JP2000347372A - Heat developing method and digital image information generating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To generate digital image information with little noise even when an image formed by imagewise exposing a silver halide photographic sensitive material, laying it on a processing material and carrying out heat development is read with a scanner and converted to digital image information. SOLUTION: A silver halide photographic sensitive material with plural photographic constituent layers including a layer containing a photosensitive silver halide emulsion, a developing agent of the formula and a compound which forms a dye by coupling reaction with the oxidized body of the developing agent is imagewise exposed and laid on a processing material containing a base and/or its precursor and heat development is carried out to form an image. The silver halide photographic sensitive material is laid on the processing material in such a way that the materials do not thoroughly overlap each other. In the formula, R1-R4 are each H, halogen, alkyl, aryl, alkylcarbonamido, arylcarbonamido, alkylsulfonamido or the like, R2 and R4 are each preferably H and R5 is alkyl, aryl or a heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for thermally developing a silver halide photographic material and a method for preparing digital image information.

[0002]

2. Description of the Related Art Heat-developable films are disclosed in
-204031, 9-258402, 9-27
No. 4295, No. 9-112265, No. 9-14624
No. 7, No. 9-230557 and the like.

As a method for developing a heat-developable photosensitive material, for example, a method described in JP-A-9-319057 is known. This method is a method of obtaining an image by thermal development substantially without using a processing solution in the development processing step of the photosensitive material. According to this method, there is no need to use a developing solution as compared with the conventional method, and The processing time is relatively short, and the operation is simple. The heat development process according to the present invention, after exposing the photosensitive material imagewise,
An image is formed by superposing and heating the photosensitive material and the processing material on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material. After image formation, the photosensitive material and the processing material are separated.

[0004] There is also a digital image information creating method in which after image formation, the image is read by a scanner and converted into digital image information. However, processing unevenness occurs when processing the photosensitive material and the processing material, which may adversely affect an electronic image obtained as a noise source at the time of reading by a scanner.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming an image by subjecting a silver halide photographic material to image exposure, superimposing it on a processing material and thermally developing the same. An object of the present invention is to provide a digital image information creating method in which noise is reduced even when the information is read by a scanner and converted into digital image information.

[0006]

The above object has been attained by the following means. 1. On a support, a photosensitive silver halide emulsion, a developing agent,
A silver halide photographic material having a plurality of photographic constituent layers including a layer containing a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent contains a base and / or a base precursor after image exposure. A method for forming an image by overlaying a processing material to be processed and performing a thermal development process, wherein the silver halide photographic light-sensitive material and the processing material are overlapped in a completely inconsistent state. Method.

[0007] 2. The developing agent has the following general formula I-1:
The thermal development method according to claim 1, wherein the thermal development method is at least one of the compounds represented by I-5.

[0008]

Embedded image In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group.
Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group.

[0009]

Embedded image In the formula, Z represents an atom group forming an aromatic ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group.

[0010]

Embedded image In the formula, R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. R ₆ represents a substituted or unsubstituted alkyl group.
X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ ,
R _8, R _9, R ₁₀ represents a hydrogen atom or a substituent, R _7,
R ₈ , R ₉ and R ₁₀ may combine with each other to form a double bond or a ring.

[0011]

Embedded image In the formula, Z represents an atom group forming an aromatic ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group.

[0012]

Embedded image In the formula, R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. R ₆ represents a substituted or unsubstituted alkyl group.
X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ ,
R _8, R _9, R ₁₀ represents a hydrogen atom or a substituent, R _7,
R ₈ , R ₉ and R ₁₀ may combine with each other to form a double bond or a ring.

3. 3. The heat development method according to the above item 1 or 2, wherein the silver halide photographic material contains a poorly water-soluble metal salt compound.

4. Compounds that form a dye by a coupling reaction between a mosaic or striped filter layer having at least two regions having different spectral absorption characteristics on a support and at least one oxidized form of a silver halide emulsion and a developing agent A method of forming an image by subjecting a silver halide photographic light-sensitive material having a layer containing, to image exposure, and superposing the same on a processing material and subjecting to heat development processing, wherein the silver halide photographic light-sensitive material and the processing material A heat development method characterized in that the images are superposed in a state where they do not completely match.

