA ₁₀ AMPS ₇ 15-44 (41) St ₃₀ BU ₆₈ IA ₂ 10 21 (42) BA ₅₀ CVD ₅₀ 10-20 (43) CVD ₉₈ IA ₂ 20-15 (44) FVD ₉₈ IA ₂ 20-38 (45) CVD ₁₀₀ 20-18 (46) FVD ₁₀₀ 20-40 The pressing roller used in the heat developing section of the developing machine for developing the heat developing material of the present invention has heat resistance, chemical resistance, Wear resistance,
Any roller having antistatic properties or the like can be employed, but a silicone rubber (organopolysiloxane) roller having particularly improved heat resistance and chemical resistance is preferable.
Silicone rubber is colored by adding various coloring agents as necessary. Carbon black and black red iron oxide are known as typical coloring agents for giving black color to silicone rubber. In addition, heat resistance is also given by adding various additives. As a method for imparting heat resistance to such a silicone rubber composition, a platinum catalyst is generally typical as a crosslinking accelerator, and a combination of a platinum catalyst with an additive such as carbon black has also been proposed. I have. For example, U.S. Pat. No. 3,652,488 mentions carbon black and U.S. Pat. No. 3,635,874 mentions titanium oxide as an auxiliary.

When black husk is added, the color changes from black to red due to an oxidation-reduction reaction with the oxidizing agent of the heat-developable material, and the mechanical strength and heat resistance tend to decrease accordingly. Therefore, the surface is preferably 1 to 33 parts by mass, more preferably 1 to 1 part by mass.
When 0 parts by mass of alumina or silica-alumina-treated hematite is used, it does not turn red even when exposed to a heat developing material and a high temperature atmosphere (80 ° C. to 200 ° C.) for a long time.
When the palladium and ruthenium catalysts are combined, the heat resistance and the mechanical strength are less reduced. Preferred examples of the organopolysiloxane formulation include (A) a part of silicon atoms having 1 carbon atom.
100 parts by mass of an organopolysiloxane which may be substituted with 30 to 30 different atoms, (B) 1 to 48 parts by mass of an iron oxide,
(C) A composition comprising a curing agent is preferred, and particularly preferred is a composition in which the above (B) is substituted or used in combination with the following (D). (D) Finely powdered hematite, preferably 0.1 to 5 parts, of which the surface is treated with 1 to 33 parts by weight, more preferably 1 to 10 parts by weight of alumina or silica-alumina
0 parts by mass.

A method for preparing a silicone rubber which is particularly preferred for the present invention will be described. The silicon atoms of the organopolysiloxane (A) are different substituted or unsubstituted carbon atoms having 1 to 1 carbon atoms.
It has a monovalent hydrocarbon group of 0, and examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group, and a monovalent group selected from a methyl group, a vinyl group, and a phenyl group is particularly preferable. . The alkenyl group is preferably contained in an amount of preferably 0.01 to 5 mol%, more preferably 0.02 to 0.5 mol%. Examples of the substituted hydrocarbon group include an alkyl group, an alkenyl group, and a group in which part or all of the hydrogen atoms bonded to carbon atoms of an unsubstituted hydrocarbon group such as an aryl group are substituted with a halogen atom, a cyano group, or the like. Examples thereof include a 3,3,3-trifluoropropyl group and a 2-cyanoethyl group, and a 3,3,3-trifluoropropyl group is particularly preferable. Examples of the molecular chain terminal groups include a hydroxy group, a trimethylsilyl group, a dimethylvinylsilyl group, and a trivinylsilyl group, but are not particularly limited thereto. The organopolysiloxane (A) has a polymerization degree of preferably 2,700 or more, more preferably 3,000 to 20,000, in order to obtain sufficient mechanical strength.
00, particularly preferably from 4,800 to 10,000.
0. As the organopolysiloxane (A), two or more kinds having different structures and degrees of polymerization can be used in combination.

The reinforcing silica as the component (B) has a specific surface area of preferably 66 m ² / g or more in order to impart appropriate hardness to the silicone rubber and improve mechanical strength such as tensile strength. Is used, but 99m ² -4
Those with 44 m ² / g are particularly preferred. As such a reinforcing silica, specifically, fumed silica, calcined silica, precipitated silica, or the like is used alone or in combination of two or more. These silicas may be surface-treated with a linear organopolysiloxane, a cyclic organopolysiloxane, hexamethyldisilazane, dichlorodimethylsilane, or the like. The compounding amount of the component (B) is preferably from 10 to 100 parts by mass, more preferably from 20 to 50 parts by mass, per 100 parts by mass of the organopolysiloxane of the component (A). If the compounding amount is out of this range, the processability of the silicone rubber composition may be deteriorated, or sufficient mechanical strength may not be obtained.

The curing agent of the component (C) cures the composition of the present invention into a silicone rubber, and generally uses an organic peroxide. When the organopolysiloxane of the component (A) contains two or more alkenyl groups in the molecule, a combination of an organohydrogenpolysiloxane and a platinum-based catalyst can be used as a curing agent. The amount of the curing agent may be an amount sufficient to cure the composition of the roller according to the present invention as described below. Examples of the organic peroxide usable in the present invention include dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, and 2,5-dimethyl-2,5-.
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
2,5-dimethyl-2,5-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-chlorobenzoyl peroxide and the like. Can be The amount of these organic peroxides is preferably in the range of 0.1 to 10 parts by mass per 100 parts by mass of the component (A) as an amount sufficient to cure the silicone rubber composition of the roller according to the present invention. Is within. When the organopolysiloxane of the component (A) contains two or more alkenyl groups in the molecule, examples of the organohydrogenpolysiloxane that can be used as a curing agent include methylhydrogenpolysiloxane having trimethylsiloxy groups at both ends and methylhydrogenpolysiloxane at both ends. Examples thereof include a dimethylsiloxane / methylhydrogensiloxane copolymer having a terminal-trimethylsiloxy group and a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of a methylhydrogensiloxy group. On the other hand, examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of chloroplatinic acid and divinyltetramethylsiloxane. The amount of the organohydrogenpolysiloxane is generally
The ratio of the number of moles of hydrogen atoms bonded to silicon atoms contained in the organohydrogenpolysiloxane to the number of moles of alkenyl groups in the component (A) is (0.5: 1) to (2).
0: 1), and the amount of the platinum-based catalyst is generally preferably about 0.1 to 3,000 ppm in terms of platinum based on the mass of the component (A). When using compounds, they can be shared.

Component (D) is a characteristic component of the silicone rubber composition of the roller according to the present invention, and its surface is preferably made of 1 to 33 parts by mass, more preferably 1 to 10 parts by mass of alumina or silica-alumina. It is a treated finely divided hematite. The component (D) may be further treated with an organic compound such as a silane coupling agent or an inorganic compound such as Al or Si to improve fluidity and chemical resistance within a range that does not impair the object of the present invention. It is. Component (D) preferably has a particle size of 0.1 to 5.0 μm, more preferably 0.1 to 2.0 μm. Those having a particle size of less than 0.1 μm have high activity and may be difficult to be blended.
If it exceeds, the mechanical strength of the cured product may be impaired.
When mixing the component (D) with the organopolysiloxane composition, a kneader such as a kneader, a Banbury mixer, or an open roll may be used. Component (D) is used in an amount of preferably 0.1 to 50 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the organopolysiloxane of component (A). If the amount is less than 0.1 part by mass, the black color will not be sufficient, heat resistance and chemical resistance will be insufficient, and if it exceeds 50 parts by mass, the elasticity of the silicone rubber will deteriorate. Further, two or more kinds of the component (D) may be used in combination. The platinum compound improves the heat resistance synergistically with the effect of the component (D), and examples thereof include chloroplatinic acid and an alcohol solution of chloroplatinic acid as described above. The amount of the platinum compound is preferably 0.0001 to 0.1 part by mass, more preferably 0.001 to 0.01 part by mass, based on 100 parts by mass of the silicone rubber composition of the roller according to the present invention in terms of platinum amount. It is. If the value is less than the lower limit of the limited range, the effect becomes insufficient, and if the value exceeds the upper limit of the limited range, the effect is not changed, and it is not economical.

The silicone rubber composition may be any of the above (A) to
In addition to the component (D), various rubber compounding agents, for example, diphenylsilanediol, which are appropriately compounded with the silicone rubber, in amounts not to impair the object of the present invention, such as diphenylsilanediol, silicone oil having a low polymerization degree and having a hydroxyl group at the molecular chain terminal. , Hexamethyldisilazane, dispersant such as alkoxysilane, ground silica,
Diatomaceous earth, zinc oxide, titanium oxide, carbon black, barium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, asbestos, glass wool, fine mica, fused silica powder, etc. may be added and blended.
Further, if necessary, an antioxidant, an antioxidant, an antistatic agent, a thermal conductivity improver such as boron nitride and aluminum oxide may be blended.

The method for producing the silicone rubber composition is not particularly limited, but the components (A) and (B) are charged into a kneading device such as a kneader and blended at room temperature.
A method of heat-treating at a temperature of about 200 ° C. for 30 minutes to 5 hours, followed by adding the component (D) and kneading with a roller mill, a Banbury mixer, or the like can be employed. After that, the component (C) may be added, and then heat-cured by a known method.
The cured silicone rubber thus obtained has good heat resistance and chemical resistance.

The photosensitive silver halide used in the heat-developable material of the present invention can be produced by any method known in the field of photographic technology such as a single jet or double jet method.
For example, it can be prepared by any method such as an ammonia method emulsion, a neutral method and an acid method. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 as protective polymers for preparing photosensitive silver halide. , 565
No. 3,713,833, No. 3,748,14
No. 3, British Patent No. 1,362,970 or the like, a method using a polymer other than gelatin such as polyvinyl acetal, or a photosensitive halogen described in British Patent No. 1,354,186. Means for enzymatically decomposing gelatin in a silver halide emulsion, or US Pat. No. 4,076,53
As described in No. 9, various methods such as a method of omitting the use of a protective polymer by preparing photosensitive silver halide grains in the presence of a surfactant can be applied.

The silver halide functions as an optical sensor, and preferably has a small grain size in order to suppress white turbidity after image formation and to obtain good image quality. The average particle size is 0.1 μm or less, preferably 0.1 μm or less.
01 μm to 0.1 μm, especially 0.02 μm to 0.08 μ
m is preferred. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, or non-normal crystals, such as spherical, rod-like, or tabular grains. The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The amount of silver halide is 50% or less, preferably 25% or less, based on the total amount of silver halide and the organic silver salt described below.
0.1%, more preferably between 15% and 0.1%.

The photosensitive silver halide used in the heat-developable material of the present invention may also be used in preparing an organic silver salt as described in GB 1,447,454. By injecting silver ions into a coexisting halogen component such as an organic silver salt-forming component and silver ions, organic silver salt can be generated almost simultaneously.

