JP2001174950A - Heat developable material and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable material excellent in scuffing resistance in development, less liable to stain, having high stability of photographic performance in storage, excellent also in the shelf stability of an image at high humidity after development and containing a spectral sensitizing dye excellent in heat decolorability and to provide a developing method in which the surface contamination of a heat roller due to the sticking and deposition of additives, the sensitizing dye, etc., from the heat developable material on the heat roller is not caused in development and the heat roller is excellent in smoothness. SOLUTION: In the heat developable material having a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder and a protective layer containing a matting agent on the substrate, a surface modifier of formula 1 is contained in the protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable material for forming an image by heat development. The present invention relates to improvement of high-humidity preservation of an image and improvement of dirt given to a heat roller or the like in a heat developing machine. Also, while achieving high sensitivity by using a thermal decoloring spectral sensitizing dye for sensitization of silver halide grains, it is decolorized after thermal development to prevent problems such as residual color on the image and color tone change. Thermal development without giving, and excellent storage stability of the heat-developable material, excellent in high-humidity preservation of the image obtained by developing the heat-developable material, less change in image color tone and deterioration of photographic performance About the material. Further, the present invention relates to a developing method using an improved heat roller which can perform long-term development without causing stains or deformation of a heat roller or the like during development by a heat developing machine.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for photothermographic materials which do not generate waste liquid due to wet processing from the viewpoints of environmental protection and workability in the fields of medical treatment and printing. There is a need for technology relating to photothermographic materials for photographic technology applications that can form images. Since these photothermographic materials are usually developed at a temperature of 80 ° C. or higher, they are called heat development materials.

Conventionally, a heat developing material of this type has a photosensitive layer containing high-sensitivity silver halide grains spectrally sensitized with a dye, an organic silver salt, and a reducing agent, and light irradiated toward the photosensitive layer. An anti-irradiation layer (A) that prevents light from passing through without being absorbed and being irregularly reflected at the interface of the support, the intermediate layer, the adhesive layer, and the like.
I) layer or a backing layer (BC), and a protective layer containing a matting agent is provided on the photosensitive layer and the BC layer.

In general, a heat-developable material requires a step of uniformly heating it after imagewise exposure in order to reduce the organic silver salt in the image area of the photosensitive layer. This step involves non-contact hot air or microwave development. Most of them are heated and developed in contact with a heat roller. At this time, it is important to prevent scratches due to the contact between the photosensitive surface and the heat roller, and to prevent the additives of the photosensitive layer from diffusing to the surface and adhering to the heat roller to cause contamination. It has become.

For this reason, it has been considered that the binder of the protective layer is crosslinked to prevent adhesion. US Pat. Nos. 4,886,739 and 4,942,115 describe crosslinking techniques.
No. 5,264,334 and the like disclose the use of a polyalkoxysilane compound. It is stated that these compounds are hydrolyzed by heat and exposed hydroxyl groups are bonded to a binder to enhance cross-linking. However, when the hydrolysis is performed by the heat, alcohol and moisture are released, and these are diffused into the support to cause curling of the support, thereby causing a conveyance failure. As a countermeasure against this, there are disadvantages such as the need for a diffusion preventing layer for water and alcohol.

On the other hand, US Pat. No. 4,828,971,
Each specification, such as US Pat. No. 5,891,610, describes the use of a polysilicate compound. Although this compound is less hydrolysable than polyalkoxysilane, it has drawbacks such as easy cracking of the dried film. Therefore, US Pat. No. 3,489,5, US Pat.
Nos. 67 and 3,885,965 disclose the addition of a polysiloxane compound as a lubricant. However, although these materials can improve the sliding of the film surface of the heat developing material, the flaw resistance of the heat developing material, contamination by the additive of the heat developing material to the heat roller, and the like are not examined at all.

On the other hand, a spectral sensitizing dye is used in a heat developing material to increase the sensitivity. However, when irradiating with image exposure, irradiation light not absorbed by the spectral sensitizing dye causes an interlayer boundary in the film to be exposed. And irregular reflection at the interface of the support, and the sharpness of the image is lost. In order to solve this, a dye that absorbs unnecessary irregularly reflected light is used for the AI layer and the BC layer. The AI layer is set mainly between the photosensitive layer and the support, and the BC layer is set on the opposite side of the photosensitive layer with respect to the support. The anti-irradiation dye and anti-halation dye used in the AI layer and the BC layer become residual colors if absorption remains in the visible part after development, hindering discrimination of a silver image. Therefore, it was necessary to reduce this absorption as much as possible.
For this reason, decolorizable dyes which are decomposed by heat during development and decolorized during development and which do not stain the thermally developed material and the heat roller during development have been studied, and many inventions have already been proposed. For example, JP-A Nos. 53-132334 and 60-111239, U.S. Pat.
5,009, 4,033,948, 4,52
4,128, 4,594,312, 4,99
4,356, 5,135,842, 5,31
4,795, 5,324,627, 5,38
4,237, EP 911,693, etc.

However, the problems such as residual color and stain after development of the above-mentioned heat developing material, and stains of the heat roller for development are not limited to the dyes of the AI layer and the BC layer, but rather to the spectral increase in the photosensitive layer. It turned out that there was a problem with the dye. As for the above spectral sensitizing dyes, conventionally, emphasis has been placed on the sensitizing effect, and dyes exhibiting sufficient thermal decoloring properties during development have not been used. Furthermore, conventional spectral sensitizing dyes are thermally decomposed during development and adhere to a heat roller, which is easily transferred to the next heat development material to cause contamination. Degradation of the storage stability of the performance, thermal decomposition products adhere to the heat roller, etc., which are repeatedly deposited and impair the uniformity of the heat roller surface, particularly the smoothness, causing uneven development, and the dye itself and decomposition products evaporate Then, it reacts with a material such as a heat roller to deteriorate physical properties. Therefore, a heat-resistant material with little chemical reaction was searched for a heat roller, and silicone rubber, norbornene-olefin rubber, and the like have been studied. However, the problem caused by the contamination of the spectral sensitizing dye has not been solved, and uniform development has been achieved. Was not done.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to provide excellent scratch resistance at the time of development, less occurrence of dirt on the heat roller, high stability of photographic performance at the time of storage, An object of the present invention is to provide a heat-developable material which is excellent in high-humidity storage stability of an image after development. A second object of the present invention is that the spectral sensitizing dye for achieving high sensitivity has an excellent thermal decoloring property, has less residual color after development, and therefore has a stable color tone of the obtained image. Another object of the present invention is to provide a heat-developable material having high photographic performance stability during storage, and particularly excellent in high-humidity storage stability of an image after development. Further, a third object of the present invention is to provide a non-uniform surface of the heat roller due to the adhesion and deposition of additives and sensitizing dyes from the heat developing material to the heat roller during development, and to provide a stable image for a long time. It is another object of the present invention to provide a developing method capable of forming a developed image. Since the heat-developable material of the present invention is subjected to image formation without being subjected to a fixing step after exposure and development, the storage stability of the heat-developable material before development and the storage stability of the image after development are important. It has become.

[0010]

The first and second aspects of the present invention are described.
The third object is achieved by the following configurations.

1. Photosensitive silver halide grains on a support,
In a heat developing material having a photosensitive layer containing an organic silver salt, a reducing agent and a binder and a protective layer containing a matting agent, the protective layer contains a surface modifier represented by the following general formula (1). A heat-developable material, characterized in that:

[0012]

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In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a group selected from an optionally substituted alkyl group, an alkoxy group, a hydroxy group, an aromatic group and a heterocyclic group;
And n represents zero or an integer of 1 to 100. However, m and n do not become zero at the same time.

2. The surface modifier has the following general formula (1-
a) a compound represented by the general formula (1-b), the general formula (1-c) or the general formula (1-d);

[0015]

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In the formula, A and B each represent a different alkylene oxide group having 1 to 4 carbon atoms which may have a substituent, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R
¹² represents a group selected from an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an aromatic group. L ¹ , L ² ,
L ³ , L ⁴ , L ⁵ and L ⁶ represent a divalent linking group and have 1 carbon atom
An alkylene group having 1 to 8 carbon atoms, an alkylene oxide group having 1 to 8 carbon atoms, m and n are integers of 1 to 1000, p,
q, r, s, s1, r1, u, v, u1 and v1 represent 0 or an integer of 1 to 100.

3. Wherein the photosensitive silver halide grains contained in the photosensitive layer of the heat-developable material are sensitized with a thermal decolorizable spectral sensitizing dye represented by the general formula (2). The heat-developable material as described above.

[0018]

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In the formula, Q ¹ and Q ² each represent an atom group necessary for forming a 5- or 6-membered ring which may have a substituent or a condensed ring belonging to the ring, and L ²¹ includes Q ¹ A divalent linking group having a methine chain linking the ring and the ring containing Q ² , R ²¹ and R
²² represents a substituent, and at least one of R ²¹ and R ²² is-
CH ₂ CO-X ₁ -R ²³ or ^{_{-CH 2 CO-N (R 24}} ) R
²⁵ , X ₁ represents an oxygen atom or a sulfur atom,
R ²³ , R ²⁴ and R ²⁵ each represent a substituent. Also, Q
On the ring containing a ring or Q ² contains a ^1, or on the condensed ring belonging to the ring containing a ring or Q ² contains a Q ^1, has a -T-R ²⁶ group. T represents SO, SO ₂ or a sulfur atom, R ²⁶ represents a substituent, and X ⁻ represents an anion.

4. The heat development according to the above item 3, wherein the photosensitive layer containing the photosensitive silver halide grains or a layer adjacent to the photosensitive layer contains a base generating precursor compound represented by the general formula (3). material.