[0015] 5. An image is formed by subjecting a silver halide photographic light-sensitive material having at least one layer containing a silver halide emulsion on each of both sides of a support to image processing, superimposing it with a processing material and subjecting it to heat development to form an image. A heat development processing method, wherein the silver halide photographic light-sensitive material and the processing material are overlapped in a state where they do not completely coincide with each other.

6. A method of forming an image by exposing a rolled silver halide photographic material to an image, superimposing it on a processing material and subjecting it to heat development processing, wherein the silver halide photographic material and the processing material are completely matched. A heat development processing method characterized in that the layers are superposed in a state where they are not used.

[7] 7. The thermal development processing method according to any one of the above items 1 to 6, wherein a notch is provided in at least one of the silver halide photographic material and the processing material.

[8] The method according to any one of claims 1 to 7, wherein a processing material having a total amount of a base and a base precursor contained in the processing material of 20 mmol / m ² or more is used.

9. 9. The heat development method according to claim 1, wherein a light-sensitive material in which the hardly water-soluble metal salt compound contained on one side of the support is 20 mmol / m < ² > or more is used.

[10] Digital image information preparation, wherein an image is formed in a silver halide photographic light-sensitive material by the heat development processing method according to any one of the above 1 to 7, and then converted into digital image information by reading with a scanner. Method.

The operation of the present invention is as follows. Conventional photothermographic materials use a dye-providing substance called DRR or ROSET to generate an imagewise diffusible dye through an image forming reaction caused by thermal development, and then diffuse and transfer it to the image-receiving material for viewing. To create negative or positive images.

On the other hand, in recent years, attempts have been made to use a heat-developable film as a photosensitive material for photography, as disclosed in the above-mentioned patent publication. It is a small-sized material that is used by loading a photographic photosensitive material into a camera or the like, and is usually stretched based on a formed image. Therefore, a high resolution is required. An image diffused and transferred to an image receiving material obtained by using a conventional photothermographic material is of high quality for appreciation, but deterioration in resolution and image blur caused by diffusion cannot be avoided. Therefore, the image itself on the photosensitive material should be used for this purpose.

However, since silver halide and other colored substances that have become unnecessary after thermal development remain on the photographic material without being removed, they are stretched as they are by analog exposure as in a normal negative film. Is difficult to do. For this reason, there has been proposed a digital image information creating method in which an image formed on a photosensitive material after thermal development is read by a scanner and converted into digital image information, and then subjected to appropriate image processing so as to endure appreciation. It has been proposed to create an image on another silver halide recording material or a non-silver halide recording material based on the digital image information thus obtained to obtain a hard copy.

When the photothermographic material is used as a film for photographing, it is preferable to use a colorless image forming substance in order to maintain a sufficient sensitivity. DRR and ROSET used in conventional photothermographic materials are not preferred because they are colored dye-providing substances. As a colorless image forming substance, a method using a color developing agent and an image forming coupler as used in a general color film is preferable.

In a heat development process in which a photosensitive material and a processing material are overlapped, after a predetermined heat development time has elapsed,
Both materials need to be quickly separated and separated. At this time, if an excessive stress is applied to the photosensitive material, the film may be destroyed, and the image may be damaged. When the formed image is read by a scanner or the like and converted into digital image information, it goes without saying that even very minute flaws or unevenness may adversely affect the image. In particular, when a photo-sensitive material is subjected to thermal development processing to be stretched or output in a size larger than that after conversion to digital image information, such an image is compared to a case where the thermally-developed photosensitive material is directly used for appreciation. Unevenness and scratches appear as major damage,
Great care must be taken when peeling the photosensitive material from the processing material.

In the image forming reaction utilizing the coupling reaction between the oxidized developing agent and the image forming coupler according to the present invention, the developing agent and the coupler are designed to be hydrophobic in order to increase the diffusion resistance. Oil protection dispersion or solid dispersion is added to the photosensitive material. In such a light-sensitive material, a large amount of a compound related to image formation is generally contained in the light-sensitive material as compared with the case where a conventional DRR or ROSET is used. As a result, it has been found that there is a problem that the ratio of the hydrophobic compound to the hydrophilic binder is increased, the film becomes brittle, and defects such as scratches and unevenness are likely to occur at the time of peeling.

In the image forming reaction utilizing the coupling reaction between the oxidized developing agent and the image forming coupler according to the present invention, a sufficient amount is required for performing the image forming reaction in a short time and obtaining a desired image density. Requires alkali. The required amount of alkali is much larger than that of a conventional light-sensitive material using DRR or ROSET.