As still another method, a silver halide forming component is allowed to act on a solution or dispersion of an organic silver salt prepared in advance or a sheet material containing the organic silver salt, so that a part of the organic silver salt is exposed to light. It can also be converted to neutral silver halide.
The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak specific to silver halide. Silver halide-forming components confirmed to be effective by such tests include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Are U.S. Pat. Nos. 4,009,039 and 3,45
7,075, 4,003,749, British Patent 1,498,956, JP-A-53-27027, and JP-A-5-27027.
No. 3-25420 can be referred to.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is preferably from 0.001 mol to 1 mol of the organic silver salt.
It is 0.7 mole, more preferably 0.03 mole to 0.5 mole. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. , Usually the reaction temperature is-
It is preferable that the reaction time is 23 ° C. to 74 ° C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is set to the atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 1 per 1 part by mass of the organic silver salt.
00 parts by mass, preferably 0.1 to 10 parts by mass.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be achieved by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, US Pat. No. 4,036,650, British Patent 1,518,850, JP-A-51-22430,
Nos. 51-78319 and 51-81124. Also, when a part of the organic silver salt is converted to a photosensitive silver halide by a silver halide forming component, as described in U.S. Pat. An amide compound having a molecular weight may coexist.

In addition, these photosensitive silver halides may be used in order to prevent illuminance failure or to adjust the gradation.
Metals belonging to group III, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof, or a complex ion can be contained. It is particularly preferable to contain ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. As the above metals, W, Fe, Co, Ni,
Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u is preferable, and when it is used for a photosensitive material for plate making, it is preferably selected from Rh, Re, Ru, Ir, and Os.

These metals can be introduced into silver halide in the form of a complex. In the present invention, the transition metal complex is [M
6 coordination complex represented by L _6] ^m type is preferred.

In the formula, M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, m is 0,-
Represents 3, -2 or -1. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate,
Examples include ligands of selenocyanate, tellurocyanate, azide and aquo, nitrosyl, thionitrosyl and the like, and preferably aquo, nitrosyl and thionitrosyl and the like. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same,
They may also be different. Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), and osmium (Os).

The content of metal ions or complex ions is generally 1 × 10 ^-9 per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

In the present invention, the protective layer and the BC layer on the photosensitive layer preferably contain a matting agent, and the material of the matting agent used in the present invention may be any of an organic substance and an inorganic substance. For example, inorganic substances include silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 and the like. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic substances, US Patent No. 2,32
2,037, etc., Belgian Patent No. 625
No. 451, British Patent No. 981,198, etc .; starch derivatives, polyvinyl alcohol described in JP-B-44-3643, etc .; polystyrene or polymethacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic matting agents such as polyacrylonitrile described in 3,079,257 and the like and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.
The matting agent used in the present invention has an average particle size of 0.5 μm
To 10 μm, more preferably 1.
0 μm to 8.0 μm. The monodispersity of the particles is 50
% Or less, more preferably 40% or less, particularly preferably 20% or less. Here, the monodispersity of the particles is represented by a number obtained by dividing the standard deviation of the particle size by the average value of the particle size and multiplying by 100. The method of adding the matting agent may be a method in which the matting agent is dispersed in a coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after the coating solution is applied. When a plurality of types of matting agents are added, both methods may be used in combination.

The heat-developable material of the present invention, which forms a photographic image by heat-development, comprises a reducible silver source (organic silver salt), a catalytically active amount of silver halide, a hydrazine derivative,
The heat developing material preferably contains a reducing agent and, if necessary, a color tone agent for suppressing the color tone of silver in a state of being usually dispersed in an (organic) binder matrix. The heat developing material of the present invention is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 200 ° C.) after exposure. Heating includes a one-step method of heating at a constant temperature for a fixed time and a method of stepwise heating such as preheating, main heating, and post-heating, and the heating method can be appropriately selected.
Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

It is preferable to add a toning agent to the heat-developable material of the present invention. Examples of suitable toning agents are Research.
h Disclosure No. 17029, which includes:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt); mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
(A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole), a merocyanine dye (for example, 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-polyhalomethane compound dione);
Combination of phthalazinone and sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate), combination of polyhalomethane compound + phthalic acid, polyhalomethane compound (addition of polyhalomethane compound) And maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic acid) Acid anhydrides); quinazolinediones; benzoxazine, naphthoxazine derivatives; benzoxazine-2,4
-Diones (for example, 1,3-benzoxazine-2,
Pyrimidines and asymmetric triazines (eg, 2,4-dihydroxypyrimidine); and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2). , 3a,
5,6a-tetraazapentalene).

The heat-developable material of the present invention includes, for example, JP-A-6
No. 3-159841, No. 60-140335, No. 63
No.-231437, No.63-259651, No.63-
Nos. 304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175,
Sensitizing dyes described in the above-mentioned 4,835,096 can be used. Useful sensitizing dyes for use in the present invention include, for example, R
essearch Disclosure No. 17643IV
-Section A (p.23, December 1978), 1831X
(August 1978, p. 437). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078,
The compounds described in JP-A Nos. 9-54409 and 9-80679 are preferably used.

As the support of the heat-developable material of the present invention,
A support such as paper, synthetic paper, nonwoven fabric, metal foil, polyester such as polyethylene terephthalate and polyethylene naphthalate, and a plastic film such as polycarbonate and polypropylene can be used. Good.

FIG. 1 shows one preferred embodiment of the layer constitution of the heat-developable material of the present invention. An undercoat layer 5 is provided on a support 6, and an AH layer 4, a photosensitive layer 3, an intermediate layer 2, and a protective layer 1 are sequentially provided. The undercoat layer 7, the conductive layer 8, the BC layer 9, and the BC protective layer 10 are provided on the opposite side of the support 6, and it is preferable that these layers are simultaneously formed on both the front and back surfaces by a known technique.

In the present invention, the exposure is preferably performed by laser scanning exposure, but it is preferable to use a laser scanning exposure machine in which the angle between the exposure surface of the photosensitive material and the scanning laser beam does not become substantially perpendicular. . here,
"Never be substantially perpendicular" means that the angle is most perpendicular to the surface during laser scanning, preferably 55 degrees or more and 88 degrees or more.
Degrees or less, more preferably 60 degrees or more and 86 degrees or less, still more preferably 65 degrees or more and 84 degrees or less, and most preferably 70 degrees or more and 82 degrees or less. The beam spot diameter on the exposed surface of the photosensitive material when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. The lower limit of the beam spot diameter is 1
0 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of unevenness like interference fringes. Exposure in the present invention is preferably performed using a laser scanning exposure machine that emits a scanning laser beam that superimposes a plurality of wavelength lights. Image quality deterioration such as exposure unevenness and interference fringe-like unevenness is reduced as compared with a single mode scanning laser beam. To superimpose a plurality of wavelengths, there are a method using a synthetic wave mixed wave, a method using return light via a reflection mirror, and a method using a high frequency superposition. The superimposed wave has a single exposure wavelength, and usually has an exposure wavelength distribution of 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm. At the time of superimposition, it is preferable to control the intensity and amplitude of the laser beam and synthesize the laser beams. FIG. 2 shows a schematic diagram of wave synthesis. Laser transmitters 11-1
The laser light 18 to 20 applied to the amplitude modulator from 3 generates a superimposed wave 21 superimposed by a light mixer at a reflection mirror, and transmits this to a polygon mirror in the case of a flat scanner. FIG. 3 shows an example of a heat developing machine used in the present invention.

As the reducing agent used in the present invention, a reducing agent that reduces silver halide can be used as a reducing agent for an organic silver salt, or can be used independently. For example, bisphenol (for example, bis (2-hydroxy-3-t-butyl-5)
-Methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1-bis (2 -Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like); ascorbic acid derivatives (for example,
There are aldehydes and ketones such as 1-ascorbyl palmitate, ascorbyl stearate) and benzyl and biacetyl; 3-pyrazolidones and certain indan-1,3-diones, tocopherols. Particularly preferred reducing agents are bisphenols.

The development of the present invention is preferably carried out in the range of 80 ° C. to 180 ° C., more preferably 100 ° C. to 160 ° C., and particularly preferably 110 ° C. to 130 ° C. From the viewpoint of enhancing the thermal development reaction and preventing the increase of only fog, 8
The temperature is preferably 0 ° C. or higher, and is preferably 180 ° C. or lower in order to prevent a large temperature difference between the surface and the inside of the photosensitive material from increasing the development fog due to overheating of the surface.
It is particularly preferable to preheat at 115 ° C. or lower for a certain period of time within 30 seconds, thermally develop at 110 ° C. to 130 ° C. within 1 minute, and then cool to 80 ° C. to 40 ° C. within 30 seconds. Heating of the heat developing material includes, in addition to airflow heating in which the heat developing material is passed under an atmosphere of heated air, direct heating in which the heat developing material is brought into contact with a heated cylindrical drum (heat drum), heat drum The heating roller is also heated using the heat of the heat developing material, and the heat developing material is heated from both sides. One preferred embodiment is described below. First, the film to be developed is sent to the heating drum by an introduction holding roller arranged to pass through the preheating section, and travels while being heated between the holding roller and the heating drum arranged on the outer periphery of the heating drum, and cooled. The part is cooled to room temperature and discharged. The surface of the heat-developable material in contact with the heat drum can be an emulsion surface or a BC surface, but is preferably a BC surface. It is preferable that the rotating drum and the pressing roller rotate in synchronization with each other. However, for dimensional stability, the number of rotations may be finely controlled to expand or contract. As a heat source, an infrared heater, a nichrome wire, or the like can be used. The adiabatic shielding of the heat drum can control the development temperature by attaching a cold mirror that reflects heat rays. The heat drum is made of a material having excellent thermal conductivity, such as copper, aluminum, and steel, and the plurality of heat rollers are preferably silicone containing iron oxides surface-treated with the above-described metal or metal oxide. A roller is used, and its surface hardness is 1 × 10 when expressed as an elastic modulus.
^-4 Pa is preferable. Further, the transfer speed of the heat developing material is preferably 1 to 100 cm / sec, and the pressure between the heat drum and the heat roller group during transfer is 10 ² to 10 ^-5.
It is preferably Pa. An example was shown in which the heat roller group was not provided with a heat source, but was pressed against a heat drum with a built-in heat source, the heat from the heat source drum was confined in a heat insulating cover, and the heat roller was heated to the developing temperature to perform development. Without a heat source, a heat roller may be provided with a heat source, and a heat insulating cover may be used to maintain the development temperature to perform development, or thermal development using a combination of the above mechanisms may be performed. In the case of direct thermal development in which an image is directly written on a thermal development material by infrared rays, development can be performed without processing with a thermal development machine.

<< Description of the Inventions of Claims 17 to 21 of the Present Invention >> The compounds represented by formula (2) of the present invention will be described.

[0126]

Embedded image

In the formula, P represents a phosphorus atom, Rt ₁ and Rt ₂ each represent an aliphatic group, an aromatic group or a heterocyclic group which may have a substituent, and A ₁ and A ₂ each represent an anionic group. Represent
R _{1 to} R ₆ each represent a hydrogen atom or a substituent of a hydrogen atom, L ₁ and L ₂ each represent a divalent linking group, and Z ₁ represents a group having an alkylene oxide unit.

In the general formula (2), Rt ₁ and Rt ₂
As the aliphatic group represented by, an alkyl group (having 1 to 1 carbon atoms)
30, for example, a methyl group, an ethyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, a dodecyl group, etc., an alkenyl group (for example, a propenyl group having 1 to 30 carbon atoms,
Butenyl group, petenyl group, octenyl group, nonenyl group, etc.), alkynyl group (eg, acetylene group, biacetylene group, etc.). Examples of the aromatic group include a phenyl group and a naphthyl group. Heterocyclic groups include pyridyl, furyl, thiophenyl, pyrimidyl,
Examples include an imidazole group, a thiazole group, an oxazole group, a triazole group, and a tetrazole group. The groups represented by Rt ₁ and Rt ₂ may have a fluorine atom.