[0021]

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In the formula, Z ¹ and Z ² each represent an atom group necessary for forming a 4- to 9-membered ring which may have a substituent;
³¹ represents a divalent linking group linking rings Z ¹ and Z ² . Y represents a substituent; n represents 0 or an integer of 1 to 4;
When adjacent to each other as described above, a ring may be formed.

5. (1) The photosensitive layer as described in (1) above, wherein the photosensitive layer containing the photosensitive silver halide grains or a layer adjacent to the photosensitive layer contains an acid anhydride represented by the general formula (4) or (5). 5. The heat-developable material according to any one of items 1 to 4,

[0024]

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In the formula, W ¹ , W ² and W ³ represent an atomic group constituting an acid anhydride nucleus, and R ⁴¹ , R ⁵¹ and R ⁵² each represent an aliphatic group which may have a substituent. Represents an aromatic group or a heterocyclic group, n and m represent 0 or an integer of 1 to 4,
Is 2 or more, adjacent substituents may form a condensed ring. L ⁵¹ represents a divalent linking group that connects the ring containing W ² and the ring containing W ³ .

6. A latex is contained in the photosensitive layer containing the photosensitive silver halide grains or in a layer adjacent to the photosensitive layer, and the glass transition temperature of the latex is from -60 ° C to 80 ° C.
The heat developing material according to any one of the above items 1 to 5, wherein the temperature is 0 ° C.

7. 7. The heat developing material as described in 6 above, wherein the latex contains a halogen atom in a molecule.

8. 8. A method for developing a heat-developable material, wherein the development of the heat-developable material according to any one of 1 to 7 is performed using a heat roller made of silicone rubber containing a metal oxide.

9. 9. The method of claim 8, wherein at least a part of the metal oxide is a surface-treated iron oxide.

10. Formula (4) or Formula (5)
10. The method for developing a heat-developable material as described in 8 or 9 above, wherein the method is carried out using a heat roller made of silicone rubber, which contains an acid anhydride represented by the formula and is heat-treated.

Hereinafter, the present invention will be described in detail. The present invention relates to a heat development material (1) for achieving the first object (claims 1 and 2), and a heat development material (2) for achieving the second object.
(Claims 3 to 7) and a development processing method (Claims 8 to 10) using the heat development material (1) or the heat development material (2) to achieve the third object.

[Thermal Developing Material (1)] The thermal developing material (1) of the present invention usually has at least one photosensitive layer and at least one non-photosensitive layer provided on a support. A protective layer containing a surface modifying agent of the general formula (1) of the present invention, particularly preferably a surface modifying agent of the general formula (2) and other matting agents provided on the photosensitive layer. It includes an undercoat layer and an AI layer provided below, a BC layer provided on the side opposite to the photosensitive layer with respect to the support, and a protective layer thereof. The photosensitive layer of the heat-developable material (1) contains photosensitive silver halide grains which may be sensitized with a spectral sensitizing dye, and the photosensitive layer or an adjacent layer contains an organic silver serving as a silver source. It contains a silver salt and a reducing agent for developing the silver salt to form a silver image, and more preferably a hydrazine compound or the like as a silver image hardening agent. The photosensitive layer and the non-photosensitive layer of the heat-developable material (1) contain a polymer binder which provides a place for thermal development, particularly preferably latex, and more preferably the polymer binder is cross-linked and cured. Acid anhydride to be added. In the first heat development material, an AI layer or a BC layer containing a dye for preventing irradiation or halation is provided as necessary. The light-sensitive layer of the first heat-developable material may contain a toning agent for adjusting the tone of the silver image, if necessary.

Hereinafter, the surface modifier of the general formula (1) contained in the protective layer of the heat-developable material of the present invention, particularly preferably the general formulas (1-a), (1-b) and (1-b) 1-c) and a surface modifier of the general formula (1-d), a matting agent, an ordinary spectral sensitizing dye which may be contained in the photosensitive layer, and further contained in an AI layer or BC layer provided as necessary. The dye will be described sequentially. The photosensitive silver halide grains contained in the photosensitive layer of the heat-developable material (1), the organic silver salt contained in the photosensitive layer or a layer adjacent thereto, a reducing agent, contained in the photosensitive layer or a layer adjacent thereto. The polymer binder, the hydrazine compound which may be contained as required, the color tone agent, the acid anhydride, and the like are common to the case of the heat development material (2) described later, and will be described in the section of the heat development material (2). I do.

<Surface Modifier of General Formula (1)> The general formula (1) representing the surface modifier of the present invention will be further described.

In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a group selected from an optionally substituted alkyl group, an alkoxy group, a hydroxy group, an aromatic group and a heterocyclic group; Represents zero or an integer of 1 to 100.
However, m and n do not become zero at the same time.

The alkyl group and the alkoxy group each preferably have 1 to 8 carbon atoms, and include a methyl group, an ethyl group,
Aromatic groups such as butyl group, octyl group, methoxy group, ethoxy group, butoxy group, octoxy group, etc. are p-methylphenyl group, p-methoxyphenyl group, p-cyanophenyl group, naphthyl group, 1,5-dimethyl Naphthyl group, 2,6
Examples of the hetero ring such as a dimethylnaphthyl group include a pyridyl group, a furyl group, an imidazole group, a triazole group, and a thiazole group. The halogen atom is preferably chlorine or bromine, and the aliphatic group may contain linear or branched, saturated or unsaturated.

<< Particularly Preferred Surface Modifier >> Of the surface modifiers of the general formula (1) of the present invention, particularly preferred surface modifiers are those represented by the general formulas (1-a), (1-b) and (1) -C) and (1-d). Each of these general formulas will be further described below.

The formula, A and B represent different alkylene oxide group having 1 to 4 carbon atoms which may have a substituent (e.g., ethylene oxide group, propylene oxide group and butylene oxide group, etc.), R ^5, R ⁶ , R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 each} represent an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group) or an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group) Group, ethoxy group, propyl group, octoxy group, etc.) and aromatic group (for example, phenyl group, naphthyl group, p-methylphenyl group, 2,6-dimethylnaphthyl group, etc.). L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ are 2
Represents an alkylene group having 1 to 8 carbon atoms (e.g., an ethylene group, a propylene group, a butylene group, and an octylene group); and an alkylene oxide group having 1 to 8 carbon atoms (e.g., an ethylene oxide group, a propylene oxide group). Group and butylene oxide, etc.), m and n are 1-10
00, preferably an integer from 1 to 300, p, q, r, s,
s1, r1, u, v, u1 and v1 are 0 or 1-1.
Represents an integer of 00.

The following general formulas (1-a), (1-b) and (1
Preferred specific examples of -c) and (1-d) are shown below for each general formula.

[0040]

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[0041]

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[0042]

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[0043]

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The silicone surface modifier of the present invention can be synthesized with reference to US Pat. Nos. 5,364,633 and 5,411,744. The method for adding these surface modifiers can be in accordance with 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. The addition amount is 1/1000 mass% to 10 mass% in the coating solution.
Is preferably added in the range of 1/100% by mass.
Is particularly preferably in the range of from 5 to 5% by mass.

<Matting Agent> The matting agent contained in the protective layer of the heat-developable material (1) of the present invention may be either an organic substance or an inorganic substance. Examples of the inorganic matting agent include Swiss Patent No. 330,158. Silica described in the specification, glass powder described in French Patent No. 1,296,995, alkaline earth metal described in British Patent No. 1,173,181 or carbonate such as cadmium, zinc or the like Salts and the like can be used. Examples of organic matting agents include starch described in US Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,198.
Starch derivatives described in each specification such as
No. 3643, polyvinyl alcohol described in Swiss Patent No. 330,158, polystyrene or polymethacrylate described in US Pat. No. 3,079,2.
No. 57, polyacrylonitrile, U.S. Pat. No. 3,022,169, polycarbonate, etc. 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 to 1
0 μm, more preferably 1.0 to
It is 8.0 μm. Further, a matting agent having a particle monodispersity of preferably 50 or less, more preferably 40 or less, and 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 following are specific examples of preferred matting agents:
Examples of types of matting agents are shown. (1) Polymethyl methacrylate (true spherical mean particle size 3μ)
m, monodispersion degree 8) (2) Silica matting agent (plate-like average particle diameter 3 μm, monodispersity degree 8) (3) Particles of (1) subjected to surface treatment (surface treatment
Perfluorooctyl methacrylate monomer fluorinated, 35% of the particle surface is coated with the monomer. (4) Surface treatment of particles of (1) (surface treatment is
It is fluorinated by the plasma method and has a fluorine ratio of 7
3%, and fluorine atoms are introduced from the particle surface to a thickness of 0.2 nm. <Spectral Sensitizing Dye> In the photosensitive layer of the heat-developable material (1) of the present invention, if necessary, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, and 6
No. 3-259651, No. 63-304242, No. 63
Nos. 15245, and US Pat. No. 4,639,4.
No. 14, No. 4,740,455, No. 4,741,
No. 966, No. 4,751,175, No. 4,83
Sensitizing dyes described in each specification such as 5,096 can be used. Useful sensitizing dyes for use in the present invention include, for example, R
search Disclosure Item17
Section 643 IV-A (p. 23, December 1978), It
em1831X (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-
No. 34078, No. 9-54409, No. 9-80679
The compounds described in (1) are preferably used.

<Dye of AI layer or BC layer optionally provided> The heat developing material (1) of the present invention may have an AI layer or a BC layer for preventing irradiation or halation of the heat developing material as necessary. The AI layer or B
The dye used in the C layer may be any dye that absorbs image exposure light, and is preferably the aforementioned U.S. Pat.
Thermal decolorable dyes described in JP-A-384,237 and the like are used. If the dye used is not heat-decolorable, the amount used is limited to a range that does not cause image damage to the heat-developable material. If the heat-decolorable dye is used, a necessary and sufficient amount of the dye is added. be able to.