In the image forming method according to the present invention, the alkali is added to the processing material as a base or a base precursor. In a preferred embodiment of the present invention, alkali is generated by the reaction of the base precursor contained in the processing material with the poorly water-soluble metal compound contained in the photosensitive material. Therefore, the solution is to increase the amount of the base precursor added to the processing material and the amount of the poorly water-soluble metal compound added to the photosensitive material in order to increase the amount of generated alkali. Is difficult. Inclusion of a large amount of the base precursor strengthens the adhesive force between the processing material and the photosensitive material. Therefore, if the peeling is not carried out immediately after the thermal development, the peeling becomes very difficult. In an extreme case, the peeling becomes impossible. This is particularly noticeable when a large amount of oil-soluble substances such as couplers are contained as in the light-sensitive material of the present invention. Also, the addition of a large amount of a poorly water-soluble metal compound to a photosensitive material makes the film of the photosensitive material brittle, so that the peeling operation under high stress or a slight change in the peeling rate during the peeling operation may cause cracks in the photosensitive material film. Defects such as scratches are more likely to occur.

When the photothermographic material according to the present invention is used as a photosensitive material for photography, even if the processing is simple and can be performed in a short time, such scratches and defects may occur before reading by a scanner. This was a problem related to the reliability of the system itself, and had to be avoided by any means. The present invention has successfully solved these disadvantages.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The silver halide photographic light-sensitive material of the present invention is a photographic light-sensitive material that can be dry-processed such that an image is obtained by heat development (heating) substantially without using a processing solution, and is provided on a support. And a plurality of photographic constituent layers including a layer containing a photosensitive silver halide emulsion, a developing agent, and a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent.

The photosensitive silver halide which can be used in the present invention is not particularly limited, and the halogen composition may be a halogen such as silver bromide, silver iodobromide, silver iodochloride, silver chloroiodobromide or silver chloride. Silver halide particles can be optionally used.

The photosensitive silver halide of the present invention can be spectrally sensitized by a spectral sensitizing dye. The spectral sensitizing dye can be added as a solution in an organic solvent,
It is also possible to add the spectral sensitizing dye as a solid fine particle dispersion. It is preferable that at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant.

The silver halide photographic light-sensitive material of the present invention contains a compound which forms a dye by a coupling reaction with an oxidized form of a developing agent. As a specific example, Research Disclosure (RD) No. No. 17643, VII-
It is described in patents described in C to G and the like.

The silver halide photographic light-sensitive material of the present invention contains a developing agent. Preferably, the above-mentioned general formulas I-1 and I-
2, at least one developing agent selected from the compounds represented by I-3, I-4, and I-5,
Among these, the compound of the general formula I-1 or I-4 is preferably used. Hereinafter, these compounds will be described in detail.

The compound represented by the formula I-1 is a compound generically called sulfonamidophenol. Where R
_{1 to} R ₄ are each a hydrogen atom, a halogen atom (for example, a chloro group or a bromo group), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group),
Aryl group (for example, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group),
Arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy Group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group, tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl) Group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoy Groups (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl, alkylsulfamoyl (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl) , Diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group) Famoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group) 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Represents a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). These substituents include those further having a substituent. Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R _{1 to} R ₄ is 0 or more.

R ₅ is an alkyl group (for example, methyl, ethyl, butyl, octyl, lauryl, cetyl,
A stearyl group), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group). These substituents include those further having a substituent.

The compound represented by the formula I-2 is a compound generically called sulfonylhydrazine. The compound represented by the general formula I-4 is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinazoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Examples thereof include a propionyl group, a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σp values of the above substituents is 1 or more. These substituents include those further having a substituent.

The compound represented by the formula I-3 is a compound generically called sulfonylhydrazone. The compound represented by the general formula I-5 is a compound generally called carbamoylhydrazone. In the formula, R ₆ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X
Represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ , R ₈ , R ₉ , R
_1O represents a hydrogen atom or a substituent, and R ₇ , R ₈ , R ₉ , R
₁₀ may combine with each other to form a double bond or a ring.

The specific examples of the compounds represented by formulas I-1 to I-5 are shown below, but the compounds of the present invention are not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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These developing agents used in the present invention are:
It is preferable to use 0.05 to 10 mmol / m ² per color-forming layer. A more preferable usage is 0.1 to 5 m.
mol / m ² , and a particularly preferred usage amount is 0.2 to
2.5 mmol / m ² .