Z ₁ represents a group having an alkylene oxide unit. As the group having an alkylene oxide unit, a single type of alkylene oxide unit may be arranged, or a plurality of types of alkylene oxide units may be alternately formed. May be arranged, may be arranged in a block shape,
They may be arranged at random. As the alkylene oxide unit, an alkylene oxide unit having 1 to 8 carbon atoms is preferable, and examples thereof include an ethylene oxide group, a propylene oxide group, and a butylene oxide group. The number of repeating units of the alkylene oxide unit is 1
~ 60 is preferable, and 4 ~ 40 is particularly preferable.
The number of repeating units is preferably 1 or more from the viewpoint of obtaining uniformity of application, prevention of dirt, and scratch resistance, and the number of repeating units is preferably 60 or less from the viewpoint of preventing deterioration of scratch resistance due to excessive hygroscopicity. preferable.

A ₁ and A ₂ each represent an anionic group. As the anionic group, a sulfonic acid group, a phosphonic acid group and a carboxylic acid group are preferable, and a sulfonic acid group is particularly preferable.

L ₁ and L ₂ each represent a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group having 1 to 30 carbon atoms (butylene group, butenylene group, pentylene group, pentenylene group). Group, octenylene group, etc.), divalent aromatic group (phenylene group, naphthalene group), divalent heterocyclic group (pyridinediyl group, furandiyl group, thiophendiyl group) and the like. The linking group may have a divalent amide group, carbamide group, sulfonamide group, ether group, ester group, thioether group, sulfine group, or the like. The linking group may be substituted with a halogen atom, an alkyl group, an alkenyl group, an aromatic group, a heterocyclic group, or the like.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent of a hydrogen atom, and the substituent of the hydrogen atom includes the aforementioned Rt ₁ and Rt ₂ And the same group as the aliphatic group, aromatic group or heterocyclic group which is a group represented by

The compound represented by the general formula (2) of the present invention preferably has an anion compound having a fluorinated chain (member β), a polyalkylene oxide chain at the center of the molecule, and cation portions at both ends. An onium phosphorus compound (member α) can be easily prepared by ionically bonding (salt forming) and used.

In the general formula (2) of the present invention, R ₁ , R ₂ , R ₃ ,
As a member α for supplying a cation moiety represented by R ₄ , R ₅ , R ₆ , L ₁ , L ₂ , Z ₁ and a phosphorus atom, for example,
As a counter ion, a halogen atom anion (chlorine ion, bromine ion, iodine ion) can be obtained from the market as a salt of an anion such as boron tetrafluoride ion or perchlorate ion, or can be synthesized by a known technique. For example, a polymer having a polyalkylene oxide group such as polyethylene glycol, polypropylene glycol, or a polyethylene-polypropylene block copolymer is obtained, and then can be synthesized by condensation or addition with a phosphonium compound.

In the general formula (2) of the present invention, R ₁ , R ₂ , R ₃ ,
Preferred specific examples of the member α for supplying a cation moiety represented by R ₄ , R ₅ , R ₆ , L ₁ , L ₂ , Z ₁ and a phosphorus atom are shown below.

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The member β for supplying the anion portions represented by Rt ₁ -A ₁ -and Rt ₂ -A _2-in the general formula (2) of the present invention is an alkali such as sodium, potassium or lithium salt. It is commercially available as a metal salt or can be obtained by a known synthesis method.

Preferred examples of the member β for supplying the anion portion represented by Rt ₁ -A ₁ -and Rt ₂ -A _2-in the general formula (2) of the present invention are shown below.

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The method of using the compound represented by the general formula (2) according to the present invention includes a method of using a member α (an inorganic salt of a cation portion) and a member β.
(2) a method of forming in a coating film by adding (an inorganic salt of an anion portion) to the same layer or a different layer of the photothermal material to form in the coating film;
A precipitation method in which the members α and β are added to water, an organic solvent, or a mixed solvent thereof and mixed to precipitate the compound represented by the general formula (2), and (3) hydrophilicity such as gelatin and gelatin derivatives. A member α and a member β are added to the hydrophilic medium, and the solid is set and solidified to leave the compound represented by the general formula (2) in the hydrophilic medium;
(4) A member α and a member β are added to a mixed solvent of water and an organic solvent such as ethyl acetate, butanol, toluene, n-hexane, dioxolan, acetonitrile, methyl ethyl ketone and methyl isobutyl ketone, and mixed. The compound represented by the formula (2) is separated from the organic phase, the inorganic salt unnecessary for the organic phase is separated into a water phase, the organic phase containing the compound represented by the general formula (2) of the present invention is separated, and the solvent is distilled off. Removal gives the target compound of the present invention represented by the general formula (2). Isoextraction or precipitation can be mentioned.

Specific examples of the compound represented by formula (2) of the present invention obtained from a preferred combination of a cation part and an anion part are shown below.

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The Rt ₁ and Rt ₂ aliphatic groups of the compound represented by the general formula (2) of the present invention preferably contain a fluorine atom. The replacement may be included. Rt ₁ may be an aliphatic group containing a fluorine atom and Rt ₂ may be an aliphatic group containing no fluorine, or vice versa.

The compound of the present invention represented by the general formula (2) can be added according to a known addition method. It can be added after being dissolved in alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, and polar solvents such as dimethyl sulfoxide and dimethylformamide. Further, fine particles having a particle size of 1 μm or less can be dispersed in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion and added. Many techniques have been disclosed for the fine particle dispersion technique. According to these techniques, a fine particle dispersion having an average particle diameter of 0.05 μm to 10 μm can be added.

The layer where the compound represented by the general formula (2) of the present invention is added to the sheet material may be located at a layer adjacent to the support, a layer via the layer adjacent to the support, a photosensitive layer or a BC layer.
It is preferred to use the protective layer of the layer, the amount added is 0.0
1 mg / m ^{2 to} 10 g / m ² , particularly preferably 0.1 mg / m ²
/ M ^{2 to 1} g / m ² . When it is added to a layer other than the protective layer, the amount is preferably 0.02 to 0.6 g / m ² .

The photosensitive silver halide used in the sheet material of the present invention can be produced by any method known in the field of photographic technology such as a single jet or double jet method.
For example, it can be prepared by any method such as an ammonia method emulsion, a neutral method and an acid method. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 as protective polymers for preparing photosensitive silver halide. , 565
No. 3,713,833, No. 3,748,14
No. 3, British Patent No. 1,362,970 or the like, a method using a polymer other than gelatin such as polyvinyl acetal, or a photosensitive halogen described in British Patent No. 1,354,186. Means for enzymatically decomposing gelatin in a silver halide emulsion, or US Pat. No. 4,076,53
As described in No. 9, various methods such as a method of omitting the use of a protective polymer by preparing photosensitive silver halide grains in the presence of a surfactant can be applied.

The silver halide grains preferably have a small grain size in order to obtain good image quality. 0.1 μm or less in average particle size, preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm.
The shape of the silver halide grains is not particularly limited,
There are cubic and octahedral so-called normal crystals and non-normal crystals, such as spherical, rod-shaped, and plate-shaped particles. The composition of the silver halide grains is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be achieved by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, US Pat. No. 4,036,650, British Patent 1,518,850, JP-A-51-22430,
Nos. 51-78319 and 51-81124. Also, when a part of the organic silver salt is converted to a photosensitive silver halide by a silver halide forming component, as described in U.S. Pat. An amide compound having a molecular weight may coexist.

In addition, these photosensitive silver halides may be used in order to prevent illuminance failure or to adjust the gradation.
Metals belonging to group III, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof, or a complex ion can be contained. It is particularly preferable to contain ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. As the above metals, W, Fe, Co, Ni,
Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u is preferable, and when it is used for a photosensitive material for plate making, it is preferably selected from Rh, Re, Ru, Ir, and Os. These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex.

The content of metal ions or complex ions is generally 1 × 10 ^-9 per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The organic silver salt used in the present invention has 16 carbon atoms.
Among them, needle-like crystals of behenic acid, arachidic acid, stearic acid and the like are particularly preferable. As is well known in photosensitive silver halide grains, the inverse relationship between the size of crystal grains and their covering power also holds for the photothermal material of the present invention. Since the image density is small and the image density is low, reducing the size of the organic silver salt gives a good result. In the present invention, the short axis of the organic silver salt is preferably 0.01 μm to 0.20 μm, the long axis is preferably 0.10 μm to 5.0 μm, the short axis is 0.01 μm to 0.15 μm, and the long axis is 0.10 μm.
It is more preferably not less than 4.0 μm. The particle size distribution of the organic silver salt is preferably monodispersed. The monodispersion of the organic silver salt is the standard deviation of the length of each of the minor axis and major axis.
The percentage of the value divided by each major axis is preferably 80.
%, More preferably 60% or less, still more preferably 4% or less.
0% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring the monodispersity, there is a method of calculating the standard deviation of the volume-weighted average diameter of the organic silver salt, and the 100-percent (coefficient of variation) of the value divided by the volume-weighted average diameter is preferably 80% or less. , More preferably 60% or less, still more preferably 40% or less. As a measuring method, for example, an organic silver salt dispersed in a liquid is irradiated with laser light, mathematically calculated from the fluctuation of the scattered light, and can be obtained from the obtained particle size (volume weight average diameter). Generally, the organic silver salt of the present invention is preferably 0.1 to 5 g / m ² ,
More preferably, it is 1 to 3 g / m ² .

The photothermal material used in combination with the organic silver salt and silver halide may be a previously prepared solution or dispersion of the organic silver salt,
Alternatively, a part of the organic silver salt can be converted to photosensitive silver halide by reacting a silver halide forming component with a sheet material containing the organic silver salt. The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. I can do things. That is, after mixing the organic silver salt and the compound to be tested and heating if necessary, X
It is to examine whether there is a peak peculiar to silver halide by a line diffraction method. Silver halide-forming components confirmed to be effective by such tests include inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Is disclosed in U.S. Pat. No. 4,009,0.
No. 39, No. 3,457,075, No. 4,003
No. 749, British Patent No. 1,498,956,
3-27027, 53-25420, etc. can be referred to.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is preferably from 0.001 mol to 0.7 mol, more preferably from 0.03 mol to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. , Usually the reaction temperature is-
It is preferable that the reaction time is 23 ° C. to 74 ° C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is set to the atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 1 per 1 part by mass of the organic silver salt.
00 parts by mass, preferably 0.1 to 10 parts by mass.

The reducing agent used in the present invention may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is used in one of the image forming layers.
-10% is preferred. In multilayer constructions, if the reducing agent is added to a layer other than the emulsion layer, a slightly higher percentage, about 2-15%, tends to be more desirable. A general reducing agent for a photothermographic material using an organic silver salt can be used. For example, bisphenol derivatives (2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1-bis (2- (Hydroxy-3,5-dimethylphenyl) -3,5,5-
Aldehydes and ketones such as trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, ascorbic acid derivatives (eg, 1-ascorbyl palmitate, ascorbyl stearate), benzyl and biacetyl , 3-pyrazolidone and indane-1,3-dione; tocopherol; Particularly preferred reducing agents are bisphenol derivatives. The reducing agent of the present invention is generally 0.1 to
It is preferably 15 g / m ² , more preferably 0.5 to 1 g / m ^2.
0 g / m ² .