[Thermo-developable material (2)] The heat-developable material (2) of the present invention is provided with a protective layer as in the case of the heat-developable material (1). General formula (2) in place of a normal spectral sensitizing dye as a sensitizer for grains
And a base-generating precursor compound of the general formula (3) having an action of accelerating the decoloring property of the decolorizable spectral sensitizing dye, if necessary. Contained in the layer.

In the case of the protective layer of the heat-developable material (1) of the present invention, among the surface modifiers of the general formula (1), the surface modifier of the general formula (2) is particularly used as the surface modifier. However, in the case of the protective layer of the heat-developable material (2) of the present invention, any of the surface modifiers contained in the general formula (1) has the effect of modifying the surface of the heat-developable material. Can be exerted almost equally. The reason is not clear,
A decolorizable spectral sensitizing dye, a base generating precursor compound, an acid anhydride, etc., contained in the photosensitive layer of the heat-developable material (2) of the present invention or an adjacent layer thereof, and a surface modifier of the general formula (1) It is presumed that this is due to the synergistic effect of the combination of.

<Thermal decolorizable spectral sensitizing dye of general formula (2)>
The general formula (2) showing the thermo-decolorable spectral sensitizing dye of the present invention will be further described.

In the formula, Q ¹ and Q ² each represent an atom group necessary for forming a 5- or 6-membered ring which may have a substituent or a condensed ring belonging to the ring, and L ²¹ includes Q ¹ A divalent linking group having a methine chain linking the ring and the ring containing Q ² , R ²¹ and R
²² represents a substituent, and at least one of R ²¹ and R ²² is-
CH ₂ CO-X ₁ -R ²³ or ^{_{-CH 2 CO-N (R 24}} ) R
²⁵ , X ₁ represents an oxygen atom or a sulfur atom,
R ²³ , R ²⁴ and R ²⁵ each represent a substituent. Also, Q
On the ring containing a ring or Q ² contains a ^1, or on the condensed ring belonging to the ring containing a ring or Q ² contains a Q ^1, has a -T-R ²⁶ group. T represents SO, SO ₂ or a sulfur atom, R ²⁶ represents a substituent, and X ⁻ represents an anion.

Preferred rings containing Q ¹ or Q ² include a pyridine ring, a pyrimidine ring, an imidazole ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, a thiadiazole ring and an isobenzofuran ring. Can be. L ²¹ represents a group that links the ring containing Q ¹ and the ring containing Q ^2, and is preferably a binding group in which 1 to 10 methine chains are arranged. R ²¹ , R ²² ,
As the substituent of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ , an aliphatic group having 1 to 30 carbon atoms which may have a substituent (for example, methyl group, ethyl group, butyl group, octyl group, Dodecyl group, eicosyl group, propenyl group, butenyl group, cyclohexyl group, acetylenyl group, etc.), aromatic group (for example, phenyl group, naphthyl group), or heterocyclic group (for example, pyridyl group, pyrimidyl group, imidazole group, Triazole group, thiazole group, benzotriazole group,
Benzimidazole group, benzoxazole group, furyl group, thiophenyl group, etc.). When R ²⁴ and R ²⁵ form a ring, a piperidine ring, morpholine ring, pyridazine ring, pyrimidine ring, piperazine ring, s-triazine ring, indole ring, benzimidazole ring, quinoline ring, carbazole ring, acridine ring, phenothiazine And a phenanthroline ring.

Preferred specific examples of the thermal decolorizable spectral sensitizing dye represented by the following formula (2) are shown below.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The heat-decolorable spectral sensitizing dye of the present invention can be synthesized according to a method for synthesizing a cyanine dye or a hemicyanine dye. The part of the substituent that contributes to decoloration can be synthesized with reference to European Patent No. 911,693. When added to silver halide, sensitization can be appropriately selected from 10 ^-2 mol to 10 ^-8 mol per mol of silver halide. The dye may be added before the chemical sensitization, but may be added after the chemical sensitization. At the time of addition, it may be added to an organic solvent such as an alcohol or a ketone, but can be added in the form of fine particles dispersed in water. The average particle diameter of the fine particles is 10 nm
It can be dispersed in a range from (nanometers) to 10 μm (micrometers), but as far as possible, fine particles and monodispersion are preferred. The monodispersity, expressed as a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter and multiplying by 100, is preferably 1 to 30, and more preferably 1 to 20.

<Base generating precursor compound of general formula (3)>
In addition, the base generating precursor compound of the general formula (3) which promotes the thermal decoloring property of the spectral sensitizing dye of the present invention has a base component and an acid component forming an ionic bond pair. Is decomposed into a base component and an acid component, whereby the decomposed base component acts on the dye as an active nucleophile and decolorizes.

The general formula (3) representing the base generating precursor compound of the present invention will be further described. In the formula, Z ¹ and Z ² represent an atomic group necessary for forming a 4- to 9-membered ring which may have a substituent, and L ³¹ represents a ring containing Z ¹ and a ring containing Z ² Y represents a monovalent substituent. n is 0 or 1
When n is 2 or more, adjacent substituents may form a ring.

Each of Z ¹ and Z ² is preferably an alkylene group having 1 to 5 carbon atoms, for example, a methylene group, a dimethylene group, a trimethylene group, a pentamethylene group and the like. Is also good. L ³¹ is a bonding group, each having 1 to 3 carbon atoms which may have a substituent.
It represents a group having two binding sites of a saturated or unsaturated aliphatic group, an aromatic group, and a heterocyclic ring. For example, ethylene group, propylene group, butylene group, isobutylene group,
Examples include an octylene group, a dodecylene group, a phenylene group, a biphenylene group, a naphthylene group, and compounds having a substituent at these carbon atoms. The base generating precursor compound of the present invention is disclosed in JP-B-7-59545 and JP-B-8-59545.
It can be synthesized according to the method described in JP-A-10321.

Preferred specific examples of the base-generating precursor compound represented by the general formula (3) are shown below.

[0066]

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[0067]

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[0068]

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The compound of the formula (3) of the present invention can be added according to a known 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. The addition amount can be selected from a range of 1/100 mol to 100 mol per mol of the thermal decoloring dye. A particularly preferable addition amount is to select a range from 1/10 mol to 10 times mol with respect to the thermal decoloring spectral sensitizing dye. In addition to dissolution in a solvent, fine particles having a particle size of 1 μm or less can be added by dispersing in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion, or homogenizer dispersion. 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 to 10 microns can be added. To use fine particles,
The monodispersity, expressed as a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter and multiplying by 100, is preferably 1 to 30, and more preferably 1 to 20.

<Materials Commonly Used in the Heat Developing Materials (1) and (2)> Next, they may be commonly used or used in the heat developing materials (1) and (2) of the present invention. An organic silver salt, a reducing agent, photosensitive silver halide particles, a hydrazine compound, a polymer binder, particularly a latex in the polymer binder, an acid anhydride of the general formula (4) or (5),
The color toning agent, other supports, and the like will be sequentially described.

<< Organic Silver Salt >> The organic silver salt contained in the heat-developable material of the present invention is a reducible silver source, and an organic acid, a heteroorganic acid and an acid polymer containing a reducible silver ion source. Salts and the like are used. Further, when the ligand is 4.0 to 1
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 0.0 are also useful. An example of a silver salt is Resea
rc Disclosure Nos. 17029 and 299
63, including: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salts of silver (eg, , 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl)
-3,3-dimethylthiourea and the like); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid (for example, formaldehyde, acetaldehyde,
Aldehydes such as butyraldehyde and salicylic acid,
Hydroxy-substituted acids such as benzylic acid 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid); silver salts or complexes of thiones (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4) -Thiazoline-2-thione and 3-carboxymethyl-4-methyl-4-thiazoline-2-thione); imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio Complexes and salts of silver and a nitrogen acid selected from -1,2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides.

<< Reducing Agent >> Examples of preferred reducing agents contained in the heat-developable material of the present invention are described in US Pat. No. 3,770,44.
No. 8, 3,773, 512, 3,593, 863
No., etc., and Research Disclo
Sure Nos. 17029 and 29996, and include:

Aminohydroxycycloalkenone compounds (eg, 2-hydroxy-3-piperidino-2-cyclohexenone); aminoreductone esters (eg, piperidinohexose reductone monoacetate) as precursors of the reducing agent; Hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea);
Aldehyde or ketone hydrazones (e.g., anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5- Dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline);
-Tetrazolylthiohydroquinones (e.g., 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g.,
1,2,3,4-tetrahydroquinoxaline); amide oximes; azines; a combination of aliphatic carboxylic acid arylhydrazides and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine; reductone and / or hydrazine; A combination of azines and sulfonamidophenols;
Cyanophenylacetic acid derivative; combination of bis-β-naphthol and 1,3-dihydroxybenzene derivative;
-Pyrazolones; sulfonamidophenol reducing agent; 2
-Phenylindane-1,3-dione and the like; chroman;
1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methyl) Phenyl) methane, bis (6-hydroxy-m-tri) mesitol (m
esitol), 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol)), ultraviolet-sensitive ascorbic acid derivatives; hindered phenols; 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0074]

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In the formula, R represents a hydrogen atom or a group having 1 to 1 carbon atoms
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, t- butyl ).

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

[0077]

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[0078]

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

<< Photosensitive Silver Halide Particles >> The photosensitive silver halide contained in the photosensitive layer of the heat-developable material of the present invention is:
Any method known in the field of photographic technology such as a single jet or double jet method, for example, an ammonia method emulsion, a neutral method, prepared in advance by any method such as an acid method, and then mixed with other components of the present invention. It can be mixed and introduced into the composition used in the present invention. In this case, in order to sufficiently contact the photosensitive silver halide and the organic silver salt,
For example, US Pat. Nos. 3,706,564 and 3,7 as protective polymers for preparing photosensitive silver halide.
No. 06,565, No. 3,713,833, No. 3,
No. 748,143 and British Patent No. 1,362,970. Means using a polymer other than gelatin such as polyvinyl acetal, and British Patent No. 1,3.
Means for enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in US Pat. No. 54,186, or photosensitive halide as described in US Pat. No. 4,076,539. By preparing silver particles in the presence of a surfactant, various means such as a means for omitting the use of a protective polymer can be applied.