The silver halide photographic material of the present invention can contain a hydrophilic binder. It is preferable to use gelatin as the hydrophilic binder.

The silver halide photographic light-sensitive material of the present invention can contain various photographic additives. In particular, in the present invention, when a compound that forms a dye by a coupling reaction with an oxidant serving as a developing agent is used, a large amount of the color developing agent and a hydrophobic additive such as oil are used.
Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978
No.) and the same No. 18716 (November 1979) and N
o. 308119 (December 1989).

The support which can be used in the silver halide photographic material of the present invention has flexibility.
For example, page 28 of RD-17643 and RD-30
8119 on page 1009. Suitable supports include polyethylene naphthalate film, polyethylene terephthalate film, cellulose triacetate film, baryta paper, polyethylene coated paper (RC base paper) and the like. The surface of these supports is used to improve the adhesion of the coating layer. An undercoat layer may be provided, or corona discharge, ultraviolet irradiation, or the like may be performed. Further, as a support, for example, JP-A-4-124645 and 5-403
No. 21, 6-35092, Japanese Patent Application No. 5-58221
And photographic information can also be recorded using a support having a magnetic recording layer described in JP-A-5-106979.
Further, it is necessary to use a support that can withstand the heat development processing temperature.

The silver halide photographic light-sensitive material of the present invention has a plurality of photographic constituent layers on a flexible support. A color photothermographic material usually has a plurality of photosensitive emulsion layers on a support. Usually, these layers are designed so that the photosensitive wavelength ranges are different from each other, and the absorption of dyes formed after the development processing is also different from each other. Generally, the photosensitive layer is a unit photosensitive layer having a sensitivity in a wavelength region of blue light, green light, red light, infrared light, ultraviolet light, and the like, and these photosensitive layers are laminated on a support. By doing so, a color photosensitive material is formed.

In the silver halide photographic light-sensitive material of the present invention, a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and the like may be provided between the silver halide emulsion layers and as the uppermost layer and the lowermost layer. Various non-photosensitive layers may be provided. Specifically, US Pat. No. 5,051,33
An undercoat layer as described in JP-A No. 5 (1994) -167878;
And an intermediate layer having a solid pigment as described in JP-A-61-20943, JP-A-1-120553 and JP-A-5-34.
And reducing agents such as described in JP-A Nos. 884 and 2-64634.
Interlayer with IR compound, US Pat. No. 5,017,4
No. 54, 5,139,919, JP-A-2-2350
An intermediate layer having an electron transfer agent as described in JP-A No. 44, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer obtained by combining them can be provided.

As a silver halide photographic light-sensitive material of the present invention, a light-sensitive material described in Japanese Patent Application No. 11-002903 is one of preferred embodiments.

The processing mode of the light-sensitive material of the present invention is a heat development processing. In the heat development, it is preferable to use a processing material different from the photosensitive material. Examples of the treatment material include a sheet having a treatment layer containing a base and / or a base precursor on a support (hereinafter also referred to as a treatment sheet). It is preferable that the treatment layer is composed of a hydrophilic binder. After imagewise exposing the photosensitive material, image formation is performed by heating the photosensitive material and the processing material on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material. Due to the presence of such a large amount of the base and / or the base precursor, the adhesiveness between the processing sheet and the photosensitive material is remarkably increased based on the heating in the superposed state. In the present invention, 1/1 of water required for maximum swelling of all coating films constituting the photosensitive material and the processing material is used.
A method of performing color development by supplying water equivalent to 0 to 1 times to a photosensitive material or a processing material, and then superposing and heating them is preferably used. Further, it is also possible to use a method in which the auxiliary developer is incorporated in the photosensitive material or the processing material as required, or is applied together with water. still,
The water may be hot water or steam.

Heat treatment of photosensitive materials is known in the art, and for photothermographic materials and their processes,
For example, basics of photo engineering (1970, published by Corona)
553-555, April 1978, Video Information 4
Page 0, Nabletts Handbook of P
photography and Reprograph
y 7th Ed. (Vna Nostrand an
d Reinhold Company) 32-33
, U.S. Pat. Nos. 3,152,904 and 3,30
Nos. 1,678, 3,392,020, 3,4
57,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pp. 9-15 (RD1702).
9). The heating temperature in the thermal development step is about 5
0 ° C to 250 ° C, but especially 60 ° C to 150 ° C is useful.