As the binder of the sheet material (photothermal material) of the present invention, a material which is preferable as a place where silver halide, organic silver salt and reducing agent react is selected. For example, hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as methylcellulose and ethylcellulose, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, styrene-maleic anhydride copolymer, polyacrylamide, poly Examples include vinyl acetate, polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, and styrene-butadiene-acryl copolymer. After drying and forming a film, the coating film preferably has a low equilibrium moisture content.

Preferred Polymer (Polymer Binder)
Further, the glass transition point of the composition of -60 ° C to 80 ° C
And particularly preferably -50 ° C to 70 ° C. This is because if the glass transition point is high, the temperature for thermal development becomes high, and if the glass transition point is low, fogging is liable to occur, resulting in a decrease in sensitivity and softness. The water-dispersed polymer (polymer binder) is preferably dispersed in the form of fine particles having an average particle diameter in the range of 1 nm to several μm. The water-dispersed hydrophobic polymer (polymer binder) is called a latex and is widely used as a binder for water-based coating. In particular, a latex having a halogen atom in the molecule is preferable.

Examples of the latex (polymer binder) containing a halogen atom in the molecule which are preferable in the present invention include homopolymers of polyvinylidene fluoride and polyvinylidene chloride, and copolymers of vinylidene fluoride and vinylidene chloride with acrylic and olefinic compounds. Is mentioned. Polyvinylidene fluoride or polyvinylidene chloride has the general formula (CX ₂ −
CH ₂ ) _n , wherein X is a fluorine atom or a chlorine atom, n
Is a positive integer), and is a fluorine compound having an average fluorine content of 50% to 60% in one molecule, preferably a methylene group and a methylene fluoride group alternately bonded in a stable manner. .

The amount of the latex used for the purpose of obtaining water resistance as a binder is determined in consideration of coatability, but is preferably as large as possible from the viewpoint of moisture resistance. The content is preferably 50% or more and 100% or less, and 80% or more and 100% or less based on the total binder mass.

In the present invention, it is preferable that the protective layer and the BC layer on the photosensitive layer contain a matting agent, and the material of the matting agent used in the present invention may be any of an organic substance and an inorganic substance. For example, inorganic substances include silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 and the like. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic substances, US Patent No. 2,32
2,037, etc., Belgian Patent No. 625
No. 451, British Patent No. 981,198, etc .; starch derivatives, polyvinyl alcohol described in JP-B-44-3643, etc .; polystyrene or polymethacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic matting agents such as polyacrylonitrile described in 3,079,257 and the like and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.
The matting agent used in the present invention has an average particle size of 0.5 μm
To 10 μm, more preferably 1.
0 μm to 8.0 μm. The monodispersity of the particles is 50
% Or less, more preferably 40% or less, particularly preferably 20% or less. Here, the monodispersity of the particles is represented by a number obtained by dividing the standard deviation of the particle size by the average value of the particle size and multiplying by 100. The method for adding the matting agent according to the present invention may be a method in which the matting agent is dispersed in advance and applied, or a method in which the matting agent is sprayed before the drying is completed after applying the coating liquid. You may. When a plurality of types of matting agents are added, both methods may be used in combination.

The sheet material (photothermal material) of the present invention is a material which forms a latent image on silver halide by light to form a photographic image by heat development, and comprises a reducible organic silver salt and a catalytically active amount of halogen. It is preferable that the photothermal material contains a silver halide, a hydrazine derivative, a reducing agent, and, if necessary, a color tone agent for suppressing the color tone of silver in a state of being usually dispersed in a binder. The photothermal material of the present invention is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C to 200 ° C) after exposure. Heating includes a one-step method of heating at a constant temperature for a fixed time and a method of stepwise heating such as preheating, main heating, and post-heating, and the heating method can be appropriately selected. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.
This reaction process proceeds without supplying a processing liquid such as water from the outside.

It is preferable to add a color tone agent to the sheet material (photothermal material) of the present invention. Examples of suitable toning agents are R
No. 17029, which includes the following:

Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (for example, 4- (1-naphthyl)
Phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,
4-polyhalomethane compound dione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-
Methyl phthalazinone + sodium p-trisulfonate); a combination of a polyhalomethane compound and phthalic acid;
Polyhalomethane compounds (including adducts of polyhalomethane compounds) with maleic anhydride and phthalic acid, 2,3-
Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinedione Benzoxazine, naphthoxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg,
2,4-dihydroxypyrimidine); and tetraazapentalene derivatives (e.g., 3,6-dimercapto-1,
4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene).

Examples of the sheet material (photothermal material) of the present invention include, for example, JP-A-63-159814 and JP-A-60-14033.
No. 5, 63-231437, 63-259651
No. 63-304242, No. 63-15245,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
No. 175 and No. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure No. 1
7643 IV-A (p. 23, December 1978) and 1831X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34
Compounds described in Nos. 078, 9-54409 and 9-80679 are preferably used.

As the support, supports such as paper, synthetic paper, nonwoven fabric, metal foil, polyester such as polyethylene terephthalate and polyethylene naphthalate, and plastic films such as polycarbonate and polypropylene can be used. A composite sheet may optionally be used.

One of the preferred embodiments of the layer constitution of the sheet material (photothermal material) of the present invention is to provide an undercoat layer on a support,
An H layer, a photosensitive layer, an intermediate layer, and a protective layer are sequentially provided. Similarly, a photosensitive layer may be provided on the opposite side of the support, or a subbing layer, a conductive layer, a BC layer, and a BC protective layer may be provided.
It is preferred that these layers be provided simultaneously on a double-sided or single-sided emulsion surface by a known technique.

In the present invention, the exposure is preferably performed by laser scanning exposure. However, it is preferable to use a laser scanning exposure machine in which the angle between the exposed surface of the photothermal material and the scanning laser beam does not become substantially perpendicular. . here,
"Never be substantially perpendicular" means that the angle is most perpendicular to the surface during laser scanning, preferably 55 degrees or more and 88 degrees or more.
Degrees or less, more preferably 60 degrees or more and 86 degrees or less, still more preferably 65 degrees or more and 84 degrees or less, and most preferably 70 degrees or more and 82 degrees or less. The beam spot diameter on the exposed surface of the photothermal material when the laser beam is scanned on the photothermal material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. The lower limit of the beam spot diameter is 1
0 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of unevenness like interference fringes. Exposure in the present invention is preferably performed using a laser scanning exposure machine that emits a scanning laser beam that superimposes a plurality of wavelength lights. Image quality deterioration such as exposure unevenness and interference fringe-like unevenness is reduced as compared with a single mode scanning laser beam. To superimpose a plurality of wavelengths, there are a method using a synthetic wave mixed wave, a method using return light via a reflection mirror, and a method using a high frequency superposition. The superimposed wave has a single exposure wavelength, and usually has an exposure wavelength distribution of 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm. At the time of superimposition, it is preferable to control the intensity and amplitude of the laser beam and synthesize the laser beams.

[0175]

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

<< Description of the Inventions of Claims 1 to 8 of the Present Invention >> Example 1 [Production of Subbed Photographic Support] A polyethylene terephthalate support having a thickness of 175 μm was coated on both sides with 8 w / m ² · min. Apply a corona discharge treatment, and apply the following undercoating solution a on one surface
-1 is applied to a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1. On the other side, the undercoat coating solution b-1 shown below has a dry film thickness of 0.8 μm. The coating was dried as described above to obtain an undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30 parts by mass) t-butyl acrylate (20 parts by mass) Styrene (25 parts by mass) Copolymer latex liquid of 2-hydroxyethyl acrylate (25 parts by mass) (Solid content: 30% by mass) 270 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finished to 1 liter with water.

<< Undercoat Coating Solution b-1 >> Butyl acrylate (40 parts by mass) Styrene (20 parts by mass) Copolymer latex liquid of glycidyl acrylate (40 parts by mass) (solid content 30% by mass) 270 g Hexamethylene-1 , 6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 w / m ² · min is applied to the upper surface of the lower layer, and the lower layer upper layer coating solution a-2 is coated on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. As the upper layer A-2, the undercoating layer B-1 having an antistatic function is coated on the undercoating layer B-1 with the following undercoating layer coating solution b-2 so as to have a dry film thickness of 0.8 μm.
2 was applied.

<< Coating Solution a-2 for Subbing Upper Layer >> Gelatin Mass of 0.4 g / m ² Silica Particles (Average Particle Size: 3 μm) 0.1 g Finished to 1 liter with water.

<< Lower Coating Upper Layer Coating Solution b-2 >> Styrene butadiene copolymer latex solution (solid content: 20% by mass) 80 g Polyethylene glycol (weight average molecular weight: 600) 6 g Finished to 1 liter with water.

Preparation of silver halide grain emulsion A 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0, and 370 ml of an aqueous solution containing 74 g of silver nitrate was added. An aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Then 4
0.3 g of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8%. 100] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, followed by addition of 0.1 g of phenoxyethanol,
The pH was adjusted to 5.9 and the pAg was adjusted to 7.5 to obtain a silver halide grain emulsion A.

Preparation of Water-Dispersed Organic Silver Salt AB 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 (mol / L) aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. . While maintaining the temperature of this organic acid sodium salt solution at 55 ° C., the above silver halide grain emulsion A
(Containing 0.038 mol of silver) and 450 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of a 1 (mol / L) silver nitrate solution was added over 2 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, washing with deionized water and filtration were repeated until the conductivity of the filtrate reached 2 μS / cm, and water was added to a predetermined concentration to complete the process, thereby obtaining a water-dispersed organic silver salt AB.

Coating on Back Side The back layer (first layer) and the back layer protective layer (second layer) are curtain-coated on the undercoating upper layer B-2 on the support such that the respective compounds have the following amounts. Simultaneous multi-layer coating and drying were performed by the method.

Back layer (first layer) Inert gelatin 1.1 g / m ² Dye: C-1 12 mg / m ² Colloidal silica 12 mg / m ² Sodium dodecylbenzenesulfonate 13 mg / m ² Back layer protective film (second layer) Inert gelatin 0.8 g / m ² Matting agent (PMMA: average particle size 3 μ) 0.02 g / m ² Surfactant: N-propyldodecylsulfonamidoacetic acid 0.02 g / m ² Hardener: 1,2- Bis (vinylsulfonamide) ethane 0.02 g / m ² Fluorinated surfactant of the present invention (described in Table 1) 67 mg / m ² Coating on photosensitive layer side AH layer (first layer), photosensitive layer (second layer) A surface protective layer (third layer) was simultaneously coated on the undercoating upper layer A-2 on the support by a curtain coating method so that the following compounds were added in the following amounts.

AH layer (first layer) Inert gelatin 0.3 g / m ² Dye: C-2 8 mg / m ² Base generator: B 13 mg / m ² Photosensitive layer (second layer) The preparation of the photosensitive layer is as follows. An aqueous dispersion of the composition was added to water to prepare a coating solution. The coating solution was maintained at 35 ° C., and 3 (mol / mol) was passed through a salt bridge composed of a silver electrode and a 10% KNO ₃ salt solution.
L) The silver potential was measured using a silver electrometer formed from a reference electrode consisting of an Ag / AgCl electrode in the concentration solution, and then applied and dried to the following amount.