The photosensitive 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. 0.1 μm or less in average particle size, preferably 0.01 to 0.1 μm, particularly 0.02 to 0.0
8 μm 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 the silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 0.1% by mass, based on the total amount of the silver halide and the organic silver salt described below. is there.

The photosensitive silver halide used in the photothermographic material of the present invention is also disclosed in British Patent No. 1,447,454.
As described in the specification, when an organic silver salt is prepared, a halogen component such as a halide ion is made to coexist with an organic silver salt-forming component, and silver ions are injected into the organic silver salt to form an organic silver salt. They 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 to expose a part of the organic silver salt 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 it. 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 specifications such as U.S. Pat. Nos. 4,009,039, 3,457,075, 4,003,749 and British Patent 1,498,956, and JP-A-53-27027. No. 53-25420, etc., one example is shown below.

[0085] generated in (1) above silver halide when inorganic halide is used: for example, halide (wherein M represented by MX _n, represents H, NH _4, and a metal atom, X is a halogen N represents M and H and NH ₄
Represents 1 when １ is a metal atom, and represents its valence when M is a metal atom. As the metal atom, lithium, sodium, potassium, cesium, magnesium, calcium, strontium,
Barium, zinc, cadmium, mercury, tin, antimony,
Chromium, manganese, iron, cobalt, nickel, rhodium, cerium, etc.) are used, and halogen molecules such as bromine water are also effective. (2) When onium halides are used: for example, quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, and trimethylbenzylammonium bromide; and quaternary phosphoniums such as tetraethylphosphonium bromide. Halides and tertiary sulfonium halides such as trimethylsulfonium iodide are used. (3)
When halogenated hydrocarbons are used: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-
2-methylpropane or the like is used. (4) When an N-halogen compound is used: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazone, N- Bromoxazolinone, N-chlorophthalazone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, N-bromo Urazole or the like is used. (5) When other halogen-containing compounds are used: For example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid,
Bromoethanol, dichlorobenzophenone and the like are used.

These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is from 0.001 mol to 0.7 mol, 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 −23 ° C. to 74 ° C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure.
This reaction is also preferably performed in the presence of the polymer used as the binder. The amount of the polymer used at this time is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.

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 performed by a chromium compound or a combination thereof. The method and procedure of this chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, and the like.
No. 22430, No. 51-78319, No. 51-811
No. 24 and other publications. Further, when a part of the organic silver salt is converted into a photosensitive silver halide by a silver halide forming component, as described in US Pat. No. 3,980,482, sensitization is achieved. A low molecular weight amide compound may coexist.

In addition, these photosensitive silver halides may be used in order to prevent illuminance failure and to adjust the gradation.
Metals belonging to Group 0, 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 preferably a six-coordinate complex represented by the following general formula.

General formula: [ML ₆ ] ^{m 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, and m is 0, 1-, 2- or 3
Represents-. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. A plurality of L may be the same or different. Particularly preferred specific examples of M include rhodium (Rh), ruthenium (Ru), and rhenium (Re).
And osmium (Os).

The content of metal ions or complex ions is generally 1 × 10 ⁻⁹ per mole 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.

<Hydrazine Compound> The photosensitive layer of the heat-developable material of the present invention or a layer adjacent thereto preferably contains a hydrazine compound as a high contrast agent for enhancing the contrast of a silver image. Examples of the hydrazine compound include column 1 of US Pat. No. 5,545,505.
Compounds H-1 to H-29 described in Nos. 1 to 20, and compounds 1 to 12 described in columns 9 to 11 of U.S. Pat. No. 5,464,738 are preferably used. These hydrazine compounds can be synthesized by a known method.

The hydrazine compound is added to the photosensitive layer and / or a layer adjacent to the photosensitive layer, and the amount of addition is uniform depending on the particle size of silver halide grains, halogen composition, degree of chemical sensitization, type of inhibitor, and the like. However, the range is preferably about 10 ^-6 to 10 ^-1 mol, and particularly preferably 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

<< Polymer Binder >> The polymer binder used in the photosensitive layer or the non-photosensitive layer of the heat-developable material of the present invention includes:
A material which is preferable as a place where silver halide, organic silver salt, and reducing agent react, a material which is preferable for a reaction in which a thermal decoloring dye is decolorized by heat of 80 to 200 ° C. or less, or a base generating precursor is rapidly heated to form a base Is selected so as to generate the Examples of the polymer binder include alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, polymers used by dissolving in polar solvents including dimethyl sulfoxide and dimethylformamide, and water-dispersed polymers. As the polymer binder of the heat developing material of the present invention, an aqueous dispersion polymer is preferable. Further, regarding the composition of the preferred polymer, the glass transition point is more preferably from -20 ° C to 80 ° C, particularly preferably from -5 ° C to 60 ° C. If the glass transition point is high, the temperature for thermal development is high, and if the glass transition point is low, fogging is likely to occur, resulting in a decrease in sensitivity and softness.

Examples of the polymer dissolved in the above-mentioned polar solvent and the like include cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, methylcellulose and ethylcellulose, starch and its derivatives, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, and polyacrylic acid. Sodium, polyethylene oxide, acrylamide-acrylate copolymer, styrene-maleic anhydride copolymer, polyacrylamide, sodium alginate,
Gelatin, casein, polystyrene, polyvinyl acetate,
Examples thereof include polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, and styrene-butadiene-acryl copolymer. After drying, after forming a film, the coating film preferably has a low equilibrium water content, and particularly preferably has a low water content, such as cellulose acetate, cellulose acetate butyrate, and poly (methyl methacrylic acid). Acrylates), poly (acrylic acid), poly (methacrylic acid), poly (vinyl chloride), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl) Acetals) (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
Examples include cellulose esters and poly (amide) s.

As the above-mentioned water-dispersed polymer, it is preferable to use fine particles having an average particle diameter in the range of 1 nm to several μm and dispersed in an aqueous dispersion medium. Latex is particularly preferred for the water-dispersed polymer because it is widely used as a binder for aqueous coating and can improve water resistance. The amount of 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.
0 mass% and 80 to 100 mass% are preferable.

<< Specific Examples of Latex >> Specific examples of preferred aqueous dispersion latex are shown below. In this example, styrene is St, methyl acrylate is MA, methyl methacrylate is MMA, ethyl acrylate is EA, and butyl acrylate is BA. , Isononyl acrylate
A, CA for cyclohexyl methacrylate, HEA for hydroxyethyl acrylate, HEMA for hydroxyethyl methacrylate, AA for acrylic acid, AAm for acrylamide, St-S for styrenesulfonic acid, AMPS for acrylamide-2-methylpropanesulfonic acid amide,
Isoprenesulfonic acid was converted to IP-S, 2-propenyl-4
-Nonylphenoxyethylene oxide (n = 10) sulfonic acid ester is abbreviated as PF-S, and the accompanying numbers represent mass composition ratios.

Specific examples of latex Monomer composition Molecular weight (million) Tg (1) EA97AA3 1-26 (2) EA100 2-29 (3) EA40BA57AA3 10-46 (4) EA97MMA3 13-23 (5) St20MMA30EA40BA8AA2 2038 (6) ) St10IP-S10MMA30EA50 246 (7) EA90AMPS10 5 -16 (8) MMA10EA88AMPS2 0.2 -15 (9) St30MMA20EA40BA5AA5 0.833 (10) CA60INA30IP-S10 3-46 (11) MMA50EA40AMP10A40MPS10A40MPS10AMAP1010A40APS10M10A40APS10APS10A40APS10APS10APS10A40APS10APS10A40APS10APM10A40APS10APS10A40APS10APM10A40APS As. S10 10 15 (13) EA90PF-S10 50-20 (14) MMA50EA40AAm10 20 22 15) St20MMA30EA50HEA10 10 23 (16) St10MMA30EA50HEMA10 10 18 (17) BA40St20EA30AA10 10 11 (18) CA60INA30MA10 20 -38 (19) CA60INA30AMPS10 4 -34 (20) CA50INA30EA10AMPS10 3 -32 (21) EA95AA5 10 -25 (22) EA97BA3 13 -26 (23) EA50BA47AA3 20 -36 (24) EA95MMA52-24 (25) St20MMA30EA39BA8AA3 532 (26) St15IP-S5MMA30EA50 0.233 (27) EA80AMPS20 0.823 (28) MM2EA8829PS32MMPS27 A20EA40BA5AA3 4 30 (30) CA50INA30IP-S20 10 5 (31) MMA40EA50AMPS10 50 33 (32) MMA25EA40St-S30 20 26 (33) EA80PF-S20 10 -16 (34) MMA50EA45AAm5 10 24 (35) St15MMA30EA50HEA5 10 23 (36) St10MMA35EA50HEMA5 20 33 (37) BA44St20EA30AA64-33 (38) CA64INA33MA33-36 (39) CA40INA40AMPS20 10-40 (40) CA53INA30EA10AMPS7 15-44 <Acid Anhydride> The acid anhydride to be added in the present invention is a monocarboxylic acid. The acid undergoes dehydration condensation of two molecules to form A-CO-O
In the formula, A and B may be substituents having a linear molecular structure, or a cyclic structure in which a part of A and B are bonded. And it may be a substituent. When the substituents A and B have a linear molecular structure, two molecules of the aliphatic monocarboxylic acid are formed by dehydration. For example, acetic anhydride, propanoic anhydride, butanoic anhydride, amylic anhydride, It includes caproic anhydride, lauric anhydride, stearic anhydride, sebacic anhydride, arachidic anhydride, behenic anhydride and the like, and the aliphatic carboxylic acid preferably has 1 to 30 carbon atoms. Substituent A
And B having a cyclic molecular structure include, for example, aromatic carboxylic acids represented by the general formula (4) or (5) including benzoic anhydride, pyridine carboxylic anhydride and derivatives thereof. Anhydrides are preferred. Hereinafter, general formula (4) or general formula (5) will be further described.