The silver halide photographic material of the present invention can contain a thermal solvent for the purpose of accelerating thermal development.
The thermal solvent is a compound that liquefies when heated and has an action to promote image formation. At room temperature, it is preferably white and in a solid state, and it is desired that volatility during heating is small. The type of the hot solvent is not particularly limited, but it is advantageous to use a hot solvent having a melting point suitable for the heat development temperature. The type and amount of the hot solvent can be easily optimized and determined so as to obtain a desired maximum concentration.

The silver halide photographic material of the present invention can contain an organic metal salt as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used. Specific examples of the organic silver salt include silver behenate and silver benzotriazole. Use of an organic silver salt is preferred because a high image density can be obtained.

In the light-sensitive material and / or processing material of the present invention, it is preferable to use a large amount of a base or a base precursor for the purpose of promoting silver development and a dye-forming reaction. Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, and compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat.
No. 657,848 and the known art No. 5 (March 1991)
(Aztec Co., Ltd., published on May 22) from page 55 to 86
Page. A method of generating a base by a combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with metal ions constituting the basic metal compound using water as a medium (referred to as a complex forming compound) is also preferably used. Such a base generation method is described in European Patent Publication 21.
0,660, U.S. Patent No. 4,740,445. When such a base generation method is used, although the adhesion between the processing sheet and the photosensitive material is significantly increased, in the present invention, a basic metal compound which is hardly soluble in water is added to the photosensitive material, and By adding a compound capable of forming a complex with metal ions constituting the basic metal compound and water as a medium (hereinafter referred to as a complex-forming compound), the storage stability of the photosensitive material can be improved.

The processing material used in the heat development step of the present invention contains the above-mentioned base and / or base precursor, and further shuts off air during heat development,
The material is prevented from volatilizing from the light-sensitive material, a processing material other than a base is supplied to the light-sensitive material, a material (YF dye, AH dye, etc.) in the light-sensitive material which becomes unnecessary after development, or is generated during development. It can also have a function of removing unnecessary components. Further, the processing material may have a desilvering function. For example, when a part or all of the silver halide and / or the developed silver is soluble when the photosensitive material is superposed on the imagewise exposed post-processing material, the processing material may contain a fixing agent as a silver halide solvent. You can leave it.

As the support and binder for the processing material, the same materials as those for the photosensitive material can be used. A mordant may be added to the processing material for the purpose of removing the above-mentioned dye or other purposes. As the mordant, those known in the field of photography can be used, and U.S. Pat. No. 4,50,626, columns 58-59, JP-A-61-88256, pages 32-41,
Examples include mordants described in JP-A Nos. 2-244043 and 62-244036. U.S. Pat.
463, 079 may be used. Further, the above-mentioned thermal solvent may be contained.

The treatment layer of the treatment material contains a base or a base precursor. The base may be either an organic base or an inorganic base. As the inorganic base, JP-A-62
Hydroxides (eg, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc.) and phosphates (eg, dipotassium hydrogen phosphate) described in US Pat. , Disodium hydrogen phosphate, ammonium or sodium hydrogen phosphate, secondary or tertiary phosphates such as calcium hydrogen phosphate, etc.), carbonates (eg, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, etc.), Borate (eg, potassium borate, sodium borate, sodium metaborate, etc.), organic acid salt (eg, potassium acetate, sodium acetate, potassium oxalate, sodium oxalate, potassium tartrate, sodium tartrate,
Sodium malate, sodium palmitate, sodium stearate, etc.), acetylides of alkali metals or alkaline earth metals described in JP-A-63-25208,
And the like.