Water-dispersed organic silver salt AB An amount of 1.4 g / m ² as silver amount Binder: styrene-butadiene latex 5.6 g / m ² Spectral sensitizing dye: A 8 mg / m ² Antifoggant-1: 2-mercaptobenzimidazole 0.3 mg / m ² antifoggant -2: isothiazolone 1.2 mg / m ² antifoggant -3: 2 tribromomethylsulfonylpyridine 120 mg / m ² reducing agent: 1,1-bis ( (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 3.3 mmol / m ² The pH of the photosensitive layer coating solution was adjusted to 5.6.

Surface protective layer (third layer) Inert gelatin 1.2 g / m ² 4-methylphthalic acid 0.7 g / m ² Tetrachlorophthalic acid 0.2 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Silica matting agent (average particle size 5 μm) 0.5 g / m ² 1,2- (bisvinylsulfone acetamide) ethane 0.3 g / m ² Fluorinated surfactant of the present invention (described in Table 1) 67 mg / m ²

[0189]

Embedded image

<< Evaluation of Photographic Performance >> The heat-developable materials prepared for the normal humidity test sample and the high humidity test sample were exposed with a semiconductor laser sensitometer, and then heated using a heat drum (contact of the heat drum with the BC side). After 2 seconds at 110 ° C., the film was subjected to thermal development at 110 ° C. for 6 seconds. The normal humidity test was performed after the coated and dried thermal developing material was placed in an atmosphere of 25 ° C. and 60% RH for 24 hours for 3 days. After the thermal development, 55 pieces (5 ×
11) After storing for 3 days while applying a pressure of 5 kPa on the upper part, the central part of the same five consecutive sheets was extracted, and the same evaluation as above was performed. Laser light having a wavelength of 810 nm whose exposure wavelength is close to the absorption maximum of the dye was used as the exposure laser light, and the angle between the exposure laser light and the exposed surface of the selected heat developing material was 90 degrees. that time,
Exposure and development were performed in a room conditioned at 25 ° C. and a relative humidity of 54%.

The density of the obtained image with respect to fog and exposure was measured by a densitometer. Sensitivity is fog +0.3
The evaluation was made based on the reciprocal of the ratio of the exposure amount giving a high density. It was expressed by relative evaluation with reference to 1.

The scratch resistance was determined by applying a 5k weight to the protective layer on the photosensitive layer side with a wire brush for scratch resistance evaluation before developing the sample stored at normal humidity.
Rubbing 5 times while applying Pa, 20 people visually evaluated the degree of scratching, and the average value is shown. The evaluation is based on a five-rank system, with 5 being the best level, 1 being the worst level, and 3 being the middle. Two or more are practical.

The evaluation of dirt was performed by placing a test piece in a developing machine for 200 m.
^{After 2} treatments, the stain on the film was visually evaluated by 20 persons in five steps, and the average value was shown. Here, similarly, in the 5-rank system, 5 indicates the best level, 1 indicates the worst level, and 3 indicates the middle level. Two or more are practical.

Table 1 shows the results of the evaluation.

[0195]

[Table 1]

As is apparent from Table 1, when the fluorine-based surfactant (copolymer compound) of the present invention is used (the constitution of the first aspect of the present invention), storage stability under high humidity and scratch resistance are improved. You can see that it is good and hard to get dirty. The total mass of all the Rf group-containing monomer units of the fluorosurfactant is 2% of the copolymer.
It is understood that when the content is 5% by mass or more, the contamination increases.

Example 2 A sample was prepared and evaluated in the same manner as in Example 1, except that an anionic fluorinated surfactant having an Rf group was selected from the preferred specific examples, and as shown in Table 2. The fluorine-based surfactant (copolymer compound) of the present invention was added to the protective layer in an equimolar amount.

[0198]

[Table 2]

As is clear from Table 2, when the fluorine-based surfactant (copolymer compound) of the present invention is used in combination with the anionic fluorine-based surfactant having an Rf group (claim 2 of the present invention). It can be seen that the composition of the present invention) has improved storage stability, scratch resistance and stain characteristics.

Example 3 A sample was prepared in the same manner as in Example 1, except that the fluorosurfactant (copolymer mixture) of the present invention further incorporating a monomer having a glycidyl group (Gy) is preferred. As selected from specific examples, as shown in Table 3, an equimolar amount of the fluorine-based surfactant (copolymer compound) of the present invention was added to the protective layer.

Further, the combined effect of the anionic fluorine-based surfactant was simultaneously evaluated. Table 3 shows the evaluation results.

[0202]

[Table 3]

As is clear from Table 3, the use of the glycidyl group-containing fluorosurfactant (copolymer compound) of the present invention improves the storage stability under high humidity, the scratch resistance, and reduces the contamination. I understand. Further, it can be seen that the use of an anionic fluorine-based surfactant (the structure of the invention according to claim 3 of the present invention) further improves scratch resistance and dirt.

Example 4 A heat developing material was prepared in the same manner as in the sample of Example 3, except that lithium ion was added to evaluate the performance.

The lithium ions were added as counter ions of (a) lithium bromide, (b) lithium iodide, and (c) an anionic fluorinated surfactant. In the counter ionization of the anionic fluorine-based surfactant, the carboxylic acid and the sulfonic acid of the fluorine-containing aliphatic group (Rf) were neutralized with lithium hydroxide and taken out as a lithium-chlorinated compound. In the cases (a) and (b), the amounts added were equimolar to the anionic fluorine-based surfactant.

Table 4 shows the above progress, and Table 5 shows the results.

[0207]

[Table 4]

[0208]

[Table 5]

As is clear from Tables 4 and 5, it can be seen that when used to contain the lithium ion of the present invention (the structure of the invention of claim 4 of the present invention), the scratch resistance and the stain characteristics are improved.

Example 5 A sample was prepared in the same manner as in Example 4, except that latex was used as a binder instead of gelatin for the surface protective layer. The ratio in which gelatin was replaced by latex was shown as a ratio to the total binder.

[0211]

[Table 6]

As is evident from Table 6, when latex is used (the constitution of the invention according to claims 6 and 7 of the present invention), it has excellent scratch resistance and is hardly stained.

Example 6 Processing was performed in the same manner as in Example 5 except that the same heat developing material as in Example 5 was used as shown in Table 7, except that a pressing roller was used instead of the heat drum of the heat developing machine. Adopted. The sample was developed by changing the material of the pressing roller. The holding roller, that is, the heat developing roller, has a platinum catalyst of 200 mm.
Using a heat developing roller containing 36% of a material having the following composition in a polyorganosiloxane having a polymerization degree of 8800 used in ppm, the dirt on the roller when the heat developing material was treated in an amount 20 times the area of the roller was visually evaluated. . The smoothness is
The change in the thickness of the roller between the portion where the test piece passed and the portion where the test piece did not pass was visually evaluated. Rank 5 represents the best level, rank 1 represents the worst level, and rank 3 represents an intermediate level. Table 7 shows the evaluation results. Specific examples of the material blended in the polyorganosiloxane roller (1): carbon black having an average particle diameter of 0.6 μm (comparative material) (2): silica having an average particle diameter of 0.5 μm (3): average particle diameter of 0.5 μm (4): Hematite particles having an average particle diameter of 0.6 μm (5): 10% by mass of the particle surface of (3) with alumina (6): 10% by mass of the particle surface of (3) with silica Partial surface treatment (7): Surface treatment of surface particles of (3) with silica and alumina at 5% by mass each. (8): Particles of (3) doped with 14% by mass of manganese. (9): Particles of (4). 10% by mass surface treatment of the particle surface with alumina (10): 10% by mass surface treatment of the particle surface with silica (11): Surface particles of (4) with silica and alumina, each of 5
Mass% surface treatment (12): For comparison (no compound material)

[0214]

[Table 7]

As is clear from Table 7, when metal oxide or surface-treated metal oxide is used for the pressing roller (constitution of the invention according to claim 8 of the present invention), it is possible to prevent the generation of dirt on the roller, It can be seen that the durability increases.

<< Description of the Inventions of Claims 9 to 16 of the Present Invention >> Example 7 Preparation of Compound of the Present Invention Represented by General Formula (1) 0.1 (mol / L) Concentration of Compound of Member A 1 part by mass of an aqueous solution and a 0.1 (mol / L) concentration aqueous solution 1 of the compound of the member B
3 parts by mass of n-butanol was mixed with 3 parts by mass of the compound, and then the compound represented by the general formula (1) of the present invention was salted out and extracted from the butanol phase. The obtained compound represented by the general formula (1) of the present invention was used in Examples.

Preparation of Subbed Photographic Support A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 8 w / m ² · min on both sides, and the following subbing coating solution a-1 was dried on one side. It is applied to a thickness of 0.8 μm and dried to form an undercoat layer A-1. On the opposite surface, an undercoat coating solution b-1 shown below is applied to a dry thickness of 0.8 μm. And dried to obtain an undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30 parts by mass) t-butyl acrylate (20 parts by mass) Styrene (25 parts by mass) Copolymer latex liquid of 2-hydroxyethyl acrylate (25 parts by mass) (Solid content: 30% by mass) 270 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finished to 1 liter with water.

<< Undercoating Coating Solution b-1 >> Butyl acrylate (40 parts by mass) Styrene (20 parts by mass) Copolymer latex liquid of glycidyl acrylate (40 parts by mass) (solid content 30% by mass) 270 g Hexamethylene-1 , 6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A corona discharge of 8 w / m ² · min is applied to the upper surface of the lower layer, and the lower layer upper layer coating solution a-2 is coated on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. As the upper layer A-2, the undercoating layer B-1 having an antistatic function is coated on the undercoating layer B-1 with the following undercoating layer coating solution b-2 so as to have a dry film thickness of 0.8 μm.
2 was applied.

<< Coating Solution for Undercoating Upper Layer a-2 >> Gelatin Mass of 0.4 g / m ² Silica Particles (Average Particle Size: 3 μm) 0.1 g Finished to 1 liter with water.

<< Undercoat Upper Layer Coating Solution b-2 >> Styrene butadiene copolymer latex solution (solid content: 20% by mass) 80 g Polyethylene glycol (weight average molecular weight: 600) 6 g Finished to 1 liter with water.

Preparation of Water-Dispersed Organic Silver Salt B 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 (mol / L) aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. . While maintaining the temperature of the above-mentioned organic acid sodium solution at 55 ° C., 760.6 ml of a 1 (mol / L) silver nitrate solution was added over 2 minutes.
After stirring for minutes, water-soluble salts were removed by filtration. afterwards,
Water washing with deionized water and filtration were repeated until the conductivity of the filtrate became 2 μS / cm, and water was added to a predetermined concentration to finish, whereby a water-dispersed organic silver salt B was obtained.

Coating on Back Side The back layer (first layer) and the back layer protective layer (second layer) are curtain-coated with the first and second layers on a support so that the respective compounds have the following amounts. Simultaneous multi-layer coating and drying were performed by the method.