Where W¹And W^TwoMay have a substituent
Lists the atoms required to form a five- or six-membered ring
Then R⁴¹, R⁵¹And R⁵²Represents a substituent, and n
Is two or more, two adjacent substituents are a 5- or 6-membered ring
May be formed. L⁵¹Is ring W ¹And W^TwoJoin 2
A valent linking group;¹And W^TwoTwo adjacent positions on
When the substituents form a 5- or 6-membered ring with each other
Represents a group.

As the substituent of R ⁴¹ , R ⁵¹ and R ^52, an optionally substituted alkoxy group (methoxy group, ethoxy group, propyloxy group, butoxy group, octoxy group, dodecanoxy group, docosanoxy group, 2-ethyl Hexanoxy group), halogenated alkoxy group (trifluoromethoxy group, perfluorooctanoxy group), cycloalkoxy group (cyclohexanoxy group, cyclooctanoxy group, cyclopentanoxy group, etc.), aromatic group (Phenoxy group, naphthenoxy group, etc.), heterocyclic group (pyridyl group, furyl group, thiophenyl group, piperazyl group, imidazolyl group, triazole group, tetrazole group, etc.), alkylamino group (methylamino group, propylamino group, octylamino) Group, tetradecyl group), dialkylamino group (dimethylamino group, Ethylamino group, dioctylamino group), alkylthio group (methylthio group, ethylthio group,
Butylthio group, octylthio group), and the alkyl group portion preferably has 1 to 25 carbon atoms. Adjacent substituent R1
When and R2 form a ring, examples of the ring include a benzene ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a furyl ring, a thiophene ring, and a piperazine ring.

L ⁵¹ represents a —SO ₂ — group, a —SO— group, a —S—
SO ₂ —, —S—, —O—, —CONH—, —SO ₂ NH
-, -CONH- groups or a combination thereof with an aliphatic group, an aromatic group, a heterocyclic group or the like.

Preferred examples of the compound represented by formula (4) or (5) of the present invention are shown below.

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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Acid anhydrides preferably used in the present invention include:
A compound having a carboxylic acid group can be synthesized by ordinary dehydration condensation, or a commercially available product can be obtained. When it is added to the heat-developable material, it 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. Also,
Fine particles having a particle size of 1 μm or less can be added by dispersing in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion, or homogenizer dispersion. 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 to 10 microns can be added.

<< Tone Agent >> The photothermographic material of the present invention includes:
It is preferred to add a toning agent. Examples of suitable toning agents are Research Disclosure No. 17029.
And the following: Imides (e.g., phthalimide); cyclic imides, pyrazoline-5
And quinazolinones (eg, succinimide,
3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt Hexamine trifluoroacetate),
Mercaptans (for example, 3-mercapto-1,2,4
N- (aminomethyl) aryldicarboximides (e.g. N- (dimethylaminomethyl) phthalimide); combinations of blocked pyrazoles, isothiuronium derivatives and certain photobleaches (e.g. , N, N '
-Hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate), and 2- (tribromomethylsulfonyl) benzothiazole ); Merocyanine dyes (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); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of a polyhalomethane compound + phthalic acid; a polyhalomethane compound (Including adducts of polyhalomethane compounds)
And maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Quinazolinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones (for example,
1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6-dimercapto-1, 4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene).

<< Support >> As the support, paper, synthetic paper,
A support such as a nonwoven fabric, a metal foil, or a plastic film can be used, and a composite sheet combining these may be used arbitrarily.

<Image Exposure> The image exposure for forming an image on the first and second heat-developable materials of the present invention is performed, for example, at an emission wavelength of 660 nm, 670 nm, 780 nm, 810 nm,
It is preferably performed by any one of 830 nm laser scanning exposure, but it is preferable to use a laser scanning exposure machine in which the angle between the exposure surface of the heat developing material and the scanning laser beam does not become substantially perpendicular. Here, "not substantially vertical" means that the laser scanning angle is preferably 55 to 88 degrees, more preferably 60 to 86 degrees, still more preferably 65 to 84 degrees, and most preferably 70 to 82 degrees. It means that. When the laser beam is scanned on the heat developing material, the beam spot diameter on the heat developing material exposed surface is
Preferably 200 μm or less, more preferably 100 μm
It is as follows. 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. Note that the lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light such as occurrence of unevenness like interference fringes.

It is also preferable that the exposure in the present invention is performed using a laser scanning exposure machine which emits a scanning laser beam which is a vertical multi. By using vertical multi-mode laser exposure, image quality deterioration such as occurrence of interference fringe-like unevenness is reduced as compared with vertical single-mode scanning laser light. In addition to the above-described method, there is a method of vertical multiplexing, such as combining, using return light, or applying high frequency superposition. In addition, the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more.
nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

[Developing Method] The developing method of the present invention will be described below.

<Heat Roller> The heat roller employed in the heat development section of the developing machine for developing the heat development material of the present invention may be any roller having heat resistance, chemical resistance, abrasion resistance, antistatic properties and the like. However, a silicone rubber (organopolysiloxane) roller having improved heat resistance and chemical resistance is particularly preferable. Silicone rubber is colored by adding various coloring agents as needed. Carbon black and black red iron (Fe ₃ O ₄ ) 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. In Japan, iron oxide (FeO) is disclosed in JP-B-51-24302.
A method of adding _x (Fe ₂ O ₃ ) _y is used. Among them, black red iron oxide (Fe ₃ O ₄ ) is described as being preferable because it is black and has excellent thermal conductivity.

However, the color of iron oxides such as the black iron oxide changes from black to red due to an oxidation-reduction reaction between the reducing agent and the oxidizing agent in the heat developing material.
There is a problem that heat resistance tends to decrease. In the present invention, when the metal oxide added to the silicone rubber roller is an iron oxide, it is preferable that the surface thereof is subjected to a treatment for preventing deterioration.

Hereinafter, preferred examples of blending of each component for producing a silicone rubber roller as a heat roller will be described.

(A) Organopolysiloxane 1 in which a part of silicon atoms may be substituted by a heteroatom having 1 to 30 carbon atoms
(B) 10 to 100 parts by mass of a metal oxide, (C) 0.1 to 10 parts by mass of a curing agent, and (D) iron oxides subjected to a surface treatment for preventing alteration. .1 to 50 parts by weight are added.

Hereinafter, the above (A), (B), (C) and (D) will be described in more detail. The organopolysiloxane of the component (A) for producing the silicone rubber roller of the present invention has a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms at the silicon atom of the organopolysiloxane, Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. Examples of the substituent that the monovalent hydrocarbon group may have include a methyl group, a vinyl group, a phenyl group, and the like. The monovalent group selected is preferred. The alkenyl group is 0.01 to 5 mol%,
In particular, it is preferably contained in an amount of 0.02 to 0.5 mol%. Furthermore, a hydrogen atom bonded to a carbon atom such as an alkyl group, an alkenyl group, or an aryl group as the above-mentioned monovalent hydrocarbon group may be partially or entirely substituted with a halogen atom, a cyano group, or the like. , For example, 3,3,3
A trifluoropropyl group, a 2-cyanoethyl group and the like, and a 3,3,3-trifluoropropyl group is particularly preferred. Examples of both terminal groups of the molecular chain of the organopolysiloxane include a hydroxy group, a trimethylsilyl group, a dimethylvinylsilyl group, and a trivinylsilyl group, but are not particularly limited thereto. The organopolysiloxane of the component (A) has a polymerization degree of at least 2,700, preferably at least 3,000, in order to obtain sufficient mechanical strength.
20,000, particularly preferably from 4,800 to 1
It is 0000. As the organopolysiloxane (A), two or more kinds having different structures and degrees of polymerization can be used in combination.

The metal oxide (B) is used to reinforce silicone rubber. Examples thereof include silica, alumina, titanium oxide, magnetite, hematite, and black bengal, and silica is particularly preferably used. Although in order to improve the mechanical strength of and such that tensile strength gives the hardness of moderate to silicone rubber, the specific surface area having its used is not less than 66m ² / g, in particular 99m ² ~444m ² / g are 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 10 to 100 parts by mass, preferably 20 to 100 parts by mass, per 100 parts by mass of the organopolysiloxane of the component (A).
50 parts by mass. If the compounding amount is out of this numerical range,
In some cases, the processability of the silicone rubber composition may deteriorate, or sufficient mechanical strength may not be obtained.

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 present invention as described below. Examples of the organic peroxide that can be used 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. The compounding amount of these organic peroxides is 0.1 to 1 based on 100 parts by mass of the component (A) as an amount sufficient to cure the composition of the present invention.
It is within the range of 0 parts by mass.

When the organopolysiloxane of the component (A) contains two or more alkenyl groups in the molecule, the organohydrogenpolysiloxane that can be used as a curing agent includes a methyl group-blocked trimethylsiloxy group at both ends. Examples thereof include hydrogen polysiloxane, a dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of a trimethylsiloxy group, a dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of a methyl hydrogen siloxy group, and the like. 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 above-mentioned organohydrogenpolysiloxane is generally such that 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 (20: 1), and the amount of the platinum-based catalyst is generally about 0.1 to 3,000 ppm in terms of platinum based on the mass of the component (A). When a platinum compound is used as the heat-resistant agent, it can be used in common.