Examples of the organic base include ammonia, aliphatic or aromatic amines such as primary amines (eg, methylamine, ethylamine, butylamine, n-hexylamine, cyclohexylamine, 2-ethylhexylamine, allylamine, ethylenediamine, , 4-
Diaminobutane, hexamethylenediamine, aniline,
Anisidine, p-toluidine, α-naphthylamine, m
-Phenylenediamine, 1,8-diaminonaphthalene,
Benzylamine, phenethylamine, ethanolamine, etc.), secondary amine (eg, dimethylamine, diethylamine, dibutylamine, diallylamine, N-methylaniline, N-methylbenzylamine, N-methylethanolamine, diethanolamine, etc.), tertiary amine ( For example, N-methylmorpholine, N-hydroxyethylmorpholine, N-methylpiperidine, N-hydroxyethylpiperidine, and N-methylmorpholine described in JP-A-62-170954.
N′-dimethylpiperazine, N, N′-dihydroxyethylpiperazine, diazabicyclo [2,2,2] octane, N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N-methyldiethanolamine, N-methyldiethanolamine Propanolamine, triethanolamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrahydroxyethylethylenediamine, N, N, N ', N'-tetramethyltrimethylene Diamine, N-methylpyrrolidine, etc.), polyamine (diethylenetriamine, triethylenetetramine, polyethyleneimine, polyallylamine, polyvinylbenzylamine, poly- (N, N-diethylaminoethyl methacrylate), poly- (N, N-dimethylvinylbenzylamido) ), Hydroxylamines (eg, hydroxylamine, N-hydroxy-N-methylaniline, etc.), heterocyclic amines (eg, pyridine, lutidine, imidazole, aminopyridine, N, N-dimethylaminopyridine, indole, quinoline, isoquinoline) , Poly-4-vinylpyridine, poly-2-vinylpyridine, etc.), amidines such as monoamidine, (eg acetamidine, 2-methylimidazole, 1,4,5,
6-tetrahydropyrimidine, 2-methyl-1,4,
5,6-tetrahydropyrimidine, 2-phenyl-1,
4,5,6-tetrahydropyrimidine, iminopiperidine, diazabicyclononene, diazabicycloundecene (DBU), etc., bis or tris or tetraamidine, guanidines such as water-soluble monoguanidine (eg guanidine, dimethylguanidine, Tetramethylguanidine, 2-aminoimidazoline, 2-amino-
1,4,5-tetrahydropyrimidine, etc.)
Water-insoluble mono- or bis-guanidine, bis- or tris-, tetraguanidine or quaternary ammonium hydroxides (for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide) described in US Pat. Oxide, trioctylmethylammonium hydroxide, methylpyridinium hydroxide, and the like).

In the case where a complex forming compound for a metal ion of a poorly water-soluble basic compound is used as the base precursor, for example, an aminocarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid or a salt thereof is used. , Aminophosphonic acid or a salt thereof,
2-picolinic acid, pyridine-2,6-dicarboxylic acid, 5
Pyridylcarboxylic acid such as -ethyl-2-picolinic acid or a salt thereof, iminodiacetic acid such as benzyliminodiacetic acid, α-picolineliminodiacetic acid or a salt thereof can be used. As the complex-forming compound, it is preferable to use a salt neutralized with an organic base such as guanidine or an alkali metal such as potassium. The preferable addition amount of the base or the base precursor or the complex-forming compound in the treatment material is 0.1 to 20 g / m ² , more preferably 0.5 to 10 g / m ² .

On the other hand, as the basic compound hardly soluble in water to be contained in the light-sensitive material, metal hydroxide or metal oxide is preferably used, and among these, zinc hydroxide or zinc oxide is particularly preferable. Is preferred.

In thermal development using the processing material, it is preferable to use a small amount of water for the purpose of promoting development, promoting the transfer of the processing material, and promoting the diffusion of unnecessary substances. As described above, when employing a method of generating a base with a combination of a basic metal compound which is hardly soluble in water and a metal ion and a complex forming compound constituting the basic metal compound, it is essential to use water. is there. The water may contain an inorganic alkali metal salt, an organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, an antifungal agent, and an antibacterial agent. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photosensitive material and the processing material of the present invention, water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-144354
No. 63-144355, No. 62-38460,
The apparatus described in JP-A-3-210555 and water may be used. Water can be applied to the photosensitive material, the processing material, or both. The amount used is an amount corresponding to 1/10 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing material. As a method of applying this water, for example,
The method described in JP-A-253159 (page 5), JP-A-63-85544 and the like are preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in a photosensitive material or a processing material or both in the form of a hydrate. The temperature of the water to be applied is as described in
The temperature may be 30 ° C. to 60 ° C. as described in Japanese Patent No. 85544 or the like. The water may be hot water or steam. In particular, it is preferable to use the catholyte used in the image forming method and the heat development processing apparatus described in JP-A-10-333300.

The processing material used in the heat development of the present invention may have a layer containing various additives known in the art.

The silver halide photographic material of the present invention comprises a mosaic or stripe filter layer having at least two regions having different spectral absorption characteristics on a support, at least one silver halide emulsion and a developing agent. It may have a layer containing a compound that forms a dye by a coupling reaction with an oxidant.