Back layer (first layer) Inert gelatin 1.1 g / m ² Dye: C-1 12 mg / m ² Colloidal silica 12 mg / m ² Sodium dodecylbenzenesulfonate 13 mg / m ² Back layer protective film (second layer) Inert gelatin 0.8 g / m ² Matting agent (PMMA: average particle size 3 μ) 0.02 g / m ² Surfactant: N-propyldodecylsulfonamidoacetic acid 0.02 g / m ² Hardener: 1,2- Bis (vinylsulfonamide) ethane 0.02 g / m ² Compound represented by formula (1) of the present invention (described in Table 8) 2 × 10 ⁻⁶ mol / m ² Photosensitive layer surface side coating AH layer (first layer) ), Photosensitive layer (second layer), intermediate layer (third layer)
Layer) and a surface protective layer (fourth layer) were simultaneously coated by a curtain coating method so that the following compounds were added in the following amounts.

AH layer (first layer) Inert gelatin 0.3 g / m ² Dye: C-2 '8 mg / m ² Base generator: B 13 mg / m ² Photosensitive layer (second layer) The preparation of the photosensitive layer is as follows. The aqueous dispersion of the composition was added to water to prepare a coating solution. The coating solution was maintained at 35 ° C., and 3 (mol / mol) was passed through a salt bridge composed of a silver electrode and a 10% KNO ₃ salt solution.
L) The silver potential was measured using a silver electrometer formed from a reference electrode consisting of an Ag / AgCl electrode in the concentration solution, and then applied and dried to the following amount.

Silver halide grain emulsion A Amount that gives 0.1 g / m ² in terms of silver Aqueous organic silver salt B Amount that gives 1.3 g / m ² in terms of silver Binder: styrene-butadiene latex 5.6 g / m 2 ² antifoggants -1: 2-mercaptobenzimidazole 0.3 mg / m ² antifoggant -2: isothiazolone 1.2 mg / m ² antifoggant -3: 2 tribromomethylsulfonylpyridine 120 mg / m ² reducing agent : 1,1-bis (2-hydroxy-3,5-dimethylphenyl-3,5,5-trimethyl) hexane 3.3 mmol / m ² The pH of the photosensitive layer coating solution was adjusted to 5.6.

Intermediate layer (third layer) Inert gelatin 0.8 g / m ² 5-isopropylphthalazine 0.2 g / m ² 4-methylphthalic acid 0.3 g / m ² Tetrachlorophthalic acid 0.1 g / m ² tetra Chlorophthalic anhydride 0.3 g / m ² Colloidal silica 0.5 g / m ² 1,2- (Bisvinylsulfone acetamide) ethane 0.2 g / m ² Surface protective layer (fourth layer) Inert gelatin 1.2 g / m ² 4-methylphthalic acid 0.7 g / m ² tetrachlorophthalic acid 0.2 g / m ² tetrachlorophthalic anhydride 0.5 g / m ² silica matting agent (average particle size 5 μm) 0.5 g / m ² 1 2,2- (bisvinylsulfone acetamide) ethane 0.3 g / m ² Compound represented by the general formula (1) of the present invention (described in Table 8) 2 × 10 ⁻⁶ / m ²

[0229]

Embedded image

<< Evaluation of Photographic Properties >> The heat-developable materials prepared for the normal humidity test sample and the high humidity test sample were subjected to imagewise exposure and heat development processing in synchronization with a YAG laser (output: 300 mJ / cm ² ). . The normal humidity test was performed after the coated and dried thermal developing material was placed in an atmosphere of 25 ° C. and 60% RH for 24 hours for 3 days. 35% 78% RH as high humidity test after thermal development
Under the atmosphere of the above, 60 pieces (5 × 12) of the same sample number were piled up 5 pieces each with the same sample number, and a pressure of 5 kPa was applied to the upper part, and stored for 3 days. A similar evaluation was performed. The density of the obtained image with respect to fog and exposure was measured by a densitometer.

The sensitivity was evaluated by the reciprocal of the ratio of fog + 0.3% of the exposure amount giving a higher density. It was expressed by relative evaluation with reference to 1.

The scratch resistance was determined by applying a 5k weight to the protective layer on the photosensitive layer side with a wire brush for evaluating scratch resistance before developing the sample stored at normal humidity.
Rubbing 5 times while applying Pa, 20 people visually evaluated the degree of scratching, and the average value is shown. The evaluation is based on a five-rank system, with 5 being the best level, 1 being the worst level, and 3 being the middle. Two or more are practical.

The transferability of the heat-developable material is as follows: a silicon core having a diameter of 2.5 cm and a silicon rubber having a thickness of 4 mm
Twenty-five pairs of the coated opposed rollers were arranged horizontally, and further 25 pieces were cut in quadrilaterals using a transport tester arranged vertically vertically, and the transportability was evaluated by treating 1000 sheets at a speed of 2 m / sec with a roller facing pressure of 5 kPa. . The charged voltage of the roller at that time was measured with a voltmeter for static electricity. Rank 5 when the voltage is less than 1 kV, Rank 1 when the voltage exceeds 5 kV, 1 kV to 2.3 k
V rank 4, rank 2.4kV-3.7kV rank 3,
3.8 to 5 kV was evaluated as rank 2. It can be practically used at rank 3 or higher.

Table 8 shows the results of the evaluation. The comparative compound a is the following compound described in JP-A-7-233268.

[0235] Comparative Compound _{a: C 8 F 17 SO 3} - · N + H
_{3 (CH 2 CH 2 O)} 12 CH 2 CH 2 N + H 3 · - O 3 SC 8 F 17

[0236]

[Table 8]

As is clear from Table 8, when the compound represented by the general formula (1) of the present invention is used (claims 9 and 10 of the present invention, particularly the constitution of the 11th invention), storage under high humidity It can be seen that they have good properties and scratch resistance and good transportability.

Example 8 A sample was prepared and evaluated in the same manner as in Example 7, except that silver halide grain emulsion A '(instead of silver halide grain emulsion A, spectral sensitizing dye was used instead of silver halide grain emulsion A) A in which 3 × 10 ^-4 mol was added per mol of silver halide). Exposure is performed with a semiconductor laser sensitometer, and then using a heat drum (contact of the heat drum with the BC side) at 100 ° C.
After preheating for 2 seconds, the film was subjected to thermal development at 110 ° C. for 6 seconds. As the laser wavelength, a laser that generates light having a wavelength of 810 nm was selected, and the angle between the exposed surface of the heat development material and the exposed laser light was 80 degrees. At that time, exposure and development were performed in a room conditioned at 25 ° C. and a relative humidity of 54%. Comparative compound a is the same as in Example 7. Here, dirt was evaluated instead of transportability. Evaluation of stain, after a test piece 200 meters ² was treated in the developing machine development temperature was raised to a temperature higher 10 ° C. 120 ° C. to facilitate detecting dirt, the dirt of the film 2
The evaluation was performed visually by a 5-point scale with 0 persons, and the average value is shown. Here, similarly, in the 5-rank system, 5 indicates the best level, 1 indicates the worst level, and 3 indicates the middle level. Two or more are practical.

The results are shown in Table 9.

[0240]

[Table 9]

As is clear from Table 9, when the compound represented by the general formula (1) of the present invention is used (claims 9 and 10 of the present invention, particularly the constitution of the 11th invention), storage under high humidity It can be seen that the film has good properties and scratch resistance and is hardly stained.

Example 9 A sample was prepared in the same manner as in Example 8, except that latex was used as the binder instead of gelatin for the surface protective layer. The ratio in which gelatin was replaced by latex was shown as a ratio to the total binder. The test for scratch resistance and dirt is the same as in Example 8, and the transportability is the same as in Example 7.

The results are shown in Table 10.

[0244]

[Table 10]

As is clear from Table 10, when latex is used (the constitution of the invention according to claims 12 to 14 of the present invention), it is excellent in scratch resistance and hardly stained.

Example 10 An experiment was carried out in the same manner as in Example 9, except that a pressing roller was used instead of the heat drum of the heat developing machine, and the material of the heat developing material was changed by changing the material of the pressing roller. Table 11
Described) was developed. That is, as the heat developing roller, a heat roller containing a polyorganosiloxane having a polymerization degree of 8800 using a platinum catalyst of 200 ppm and containing a material having the following composition at 36% by mass was used, and the heat developing material was treated in an amount 20 times the area of the roller. The dirt on the roller was visually evaluated. As for the smoothness of the roller, a change in the thickness of the roller between a portion where the test piece passed and a portion where the test piece did not pass was visually evaluated. Rank 5 represents the best level, rank 1 represents the worst level, and rank 3 represents an intermediate level.

Specific examples of materials mixed in polyorganosiloxane roller (1): No compounding material for comparison (comparative material) (2): Carbon black having an average particle diameter of 0.6 μm (comparative material) (3): Average particle Silica having a diameter of 0.5 μm (4): Hematite particles having an average particle diameter of 0.6 μm (5): Surface treatment of the particle surface of (3) with alumina at 10% by mass (6): Particle surface of (3) with silica 10% by mass surface treatment (7): Surface particles of (3) are each treated with 5% by mass of silica and alumina. (8): (4) Particle surface is treated with 10% by mass of alumina. (9): (4) (10): Surface particles of (4) are treated with silica and alumina for 5% each.
Table 11 shows the results of the mass% surface treatment.

[0248]

[Table 11]

As is clear from Table 11, when metal oxide or surface-treated metal oxide is used for the pressing roller (the structure of the invention of the sixteenth aspect of the present invention), it is possible to prevent the roller from being stained. It can be seen that the durability of the film increases.

<< Description of the Inventions of Claims 17 to 21 of the Present Invention >> Preparation of the Compound Represented by the General Formula (2) of the Present Invention
(Mol / L) 1 part by mass of an aqueous solution and the member β
0.1 (mol / L) of the compound of (inorganic salt of anion part)
One part of an aqueous solution having a concentration of 3 parts was mixed with 3 parts of an n-butanol solution, and the compound represented by the general formula (2) was salted out or extracted from the butanol phase. The obtained compound was used in the following examples.

Example 11 A polyethylene terephthalate sheet having a thickness of 100 μm was subjected to a corona discharge treatment of 30 w / m ² · min on both sides, and then a coating solution having the following composition was wet-coated at a thickness of 25 μm using a slit extruder. It was applied and dried under a blowing air of 60 ° C.

Butyl acrylate (30 parts by mass) t-butyl acrylate (20 parts by mass) Styrene (25 parts by mass) 2-hydroxyethyl acrylate (25 parts by mass) Copolymer latex liquid of glycidyl methacrylate 25 (2 parts by mass) ( (Solid content: 30% by mass) 1 g / m ² Silica matting agent (average particle size: 2.5 μm) 0.03 g / m ² Compound represented by formula (2) of the present invention (described in Table 12) 0.13 g / m ⁽² ) Evaluation of transportability In a room at 25 ° C. and a relative humidity of 15%, a stainless steel cylindrical rod having a diameter of 2 cm and a thickness of 3 mm was coated with silicone rubber.
50 cm pairs of opposing rollers of 0 cm are arranged at an interval of 1 mm, and the conveying device is set to 30 cm ×
A 25 cm sample is inserted, and the ejected sample is
A test was conducted in which the samples were stacked on a stocker, and samples were taken out with two catchers deaerated from the upper part of a 1 cm-diameter bowl shape molded of silicone rubber. The level at which 100 catchers can be reliably transported by the catcher was evaluated as 5, the rank with one or two catcher failures was evaluated as 4, 3, 3 to 5 as rank 3, the 6 to 10 as rank 2, and more than 1 as rank 1.