The component (D) is a preferable component of the silicone composition. Magnetite, hematite, and the like, which are surface-treated with a metal oxide such as alumina, silica, silica-alumina, titanium oxide, and tin oxide to prevent deterioration, 0.1 to 50% by mass of iron oxides such as black red iron oxides or magnetite, hematite, black red iron oxides and the like, which are doped with a metal such as manganese, antimony, tin, zinc, etc. Contained.

Particularly preferred components of the silicone composition of the present invention include magnetite treated with 1 to 10% by mass of alumina or silica-alumina and / or 10 to 20% by mass.
Hematite in the form of fine powder doped with manganese by mass%. In general, when magnetite or hematite is in contact with an oxidizing agent, the surface is oxidized and changes color from black to red when 80 ° C. is exceeded, and magnetite or hematite surface-treated as described above has excellent heat resistance, It does not cause browning or redness in the heat resistance test and chemical resistance of the silicone rubber roller obtained from the silicone composition containing these compounds, and furthermore shows excellent heat resistance when used in combination with a platinum compound, and after exposure to high temperatures The characteristic that the decrease in mechanical strength is small is exhibited. As described above, the treatment amount of alumina or silica-alumina is 1 to 10 with respect to magnetite.
If the amount is less than 1% by mass, sufficient heat resistance cannot be imparted to the silicone rubber roller, so that 10% by mass
If it exceeds 3, sufficient dispersibility of the surface-treated magnetite cannot be obtained, and a silicone rubber roller having a uniform mechanical strength cannot be obtained.

Hematite is usually red, but fine powdered hematite doped with 10 to 20% by weight of manganese as described above becomes excellent black. When the manganese doping amount is less than 10% by weight, a silicone rubber roller is used. If it does not give a sufficient black color and exceeds 20% by mass, hematite tends to agglomerate and dispersibility decreases. The surface treatment can be performed using commercially available manganese or hematite.

The component (D) is further treated with an organic compound such as a silane coupling agent or an inorganic compound such as Al or Si to the extent that the object of the present invention is not impaired, thereby improving fluidity and chemical resistance. Things can also be used. (D)
The particle size of the component is preferably from 0.1 to 5.0 μm, more preferably from 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 m, the mechanical strength of the cured product may be impaired. In the present invention, a kneader, such as a kneader, a Banbury mixer, or an open roll, which is usually used when compounding the component (D) with the organopolysiloxane composition, can be used. As described above, the compounding amount of the component (D) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 5 parts by mass based on 100 parts by mass of the organopolysiloxane of the component (A). Can be If the amount is less than 0.1 part by mass, the black color will not be sufficient, and the heat resistance and chemical resistance will be insufficient.
If the amount is more than 10 parts by mass, the elasticity of the silicone rubber roller deteriorates. Further, two or more kinds of the component (D) may be used in combination.

The above-mentioned platinum compound synergistically improves the heat resistance effect of the silicone rubber together with the component (D), and may be in the form of chloroplatinic acid or an alcohol solution of chloroplatinic acid as described above. No. The amount of the platinum compound is 0.0001 to 0.1 part by mass, preferably 0.001 to 0.01 part by mass, based on 100 parts by mass of the silicone rubber composition of the present invention in terms of platinum. 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 contain, in addition to the components (A) to (D), various rubber compounding agents which are appropriately mixed with the silicone rubber in an amount which does not impair the object of the present invention. For example, diphenylsilanediol, low polymerization degree silicone oil having a molecular chain terminal hydroxyl group, hexamethyldisilazane, dispersant such as alkoxysilane, pulverized silica, diatomaceous earth, zinc oxide, titanium oxide, carbon black, barium oxide, carbonic acid Calcium, magnesium carbonate, zinc carbonate, asbestos, glass wool, fine mica, fused silica powder and the like 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 in which heat treatment is performed at a temperature of 200 ° C. for 30 minutes to 5 hours, and then the component (D) is added and kneaded 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.

<Heat Developing Apparatus> FIG. 1 is a cross-sectional view of an essential part showing an example of a heat developing apparatus for explaining a developing method of the present invention.
Is preferably introduced with the emulsion layer side down into the developing unit 7 by the carry-in roller 2, heated and transported by the developing unit 7, developed, and discharged by the discharge roller 4. The developing unit 7 has a heat source 3 such as a far-infrared heater or a nichrome wire heater, and a heat drum 5 rotating in the direction of an arrow.
And a plurality of heat roller groups 6 rotating on the outer periphery in synchronization with the heat drum 5 to be conveyed. Reference numerals 8 and 8 'denote heat insulating covers, and the rear surface of the heat insulating cover 8 is a cold mirror for reflecting heat. It is preferable to provide a preheating means (not shown) before introducing the heat developing material 1 into the developing unit 7 and a cooling means (not shown) after developing the heat developing material 1.

Here, the heat drum 5 is made of copper, aluminum,
A material having excellent thermal conductivity such as steel is used, and the plurality of heat roller groups 6 are preferably silicone rollers containing iron oxides surface-treated with the above-described metal or metal oxide. It is preferable that the surface hardness is 1 × 10 ⁻⁴ to 1 Pa when expressed as an elastic modulus. The transport speed of the heat developing material 1 is 1 to 100 cm / sec.
Preferably at 80 to 180 ° C. for 5 to 100 sec.
It is preferable to carry out development by heating and conveying for c. The pressure between the heat drum 5 and the heat roller group 6 during conveyance is preferably 10 ² to 10 ² .
The pressure is preferably set to 10 ⁵ Pa. In the above description, the heat roller group 6 is not provided with a heat source, and the heat roller group 6 is pressed against the heat drum 5 having a built-in heat source, and the heat is heated by heat reflection of a cold mirror on the inner surface of the heat insulating cover 8 to perform development. Although an example of performing the processing has been described, in the development processing method of the present invention,
A heat source may be provided in the heat roller group 6 for development.

[0132]

EXAMPLES Examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example of Thermal Developing Material (1) Example 1 <Preparation of Subbed 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 one surface, the following undercoating coating solution a-1 is applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1, and on the other surface, the following undercoating coating solution b −
1 was applied so as to have a dry film thickness of 0.8 μm, and dried to form an undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Co-weight of butyl acrylate (30% by mass), t-butyl acrylate (20% by mass), styrene (25% by mass), and 2-hydroxyethyl acrylate (25% by mass) Combined latex liquid (solid content 30%) 270 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished to 1 liter with water.

<< Undercoat Coating Solution b-1 >> Copolymer latex liquid of butyl acrylate (40% by mass), styrene (20% by mass), and glycidyl acrylate (40% by mass) (solid content: 30%) 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 described below is coated and dried on the lower layer A-1 so as to have a dry film thickness of 0.1 μm. An undercoating layer A-2 is provided, and the undercoating layer B-1 is coated with the following undercoating upper layer coating solution b-2 to a dry film thickness of 0.8 μm and dried to have an antistatic function. An undercoating upper layer B-2 was provided.

<< Coating solution a-2 for lower undercoat >> Gelatin 0.4 g / m ² mass Silica particles (average particle size 3 μm) 0.1 g Finish up to 1 liter with water << Coating solution b-2 for lower undercoat >> Styrene butadiene copolymer latex liquid (solid content: 20%) 80 g Polyethylene glycol (mass average molecular weight: 600) 6 g Finished to 1 liter with water.

<Preparation of silver halide grain emulsion A>
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 0 ml and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (98 /
An aqueous solution containing potassium bromide and potassium iodide in the molar ratio of 2) was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8
%, And a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
After adjusting the pAg to 5.9 and pAg 7.5, a silver halide grain emulsion A was obtained.

<Preparation of water-dispersed organic silver salt> Behenic acid (111.4 g) and arachidic acid (83.8) were added to 4720 ml of pure water.
g and 54.9 g of stearic acid were dissolved at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 mol 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 acid solution at 55 ° C., the 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 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 finish.

<Coating of photosensitive layer and non-photosensitive layer> The following layers were sequentially formed on the support provided with the undercoat layer to prepare a sample. The drying was performed at 45 ° C. for 1 minute.

<< Coating of BC Layer >> On the back surface side, a coating solution prepared by further adding water to the following aqueous solution or water dispersion of the thermal decolorizable dye (C) composition was applied so as to have the following coating amount. After drying, a BC layer was formed.

Inert gelatin 1.1 g / m ² Dye C 12 mg / m ² << Coating of BC layer protective film >> Inert gelatin 0.8 g / m ² Four types of matting agents shown in Table 1 0.02 g / m ² Activator: N-propyl perfluorooctylsulfonamidoacetic acid 0.02 g / m ² dihexyl sulfosuccinate sodium salt 0.02 g / m ² Hardener: 1,2-bis (vinylsulfonamide) ethane 0.02 g / m ² << photosensitivity Application of Layer> For forming a photosensitive layer, water was added to an aqueous dispersion of the following composition to prepare a coating solution. Apply this coating solution to 35
C., and measured silver potential 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. The coating was dried so that the following amounts were obtained. The aqueous dispersion of the prepared organic silver salt was mixed with a polymer binder in an amount of 1.4 g / m ² in terms of silver. In the above preparation, the content of silver halide was 1/10 equivalent to the organic silver salt.

[0143] Binder: styrene - butadiene latex 2.6 g / m ² sensitizing dye A 2 × 10 ^-5 mol / m ² antifoggant -1: pyridinium hydrobromide perbromide 0.3 mg / m ² antifoggant - 2: Isothiazolone 1.2 mg / m ² Antifoggant -3: 2-Tribromomethylsulfonylquinoline 120 mg / m ² Reducing agent: A-4 3.3 mmol / m ² The pH of the photosensitive layer coating solution was 5.6. It was adjusted.