The method for producing the filter layer of the present invention includes a method using dyed starch particles, a method for forming a stripe or mosaic pattern by printing, a method using thermal transfer, a method using ink jet,
Various methods such as a method using a photoresist (photo-curable resin) and a method using a photograph, such as a color liquid crystal display device and a color CCD photographing device, can be used. These methods are described in JP-A-55-6342 and JP-A-63-261361. JP-A-5-127016, JP-A-6-100811, and JP-A-7-107
294714, 8-22108, 9-1850
No. 77, 9-145909 and 9-178925.

As the spectral transmission characteristics of the filter layer of the present invention, the combination of Y (yellow), M (magenta), and C (cyan), which are the three primary colors of light of the subtractive color method, is preferable.
B (blue), G (green), and R, which are the three primary colors of light of the additive method
A combination of (red) may be used, and in addition to these, a black matrix portion may be provided.

As the pattern of the filter layer of the present invention, any of a stripe shape and a mosaic shape may be used. The size of the filter layer of the present invention is preferably from 1 to 50 μm, more preferably from 5 to 30 μm per color in the case of a stripe. In the case of a mosaic shape, the thickness is preferably 1 μm to 50 μm per unit area, and more preferably 5 μm to 40 μm. Also, as the thickness of the color filter layer,
0.1-1 for both stripe and mosaic
0 μm is preferred, and 0.2-5 μm is more preferred.

The color filter array may be a striped color filter array having a set of red, green, blue, and green line patterns in which a green line is added after red, green, and blue. . In this case, for the number of red and blue lines,
The number of green lines is twice as large, and the repetition width of the green stripes is reduced, so that an image quality improving effect close to a Bayer array can be obtained even in a stripe array.

The silver halide photographic light-sensitive material of the present invention can have at least one layer containing a silver halide emulsion on both sides of the support. More specifically, a photosensitive emulsion layer and a base generating layer containing a hardly soluble metal salt compound can be provided on both sides of the support. Preferably, one of the supports contains, in addition to the silver halide emulsion, a developing agent and a compound that forms a dye by a coupling reaction with an oxidized form of the developing agent. It is a silver halide photographic light-sensitive material constituted. A light-sensitive emulsion layer having the same color sensitivity or a light-sensitive emulsion layer having different color sensitivity may be provided on both sides of the support. Various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer can be appropriately provided on one or both sides of the support according to the purpose.

Preferred examples of the layer structure of a silver halide photographic light-sensitive material having at least one layer containing a silver halide emulsion on both sides of the support of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Not limited. (Exposed surface) Protective layer / base generating layer / blue-sensitive emulsion layer / yellow filter layer / undercoat layer / transparent support / undercoat layer / green-sensitive emulsion layer / magenta dye layer / red-sensitive emulsion layer / cyan dye layer / base generation Layer / Protective layer (exposed surface) Protective layer / Base generating layer / Blue-sensitive emulsion layer / Yellow filter layer / Undercoat layer / Transparent support / Undercoat layer / Green-sensitive emulsion layer / Intermediate layer / Red-sensitive emulsion layer / Magenta and cyan Dye layer / Base generating layer / Protective layer The light-sensitive material of the present invention can be used by winding it into a roll. When used in the form of a roll, it is preferable to take the form housed in a cartridge.

The most common cartridge is
This is a 135 format or IX-240 format cartridge. Other cartridges proposed in the following patent documents can also be used. That is, the actual opening 58
-67329, JP-A-58-181035, JP-A-58-182634, Japanese Utility Model Application Laid-Open No. 58-195.
No. 236, U.S. Pat. No. 4,221,479, and Japanese Patent Application Nos. 63-57785 and 63-1833.
No. 44, No. 63-325638, Japanese Patent Application No.
No. 21852, No. 1-25362, No. 1-3
Nos. 0246 and 1-20222 and 1-21
No. 863, No. 1-37181, No. 1-331
Nos. 08, 1-85198, 1-1725
Nos. 95, 1-172594 and 1-172
No. 593, U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832.
Reference can be made to the cartridge technology disclosed in US Pat.