Evaluation of Scratch Resistance A room having a diameter of 30 μm and a length of 20 in a room at 25 ° C. and a relative humidity of 80%.
A slit brush in which 300 mm nylon fibers were bundled was set so that a load of 200 g was applied to every fifth pair of opposing rollers, and the degree of damage to the film film was examined. 5 wounds
The evaluation was made based on the evaluation sample by stepwise visual evaluation. 5 scratch-free levels, 1 to 5 are rank 4, rank 6 to 10
Books were ranked 3, and ranks 2 from 11 to 20, and rank 1 was 21 or more. Here, the generation of a flaw is compulsory for the test.

Evaluation of sticking As a compulsory test method, 5 cm × 5 in a room at 25 ° C. and 58% humidity.
After humidifying the sample pieces of 5 cm in size for 5 hours, five sample pieces were stacked and heat-sealed with a polyethylene sheet having a thickness of 30 μm, and a load of 10 kPa was applied from both ends and left at 40 ° C. for 3 days. After that, remove the sample and check the sticking condition of the sample by 5
Stepwise visual evaluation. Rank 5 is a level without sticking,
In terms of area, 1 to 9% was evaluated as rank 4, 10 to 24% was evaluated as rank 3, 25 to 44% was evaluated as rank 2, and 45% or more was evaluated as rank 1.

The results are shown in Table 12.

[0256]

[Table 12]

* Comparative compound a: JP-A-7-233268
The following compounds of Nos wherein ^{_{C 8 F 17 SO 3 - ·}} N + H 3 (CH 2 CH 2 O) 12 CH 2 CH 2
_{^{N + H 3 · - O 3}} SC 8 F 17 As apparent from Table 12, using the compound represented by the general formula (2) of the present invention (structure of the invention of claim 17 of the present invention), transport It is clear that it has good properties, scratch resistance, and stickiness.

Example 12 A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 10 w / m ² · min on one side thereof, and the other side was coated with the undercoating solution a-1 shown below and dried to form an undercoat layer A- It was set to 1. Also, the undercoating solution b-
1 was applied and dried to obtain an undercoat layer B-1.

Undercoating coating liquid a-1 butyl acrylate (30 parts by mass) t-butyl acrylate (20 parts by mass) styrene (25 parts by mass) copolymer latex of 2-hydroxyethyl acrylate (25 parts by mass) 0.6 g / m ² silica matting agent (average particle diameter 1 μm) 0.02 g / m ² sodium sulfate sodium salt of lauryl alcohol 0.02 g / m ² subbing coating solution b-1 butyl acrylate (40 parts by mass) styrene (20 parts by mass) Glycidyl acrylate (40 parts by mass) copolymer latex 0.06 g / m ² Silica particles (average particle size 1 μm) 0.02 g / m ² Lauryl alcohol sulfate sodium salt 0.02 g / m ² Subsequently, undercoat layer A -1 and undercoat layer B-1 were subjected to a corona discharge of 10 w / m ² .min.
-1, the following undercoating upper layer coating solution a-2 is applied and dried to form an undercoating upper layer A-2. On the undercoating layer B-1, the following undercoating upper layer coating solution b-2 is applied and dried. Upper layer B
-2.

Undercoating upper layer coating solution a-2 Gelatin 0.4 g / m ² Silica particles (average particle size 3 μm) 0.1 g / m ² Compound represented by formula (2) of the present invention (described in Table 13) 1 × 10 ^-4 mol / m ² 2-hydroxy-1,3-bis (vinylsulfonamido) propane 1 × 10 ^-4 mol / m ² Dodecylbenzenesulfonic acid sodium salt 0.015 g / m ² Undercoating upper layer coating solution b- 2 Styrene butadiene copolymer latex 0.04 g / m ² Tin oxide doped with 100 ppm indium (average particle diameter 30 nm) 0.14 g / m ² Copolymer of styrene sulfonic acid and maleic acid 0.2 g / m ² Compound represented by general formula (2) (described in Table 13) 1 × 10 ⁻⁴ mol / m ² The sample prepared above was subjected to a transport test in the same manner as in Example 11,
A scratch resistance test and a sticking test were performed.

The results are shown in Table 13. Comparative compound a is the same as in Example 11.

[0262]

[Table 13]

As is clear from Table 13, when the compound represented by the general formula (2) of the present invention is used (the constitution of the invention of claims 17, 20 and 21 of the present invention), transportability, scratch resistance,
It can be seen that the sticking is improved. Further, it can be seen that the performance is further improved when a fluorine atom is introduced (the structure of the invention of claim 21 of the present invention).

Example 13 Before preparing a sample, 100 p indium and rhodium were used.
An emulsion containing pm-doped silver iodobromide grains having an aspect ratio of 6 (average grain size of 2 μm) was prepared. This emulsion was chemically sensitized with tetraphenylselenourea and chloroauric acid so that the addition amount of selenium and gold atoms per silver halide grain was 134 ppm. On the undercoat layer B-1, a photosensitive layer and a protective layer having the following compositions were simultaneously applied. Coating speed is 2
The drying temperature was 36 m / min, the drying temperature was 43 ° C., and the drying time was 48 seconds.

Photosensitive layer Emulsion (as silver) 3 g / m ² sensitizing dye: B 1 × 10 ^-5 mol / silver 1 mol 1-phenyl-5-mercaptotetrazole 1 × 10 ^-4 mol / silver 1 mol 3- Methyl-5-hydroxy 1,3,3a, 7-tetrazaindene 6 × 10 ^-4 mol / silver 1 mol Protective layer of photosensitive layer Gelatin 1 g / m ² Silica matting agent (average particle diameter 3 μm) 0.2 g / m ² Dodecylbenzenesulfonic acid sodium salt 0.023 g / m ² 2-Hydroxy-1,3-bis (vinylsulfonamido) propane 0.1 g / m ² Compound represented by formula (2) of the present invention (Table 14) Description) 2 × 10 ⁻⁵ mol / m ^{2 On} the opposite side of the support, the following BC layer and a protective layer of the BC layer were coated in a multilayer manner under the same conditions as in the photosensitive layer and the protective layer.

BC layer Gelatin 1.0 g / m ² Dye: C-1 0.2 g / m ² Sodium dodecylbenzenesulfonate 0.02 g / m ² Copolymer of sodium styrenesulfonate and maleic acid 0.3 g / Protective layer of m ² BC layer Gelatin 1.0 g / m ² Silica matting agent 0.2 g / m ² Compound represented by formula (2) of the present invention (described in Table 14) 2 × 10 ⁻⁵ mol / m ²

[0267]

Embedded image

The obtained sample was evaluated for transportability, scratch resistance and sticking in the same manner as in Example 11. The evaluation of photographic performance was performed using an infrared semiconductor laser of 810 nm.
Exposure and development were performed while changing the exposure amount for an exposure time of ^-7 seconds. The sensitivity was calculated from the reciprocal of the fog + exposure amount of density 0.3 at this time, and the relative sensitivity was calculated as a reference 100.
Fog was determined by developing an unexposed sample. Development and fixing were performed using commercially available CDM671 and CFL691, and were performed at a developing temperature of 35 ° C., a developing time of 20 seconds, a fixing temperature of 25 ° C., a fixing time of 13 seconds, and washing with water for 20 seconds. The storability was evaluated by photographic performance after storage for 3 days at a temperature of 48% at 80% humidity, and the difference in fog before and after storage and the difference in sensitivity. Table 14 shows the obtained results. The same compound as in Example 11 was used as Comparative Compound a. The compound represented by the general formula (2) was used for both the photosensitive layer side and the BC layer side with the same type.

The results are shown in Table 14.

[0270]

[Table 14]

As is clear from Table 14, even in the case of the photosensitive layer containing no silver halide grains and no organic silver salt, good results can be obtained in both physical properties and photographic performance.

Example 14 Here, a sheet material having a photosensitive layer containing only organic silver was prepared using a polyethylene terephthalate support by the following method.

Coating on BC Layer Surface Side The BC layer (first layer) and the protective layer (second layer) of the BC layer were simultaneously coated and dried by a curtain coating method on a support so that the following compounds were applied in the following amounts. did.

BC layer (first layer) Inert gelatin 1.1 g / m ² Dye: C-2 12 mg / m ² Base generator: B 10 mg / m ² Colloidal silica 12 mg / m ² Sodium dodecylbenzenesulfonate 13 mg / m ² BC layer protective film (second layer) Inert gelatin 0.8 g / m ² Matting agent (PMMA: average particle size 3 μ) 0.02 g / m ² Surfactant: N-propyl dodecylsulfonamidoacetic acid 0.02 g / m ² Hardener: 1,2-bis (vinylsulfonamido) ethane 0.02 g / m ² Compound of the present invention represented by formula (2) (described in Table 15) 2 × 10 ⁻⁶ mol / m ² photosensitive Layer Coating The following compounds were simultaneously multi-layer coated by the curtain coating method so as to have the following amounts.

AH layer (first layer) Inert gelatin 0.3 g / m ² Dye: C-2 8 mg / m ² Base generator: B 13 mg / m ² Photosensitive layer (second layer) The preparation of the photosensitive layer is as follows. An aqueous dispersion of the composition was added to water to prepare a coating solution. The coating solution was kept at 35 ° C. and silver was measured using a silver electrometer formed from a silver electrode and a reference electrode consisting of a Ag / AgCl electrode in a 3 molar solution via a salt bridge consisting of a 10% KNO ₃ salt solution. After measuring the potential, it was applied and dried so as to have the following amount.

Water-dispersed organic silver salt B Amount which becomes 1.2 g / m ² in terms of silver binder: Styrene-butadiene latex 4.6 g / m ² Sensitizing dye: B 1.2 × 10 ^-5 mol / silver 1 mol antifoggants -1: 2-mercaptobenzimidazole 0.3 mg / m ² antifoggant -2: isothiazolone 1.2 mg / m ² antifoggant -3: 2 tribromomethylsulfonylpyridine 120 mg / m ² reducing agent: The pH of the 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 3.3 mmol / m ² photosensitive layer coating solution was adjusted to 5.6.