[0144]

Embedded image

<< Surface Protective Layer >> A coating solution prepared by adding the following composition was applied onto the photosensitive layer so as to have the following coating amount and dried to form a surface protective layer. -14
I got

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- (bisvinylsulfonacetamido) ethane 0.3 g / m ² Sodium salt of diethylsulfosuccinate 0.02 g / m ² Surface modifier described in Table 1 0.06 g / m ² <Evaluation of photographic performance>
After storing for 3 days in an atmosphere of% RH, the substrate was exposed with a 810 nm semiconductor laser exposure sensitometer, the angle between the exposed surface of the sample and the exposed laser beam was set to 80 degrees, and after exposure, the heat developing apparatus shown in FIG. 1 was used. (Contact the heat drum with the BC side)
After heating for 2 seconds, development processing was further performed at 110 ° C. for 6 seconds, and the obtained sample was used as a normal humidity sample. Next, the above normal humidity sample was added to 35
In a high humidity atmosphere at 78 ° C. and 78% RH, 70 pieces (5 × 14) of the same sample number were stacked on each other for 5 samples, and a pressure of 5 kPa was applied to the upper portion for storage for 3 days.
The central portion of each sheet was extracted, and the obtained sample was used as a high humidity sample. The laser exposure and development processing of the normal humidity sample were performed in a room conditioned at 25 ° C. and a relative humidity of 54%.

The evaluation (sensitivity and fog) of the images of the normal humidity sample and the high humidity sample were measured by a densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the exposure amount giving a density 0.3 higher than the fog (minimum) density (Dmin).
0) was expressed as a relative evaluation, and the evaluation results are shown in Table 1. The scratch resistance was determined by rubbing the surface of the heat-developable material 5 times with a nylon scourer under a pressure of 100 Pa, and visually evaluating the scratches after the heat development. Rank 5.0 is a level at which no scratch or blackening is observed, Rank 1.0 is a level at which blackening of the scratch is greatest,
3.0 is a level at which scratches and blackening are slightly observed but do not cause practical problems. The evaluation results are shown in Table 1.

[0148] For the contamination of the heat-developable material, 17 silicone rubber heat rollers (without heat source) having a diameter of 2.5 cm were arranged around a heat drum having a diameter of 12 cm, and a weight of 3 k was applied.
Using a test developing device for developing at 150 ° C. by applying Pa, 14 kinds of samples of 20 × 30 cm size were sequentially subjected to 20 times.
Evaluate the stain on the sample when heat development processing is performed for each sheet,
The results are shown in Table 1. Here, the level with the least stain is rank 5.0, the level with the most stain is 1.0,
The case where there was no practical problem even if there was a slight stain was set to 3.0.

[0149]

[Table 1]

Table 1 shows that Samples 1-2 to 1-14 are excellent in scratch resistance during heat development, stains on the samples, and photographic performance (sensitivity and fog characteristics) of the normal humidity sample and the high humidity sample. Sample 1-1, which does not contain the surface modifier and matting agent, is inferior to the other samples in the scratch resistance during thermal development, the contamination of the sample, and the photographic performance of the normal humidity sample and the high humidity sample. I understand.

Example of Thermal Developing Material (2) Example 2 <Preparation of Samples 2-1 to 2-19> As the matting agent added to the protective layer, all the matting agents (1) of the specific examples were used. Using the surface modifier shown in Table 2 and the spectral sensitizing dye A of Example 1 in place of the spectral sensitizing dye A of Example 1, 3 × 10 ⁻⁵ each of the thermal decolorizable spectral sensitizing dyes B (comparative spectral sensitizing dyes) were used. The base-generating precursor compound shown in Table 2 is added to the layer (photosensitive layer) containing the heat-decolorable spectral sensitizing dye or an AI layer as a lower layer or an upper protective layer. Samples 2-1 to 2-19 were obtained in the same manner as in Example 1 except that the layer had the following formulation. Here, the location of the base-generating precursor compound shown in Table 2 is represented by p for the photosensitive layer, q for the AI layer as the lower layer of the photosensitive layer, and r for the protective layer as the upper layer. When the compound was separately added to the photosensitive layer p and the protective layer r, the compound was added in two parts to the photosensitive layer p and three parts to the protective layer r.

Formulation of lower layer (AI layer) q of photosensitive layer Inert gelatin 0.6 g / m ² 1,2- (bisvinylsulfone acetamide) ethane 0.3 g / m ² Diethyl sulfosuccinate sodium salt 0.02 g / m ⁽²⁾ Equimolar addition of the base-generating precursor compound shown in Table 2 to the thermal decolorizable sensitizing dye

[0153]

Embedded image

<Evaluation of Photographic Performance> First, in Example 2, the photographic performance of a normal humidity sample, the photographic performance of a high humidity sample, and the scratch resistance of the sample were evaluated in the same manner as in Example 1, and the results were tabulated. 3 is shown. However, the image exposure at the time of the evaluation of the photographic performance is performed at a wavelength of laser light close to the absorption maximum of the thermal decolorizable spectral sensitizing dye, so that the exposure is 670 nm, 780 nm, 810 nm.
Exposure light selected from a semiconductor laser having a wavelength of 630 nm or a helium neon gas laser having a wavelength of 633 nm is used. As for the reference value of the relative exposure amount by changing the laser light, the exposure amount at which the density of the developed sample becomes 1.0 is obtained. The results were corrected and evaluated as a reference, and the results are shown in Table 3. In Example 2, the thermal decoloring property of the sample was evaluated. In the evaluation of the thermal decoloring property, the sample before exposure was developed under the conditions of Example 1, and the remaining color of five samples cut to a size of 3 × 3 cm after the processing was visually determined. In the above-described visual judgment, the level at which the pigment was most destained was set to rank 5.0, and the worst decoloration level was set to rank 1.0.
The level at which color fogging was about 0.003 was ranked 3.0, and the results are shown in Table 3. Furthermore, using the resolution test chart in which lines of 1 line / mm to 20 lines / mm were lined up with 19 kinds of samples in Table 2, the color tone of 19 kinds of silver images obtained by exposure and development in the same manner as in Example 1 ( (Black level) was visually evaluated. At this time, the cool black tone level of strong black was set to rank 5.0, the strong level of brown or magenta color was set to 1.0, and the level where slight brown or magenta color was recognized but no problem was caused in practical use was set to rank 3. The evaluation was made as 0, and the results are shown in Table 3.

[0155]

[Table 2]

[0156]

[Table 3]

From Table 3, it can be seen that Samples 2-3 to 2-19 have excellent thermal decolorability, color tone, scratch resistance, and photographic performance (sensitivity and fog characteristics) of the normal humidity sample and the high humidity sample during thermal development. In addition, the samples have excellent scratch resistance at the time of development, but the samples 2-1 and 2-2 using the ordinary spectral sensitizing dye B are inferior in thermal decolorability.

Example 3 <Preparation and Evaluation of Samples 3-1 to 3-12> A surface modifying agent and a matting agent shown in Table 4 were exposed to a protective layer, and a heat-decolorable spectral sensitizing dye shown in Table 4 was exposed. In the layer (p), the base generating precursor compound and the acid anhydride shown in Table 4 were added to the addition positions (the photosensitive layer (p), the AI layer (q), or the protective layer (r)) shown in Table 4 to obtain a sample. 3-1 to 3-12 were prepared, and the thermal decolorability, the color tone, the scratch resistance, the photographic performance of the normal humidity sample, and the photographic performance of the high humidity sample were evaluated in the same manner as in Example 2. Table 5 shows the results. The amounts of the base-generating precursor compound and the acid anhydride were added so as to be equal to the amount (molar number) of the heat-decolorizable sensitizing dye per unit area. The base generating precursor compound and the acid anhydride are combined with the photosensitive layer p and the protective layer r.
To the photosensitive layer p, and the protective layer r
Was added in three portions.

[0159]

[Table 4]

[0160]

[Table 5]

From Table 5, it can be seen that Samples 3-3 to 3-12 are excellent in thermal decoloring property during heat development, scratch resistance and color tone.
Both the normal humidity sample and the high humidity sample obtained by processing in the same manner as in Example 1 have excellent photographic performance (sensitivity and fog characteristics), but the base generating precursor compound or the acid anhydride of the present invention. It can be seen that Samples 3-1 and 3-2 containing no substance are inferior to other samples.

Example 4 <Preparation and Evaluation of Samples 4-1 to 4-12> A surface modifying agent and a matting agent shown in Table 6 were exposed to a protective layer, and a heat-decolorable spectral sensitizing dye shown in Table 6 was exposed to light. In the layer (p), the base generating precursor compound, acid anhydride and latex shown in Table 6 are added (photosensitive layer (p), AI layer (q) or protective layer (r)) as shown in Table 6.
4-1 to 4-12 were prepared, and the thermal decolorability, color tone, scratch resistance, photographic performance of a normal humidity sample, and a photograph of a high humidity sample were obtained in the same manner as in Example 2. The performance was evaluated, and the results are shown in Table 7. Incidentally, a base generating precursor compound,
The amount of the acid anhydride added was equal to the amount (molar number) of the heat-decolorizable sensitizing dye per unit area. When the base-generating precursor compound and the acid anhydride were separately added to the photosensitive layer p and the protective layer r, they were added in two portions to the photosensitive layer p and three portions to the protective layer r. Regarding the use of latex as a binder, when it is contained in the photosensitive layer (p), the latex of Table 6 is used instead of the styrene-butadiene of Example 1, and the AI layer (q) and the protective layer (r) Is used, the latex shown in Table 6 is used instead of the inert gelatin. When the latex was separately added to the photosensitive layer p and the protective layer r, the latex was added in two portions to the photosensitive layer p and three portions to the protective layer r.