Intermediate layer (third layer) Inert gelatin 0.8 g / m ² 5-isopropylphthalazine 0.2 g / m ² 4-methylphthalic acid 0.3 g / m ² Tetrachlorophthalic acid 0.1 g / m ² tetra Chlorophthalic anhydride 0.3 g / m ² Colloidal silica 0.5 g / m ² 1,2- (Bisvinylsulfone acetamide) ethane 0.2 g / m ² Surface protective layer (fourth layer) Inert gelatin 1.2 g / m ² 4-methylphthalic acid 0.7 g / m ² tetrachlorophthalic acid 0.2 g / m ² tetrachlorophthalic anhydride 0.5 g / m ² silica matting agent (average particle size 5 μm) 0.5 g / m ² 1 2,2- (Bisvinylsulfone acetamide) ethane 0.3 g / m ² Compound of the present invention represented by formula (2) (described in Table 15) 2 × 10 ⁻⁶ / m ^{2 <<} Evaluation of photographic performance >> Normal humidity Test sample, The photothermal material produced in humidity test sample YAG laser (output 300 mJ /
cm ² ), imagewise exposure and heat development were performed in synchronization. In the normal humidity test, the photothermal material after coating and drying was applied for 24 hours and 25 hours.
The test was carried out after being placed in an atmosphere at 60 ° C. and a relative humidity of 60% for 3 days. After heat development, as a high humidity test, 75 pieces (5 × 15) of the same sample number were stacked on each other in an atmosphere of 35 ° C. and 78% RH, and a pressure of 5 kPa was applied to the upper portion and stored for 3 days. Five central portions of the same number were respectively extracted, and the same photographic performance evaluation as in Example 13 was performed. For the storage stability, the difference in fog and the difference in sensitivity between normal humidity storage and high humidity storage were determined.
Evaluation of physical properties was performed in the same manner as in Example 11. Comparative compound a
Was the same as in Example 11. The general formula (2)
The compounds represented by the same formulas were used for both the photosensitive layer side and the BC layer side.

The results are shown in Table 15.

[0279]

[Table 15]

As is clear from Table 15, when the compound represented by the general formula (2) of the present invention is used, physical properties (transportability,
It can be seen that both scratch resistance and sticking) and photographic performance (storability under high humidity) are good. It can also be seen that good results were obtained even in the case of a photosensitive layer containing only organic silver.

Example 15 Here, a photothermal material having a photosensitive layer containing silver halide grains and an organic silver salt was prepared. A sample was prepared and evaluated in the same manner as in Example 14, except that a water-dispersed organic silver salt AB was used in an amount of 1.2 g / m ² in terms of silver, and a silver halide grain emulsion A ′ was used in terms of silver. The amount used was 0.2 g / m ² . Exposure was performed using a semiconductor laser sensitometer, and then using a heat drum (contact of the heat drum with the BC side) at 100 ° C. for 2 hours.
After preheating for 2 seconds, the film was subjected to thermal development at 110 ° C. for 6 seconds. As the laser wavelength, a laser that generates light having a wavelength of 810 nm was selected, and the angle between the exposed surface of the photothermal material and the exposed laser light was 80 degrees. At that time, exposure and development were conducted at 25 ° C and relative humidity of 54%.
Went in a conditioned room. The storage property, transportability, scratch resistance and sticking were carried out in the same manner as in Example 13. Comparative compound a is the same as in Example 11. Table 16 shows the results.

[0282]

[Table 16]

As is clear from Table 16, when the compound represented by the general formula (2) of the present invention is used, it is found that transportability, scratch resistance, sticking property and storage stability are good.

[0284]

According to the first to eighth aspects of the present invention, the heat-developable material has a uniform and good coating surface after coating and drying, low fog, high sensitivity, and excellent storage stability before and after processing. It is possible to provide a heat-developable material which is excellent in transportability in the machine, hardly scratches on the surface and is not easily stained, and further, a heat development method which is excellent in transportability in the upper heat developer and is hardly stained.

According to the ninth to sixteenth aspects of the present invention, the coated surface of the heat-developable material after coating and drying is uniformly good, low fog, high sensitivity, and excellent preservability before and after processing. It is possible to provide a heat developing material which is excellent in transportability, is hardly scratched on the surface and is hardly stained, a heat development method which is excellent in transportability in an upper heat developing machine and is hardly stained, and an image forming method which suppresses exposure unevenness.

According to the seventeenth to twenty-first aspects of the present invention,
A sheet material with improved transportability can be supplied. In particular, sheet materials for recording printed images and medical images can be supplied. Further, it is possible to supply a sheet material for recording an image with light heat or heat rays which has not been subjected to improved wet processing without adversely affecting the photographic performance of the transportability.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of the structure of a heat developing material according to the first to eighth and ninth to sixteenth aspects of the present invention.

FIG. 2 converges and binds laser light having a plurality of spectra according to claims 9 to 16 of the present invention;
The figure which shows an example of the structure which exposes like an image.

FIG. 3 is a view showing an example of a heat developing machine used in the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Protective layer of photosensitive layer 2 Intermediate layer 3 Photosensitive layer 4 AH layer 5 Undercoat layer 6 Support 7 Undercoat layer 8 Conductive layer 9 BC layer 10 BC protective layer 11-13 Laser transmitters with different wavelengths 14-16 Laser light 18, 19, and 20 amplitude modulators 17 Light superimposing devices of different wavelengths 21 Superimposed laser light 31 Thermal insulation shielding of heat drum 32 Holding roller 33 Heat source 34 Heat drum 35 Preheating source 36 Cooling source 37 Preheating unit 38 Cooling unit 39 Introduction Film 40 Ejection film

Claims (21)

[Claims] 1. A heat-developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on a support, wherein at least one layer of the heat-developable material contains a fluorine-based surfactant. And the fluorine-based surfactant has an average molecular weight of 1,800 or more and less than 15,000, and the (i) group: an acrylate or Rf group having a fluorine-containing aliphatic group (hereinafter, also abbreviated as Rf group). And a group (ii): poly (oxyalkylene)
A copolymer with acrylate or poly (oxyalkylene) methacrylate, wherein all the monomer units of the acrylate having the Rf group or the methacrylate having the Rf group are 2 to 24% by mass of the copolymer, and the Rf A heat-developable material, wherein the group has from 1 to 26 carbon atoms and the Rf group has from 18 to 83% by mass of the Rf group of fluorine atoms. However, the fluorine-based surfactant, N- butyl perfluorooctane sulfonamide ethyl acrylate _{(C 8 F 17 SO 2 N} (C 4 H 9) CH 2 C
H ₂ OOCCH ＝ CH ₂ ) and (methyl-hepta-oxyethylene) acrylate (CH ₃ (OC ₂ H ₄ ) ₇ OOCCH
= CH ₂ ) and an average molecular weight of 15,000. 2. A photothermographic material comprising at least one layer on a support containing photosensitive silver halide grains, an organic silver salt and a reducing agent, wherein at least one layer of the photothermographic material contains at least two fluorine-based interfaces. A surfactant of the first type, wherein the first kind of the fluorosurfactant is a group (i): an acrylate having a fluorine-containing aliphatic group (Rf group) or a methacrylate having an Rf group; and a group (ii): A copolymer with poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate, wherein the total monomer units of the acrylate having the Rf group or the methacrylate having the Rf group are 2 to 86% by mass of the copolymer. And the Rf group has from 1 to 26 carbon atoms, and the Rf group has from 18 to 83% by mass or more of the fluorine atom of the Rf group, and the fluorine-based surfactant The second species, an anion surfactant having a fluorine-containing aliphatic group (Rf group), the Rf
A heat-developable material, wherein the group has a fluorine atom in an amount of 18 to 83% by mass of the Rf group. 3. A heat-developable material containing photosensitive silver halide grains, an organic silver salt and a reducing agent in at least one layer on a support, wherein at least one layer of the heat-developable material has at least two fluorine-based interfaces. A surfactant of the first type, wherein the first kind of the fluorosurfactant is a group (i): an acrylate having a fluorine-containing aliphatic group (Rf group) or a methacrylate having an Rf group; and a group (ii): Group (iii): a copolymer of poly (oxyalkylene) acrylate or poly (oxyalkylene) methacrylate and acrylate or methacrylate having a glycidyl group, and acrylate or Rf group having an Rf group. Methacrylate has a total monomer unit content of 2 to 86% by mass of the copolymer, and glycidyl group-containing acrylate or acrylate. Is 2 to 70% by weight of the total monomer units the copolymer of glycidyl methacrylate,
The Rf group has 1-26 carbon atoms and one of the Rf groups
The second type of the fluorine-containing surfactant having 8 to 83% by mass of fluorine atoms is an anionic surfactant having a fluorine-containing aliphatic group (Rf group), and the Rf group has a fluorine atom of the Rf group. 1
A heat-developable material having 8 to 83% by mass of fluorine atoms. 4. The heat-developable material according to claim 1, wherein the heat-developable material contains lithium ions in an amount of 1/1000 to 100 times the total amount of the fluorine-based surfactant. 5. The acrylate having a fluorine-containing aliphatic group (Rf group) or the methacrylate having an Rf group has an alkylsulfonamide group having 1 to 4 carbon atoms in a molecule thereof. 5. The heat-developable material according to 3 or 4. 6. The heat-developable material has a photosensitive layer and a protective layer, and contains latex as a binder in the photosensitive layer and the protective layer. The latex has a glass transition temperature of -60 ° C. to 80 ° C.
The heat-developable material according to claim 1, wherein the temperature is ° C. 7. The heat-developable material according to claim 6, wherein the latex contains a halogen atom in a molecule. 8. The method of claim 1, 2, 3, 4, 5, 6, or 7.
4. A heat development method, wherein the heat development material is processed using a pressing roller containing a metal oxide in silicone rubber as a heat development roller disposed opposite to a heat drum of a developing machine for processing the heat development material according to 1. 9. A heat-developable material containing a compound represented by the following general formula (1). Embedded image [Wherein, Q represents a nitrogen atom or a phosphorus atom, and R ₁ , R ₂ , R
₃ and R ₄ each represent a substituent to Q, and at least one of the substituents represents a group having a fluorine atom. A ₁ and A ₂ each represent an anionic group, L ₁ and L ₂ each represent a divalent linking group, and Z represents a group having an alkylene oxide unit. ] 10. The heat developing material according to claim 9, which contains an organic silver salt. 11. The heat-developable material according to claim 9, comprising an organic silver salt and silver halide grains. 12. The heat developing material according to claim 9, which comprises an organic silver salt, silver halide particles, a reducing agent and a latex. 13. The heat-developable material according to claim 9, wherein the latex is contained in an amount of 65 to 100% by mass based on the total mass of the binder. 14. The heat-developable material according to claim 12, wherein the latex has a halogen atom. 15. An image forming method, wherein a laser beam having a plurality of spectra is converged and bound on the heat-developable material according to any one of claims 9 to 14, and imagewise exposed. Method. 16. A temperature of 80 to 1 after exposing the heat-developable material according to claim 9 to a laser beam.
A heat development method, wherein heat development is performed by a drum or a roller heated to 80 ° C. 17. A sheet material characterized in that a layer on a support contains a compound represented by the following general formula (2). Embedded image [Wherein, P represents a phosphorus atom, Rt ₁ and Rt ₂ each represent an aliphatic group, an aromatic group or a heterocyclic group which may have a substituent, A ₁ and A ₂ each represent an anionic group, R _{1 to} R ₆ each represent a hydrogen atom or a substituent of a hydrogen atom, L ₁ and L ₂ each represent a divalent linking group, and Z ₁ represents a group having an alkylene oxide unit. ] 18. The sheet material according to claim 17, containing silver halide grains. 19. The sheet material according to claim 17, further comprising an organic silver salt. 20. The method according to claim 17, wherein the total number of repeating alkylene oxide units of the group having an alkylene oxide unit represented by Z ₁ in the general formula (2) is from 4 to 40. 20. The sheet material according to 19. 21. The method according to claim 17, wherein Rt ₁ and Rt ₂ are each an aliphatic group containing a fluorine atom.
21. The sheet material according to 8, 19 or 20.