[0163]

[Table 6]

[0164]

[Table 7]

From Table 7, it can be seen that Samples 4-2 to 4-12 are excellent in thermal decolorability during heat development, color tone, scratch resistance, and photographic characteristics (sensitivity and fog characteristics) of a normal humidity sample and a high humidity sample. However, it can be seen that the performance of Sample 4-1 containing no latex of the present invention is inferior to those of other samples.

Example of Developing Method Example 5 <Development Processing Tests 1-1 to 1-13 and Evaluation of Test Results> As test samples, three types of samples 4-8, 11 and 12 of Example 4 were used. And 13 kinds ((1) to (13)) of heat rollers obtained by changing the material of the heat roller by adding the following 13 kinds of materials, using an apparatus having the following configuration as a development test machine Was used to conduct a development test of the test sample. In the above development test, 2 cm of a silicone rubber containing 13 mass% of a material having the following composition in a polyorganosiloxane having a polymerization degree of 8800 using a platinum catalyst as a heat roller and 200 ppm was used.
Stainless steel cylindrical rod with a thickness of 3 mm and a width of 40
cm, and 50 pairs of the heat roller pairs are arranged at an interval of 1 mm. The test sample is conveyed at a conveyance speed of 2 mm / sec while rotating the heat roller pairs with a drive motor. This was done by developing. In the development test, a sample of 25 × 30 cm at a temperature of 130 ° C. and a load of the current roller pair of 5 kPa was used.
Evaluation of dirt and smoothness of the current roller after the processing of 00 sheets was visually performed. The smoothness of the heat roller was evaluated by visually checking the change in the thickness of the heat roller between the portion where the test sample passed and the portion where the test sample did not pass. The dirt and smoothness of the heat roller were evaluated in a rank system with a decimal point of 1.0 to 5.0, where 5.0 was the best dirt and smoothness of the heat roller, and 1.0 was dirt and smoothness of the heat roller. When the smoothness is the worst, 3.0 indicates the middle. Table 8 shows the obtained evaluation results.

<< Specific Examples of Materials Mixed with Silicone Heat Roller >> (1) Alumina having an average particle diameter of 0.6 μm (2) Silica having an average particle diameter of 0.3 μm (3) Magnetite particles having an average particle diameter of 0.5 μm ( 4) Hematite particles having an average particle diameter of 0.6 μm (5) Surface treatment of the particles of (3) with 10% by mass of alumina (6) Surface treatment of the particles of (3) with silica at 10% by mass (7) (3) (5) Surface treatment of 5% by mass with silica and alumina (8) Particles obtained by doping 14% of manganese to the particles of (3) (9) Surface treatment of 10% by mass of particles of (4) with alumina (10) (4) Particle surface of (4) is treated with 10% by mass of silica. (11) Particle surface of (4) is treated with 5% by mass of silica and alumina. (12) The particles of (4) are doped with 14% of manganese. Particles (13) Compounding material Tooth

[0168]

[Table 8]

From Table 8, it was found that Tests 1-2 to 1-13 which were heat-developed using a heat roller containing a metal oxide, particularly a metal or an iron oxide surface-treated with a metal oxide, showed that the heat roller was stained. Although generation is small and the smoothness of the heat roller is excellent, in the case of Test 1-1 using the heat roller not containing the metal oxide, the performance such as dirt and smoothness is inferior. .

Example 6 <Development Tests 2-1 to 2-13 and Evaluation of Test Results> Samples 4-8, 11 and 12 of Example 4 were used as test samples. In the same manner as described above, in addition to containing 13% by mass of a metal oxide or iron oxides surface-treated with a metal or a metal oxide in silicone, the acid anhydride of Compound Example (5-1) was added to the mass of Table 9 %, Kneaded with a kneader for 4 hours, and formed into a stainless steel shaft. The development process was performed in the same manner as in Example 5 except that 12 types of heat rollers shown in Table 9 were used. ,
In addition, dirt and smoothness of the heat roller were evaluated, and the obtained results are shown in Table 9.

[0171]

[Table 9]

Table 9 shows that Tests 2-2 to 2 were carried out by using a heat roller containing a metal oxide, particularly an iron oxide surface-treated with a metal or a metal oxide and simultaneously containing an acid anhydride. In the case of -13, the generation of dirt on the heat roller is small,
In addition, the smoothness of the heat roller is excellent, but in the case of the test 2-1 using the heat roller not containing the acid anhydride, the performance such as dirt and smoothness is inferior.

[0173]

As has been proved by the examples, the heat-developable material (1) of the present invention has excellent scratch resistance at the time of development, causes less stain on the heat-developable material, and preserves. The stability of the photographic performance at the time of the development is high, and the image after development is also excellent in the high-humidity storage stability.
Further, according to the heat-developable material (2) of the present invention, the spectral sensitizing dye for achieving high sensitivity has excellent thermal decoloring properties, has little residual color after development, and has stable color tone of the obtained image. Therefore, it is possible to exhibit effects such as high stability of photographic performance at the time of storage, and particularly, excellent stability at high humidity of an image after development. Furthermore, according to the development processing method of the present invention, during development, additives and sensitizing dyes from the heat-developable material are not adhered to the heat roller and are not stained on the heat roller surface due to deposition, and the smoothness is improved. And the like.

[Brief description of the drawings]

FIG. 1 is a sectional view of an essential part showing an example of a developing device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermal developing material 2 Carry-in roller 3 Heat source 4 Discharge roller 5 Heat drum 6 Heat roller group 7 Developing part 8, 8 'Heat insulation cover

Claims (10)

[Claims] 1. A heat-developable material having a photosensitive layer containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder and a protective layer containing a matting agent on a support, wherein the protective layer A heat-developable material comprising a surface modifier represented by the following general formula (1). Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ each represent a group selected from an optionally substituted alkyl group, alkoxy group, hydroxy group, aromatic group or heterocyclic group, and m and n are each zero. Or an integer of 1 to 100, provided that m and n are not zero at the same time.) 2. The method according to claim 1, wherein the surface modifier is represented by the following general formula (1-
The heat-developable material according to claim 1, wherein the heat-developable material is a compound represented by formula (a), formula (1-b), formula (1-c) or formula (1-d). Embedded image (In the formula, A and B each have 1 to 4 carbon atoms which may have a substituent.
Represents an alkylene oxide group different from each other, R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 each} have 1 carbon atom
Represents a group selected from an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an aromatic group. L ¹ , L ² , L ³ , L ⁴ , L ⁵
And L ⁶ represent a divalent linking group, an alkylene group having 1 to 8 carbon atoms, an alkylene oxide group having 1 to 8 carbon atoms, m and n are integers of 1 to 1000, p, q, r, s ,
s1, r1, u, v, u1 and v1 are 0 or 1 to 10.
Represents an integer of 0. ) 3. The method according to claim 1, wherein the photosensitive silver halide grains contained in the photosensitive layer of the heat-developable material are sensitized with a thermo-decolorable spectral sensitizing dye represented by the general formula (2). The heat development material according to claim 1. Embedded image (In the formula, Q ¹ and Q ² are an atom group necessary for forming a 5- or 6-membered ring which may have a substituent or a condensed ring belonging to the ring, and L ²¹ is a ring containing Q ¹ A divalent linking group having a methine chain linking the ring containing Q ² , R ²¹ and R ²² represent a substituent, and at least one of R ²¹ and R ²² is —CH ₂ CO
—X ₁ —R ²³ or —CH ₂ CO—N (R ²⁴ ) R ²⁵ ,
X ₁ represents an oxygen atom or a sulfur atom, and R ²³ , R ²⁴ and R ²⁵ each represent a substituent. Further, on the ring containing a ring or Q ² contains a Q ^1, or on the belonging fused ring to the ring containing a ring or Q ² contains a Q ^1, has a -T-R ²⁶ group. T is S
O, SO ₂ or a sulfur atom; R ²⁶ represents a substituent;
X ^- represents an anion. ) 4. The photosensitive layer containing the photosensitive silver halide grains or a layer adjacent to the photosensitive layer contains a base-generating precursor compound represented by the general formula (3). 4. The heat development material according to item 3. Embedded image (Wherein, Z ¹ and Z ² each may have a substituent;
L ³¹ represents a group of atoms necessary to form a member ring, and L ³¹ represents a ring Z ¹
And Z ² represent a divalent linking group. Y represents a substituent, n represents 0 or an integer of 1 to 4, and when n is 2 or more and adjacent to each other, a ring may be formed. ) 5. The photosensitive layer containing the photosensitive silver halide grains or a layer adjacent to the photosensitive layer contains an acid anhydride represented by the general formula (4) or (5). The heat-developable material according to any one of claims 1 to 4, characterized in that: Embedded image (Wherein, W ^1, W ² and W ³ is a group of atoms forming an acid anhydride nucleus, R ^41, R ^{5 1} and R ^52, an aliphatic group which may have a substituent, Represents an aromatic group or a heterocyclic group, n and m each represent 0 or an integer of 1 to 4, and when n is 2 or more, adjacent substituents may form a condensed ring.
⁵¹ represents a divalent linking group which connects the ring containing W ² and the ring containing W ³ . ) 6. A photosensitive layer containing the photosensitive silver halide grains or a latex in a layer adjacent to the photosensitive layer, wherein the latex has a glass transition temperature of -60 ° C. to 80 ° C.
The heat development material according to any one of claims 1 to 5, wherein the temperature is ℃. 7. The heat developing material according to claim 6, wherein the latex contains a halogen atom in a molecule. 8. A heat-developable material according to claim 1, wherein the heat-developable material is developed using a heat roller made of silicone rubber containing a metal oxide. Development processing method. 9. The method according to claim 8, wherein at least a part of the metal oxide is a surface-treated iron oxide. 10. The method is carried out by using a heat roller made of silicone rubber containing an acid anhydride represented by the general formula (4) or (5) and obtained by heat treatment. The method for developing a heat-developable material according to claim 8.