When the photosensitive material of the present invention is thermally developed, known heating means can be applied, for example, a method of contacting with a heated heat block or a surface heater, or a method of contacting with a heat roller or a heat drum. A method of contacting with an infrared or far-infrared lamp heater, a method of passing through an atmosphere maintained at a high temperature, a method of using a high-frequency heating method, or the like can be used. In addition, a method in which a heat-generating conductive substance such as a carbon black layer is provided on the back surface of the photosensitive material or the image receiving member, and Joule heat generated by energization can be applied. As the heat-generating elements, those described in JP-A-61-145544 can be used. A method of superposing a photosensitive material and a processing material in such a manner that the photosensitive layer and the processing layer face each other is disclosed in JP-A-62-25315.
Nos. 9 and 61-147244 (page 27) can be applied. The heating temperature is preferably from 70C to 100C.

For processing the silver halide photographic light-sensitive material of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75247 and JP-A-59-17747.
No. 59-181353, No. 60-18951,
No. 10-333300, Japanese Utility Model Publication No. 62-25944,
Japanese Patent Application Nos. 4-277517, 4-243072, 4-24493, 6-164421, and 6-1
An apparatus described in No. 64422 or the like is preferably used. Commercially available devices include a Pictrostat 100 and a Pictrostat 20 manufactured by Fuji Photo Film Co., Ltd.
0, Pictrostat 300, Pictrostat 3
30, the same Pictrostat 50, the same Pictography 3000, the same Pictography 2000, etc. can be used.

In order to use the light-sensitive material of the present invention for storage or appreciation for a long period of time after processing, it is preferable to perform a bleaching process or a fixing process. When used for the purpose of reading and converting to an electronic image, bleaching processing and fixing processing are not necessarily required. However, it is usually preferable to perform the fixing process. This is because the remaining silver halide has an absorption in the visible wavelength range and adversely affects an electronic image obtained as a noise source at the time of scanner reading. In order to realize a simple process of developing only without performing a fixing process, it is preferable to use thin tabular silver halide grains or silver chloride grains.

The image obtained by the present invention can be read using a scanner or the like and converted into electronic image information. In the present invention, the scanner is a device that optically scans a photosensitive material and converts the optical density of reflection or transmission into image information. When scanning, it is common to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material, and it is recommended that the photosensitive material be fixed. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner. Alternatively, a combination of these may be used.

The image data thus obtained can be viewed using various image display devices. As the image display device, an arbitrary device such as a color or monochrome CRT, a liquid crystal display, a plasma light emitting display, and an EL display is used.

According to the present invention, an image signal thus read can be output to form an image on another recording material. The output material is silver halide photosensitive material,
Various hard copy devices are used. For example, various systems such as an ink jet system, a sublimation type thermal transfer system, an electrophotographic system, a cycolor system, a thermoautochrome system, a method of exposing a silver halide color paper, and a silver halide heat development system are used. Further, the image information obtained in this way can be transmitted by electronic transmission or stored in a floppy disk or a hard disk.

In the present invention, after photographing, the photosensitive material is transferred to a developing station having a heat development processing device to perform a heat development process, and the information is electrically or optically converted into digital data. It can also be stored in the line database. Therefore, a user who is a photographer can view and print out his or her photographed image by accessing the database of the communication line.
Alternatively, digitally converted image information can be input to a recording medium and sent to a location specified by the user.

The present invention relates to a method for forming an image by superposing a photosensitive material on an image, superposing the same on a processing material and thermally developing the same, wherein the photosensitive material and the processing material are superimposed in a completely inconsistent state. Is a heat development processing method.

In the present invention, when the photosensitive material and the processing material are overlapped in a state where they do not completely coincide with each other, the area where the two do not coincide with each other when the two are overlapped is 0.1% of the area where both coincide. %. In this case, the photosensitive material may have a portion that does not overlap with the processing material, the processing material may have a portion that does not overlap with the photosensitive material, or a portion where the photosensitive material does not overlap with the processing material. Both portions where the processing material does not overlap with the photosensitive material can be present. In the present invention, portions where the photosensitive material and the processing material do not completely match may be in the width direction, the front-back direction, or may be present in both the width direction and the front-back direction.

In the present invention, at least one of the light-sensitive material and the processing material may have a notch. Due to the presence of the notch, when the photosensitive material and the processing material are overlapped, there may be a portion where they do not match. The shape of the notch is not particularly limited, and examples thereof include a circle, a semicircle, a square, a rectangle, a triangle, and a rhombus. Examples of the position where the cutout portion exists include an end portion of the material, a vicinity of the end portion, and a corner of the end portion. Further, the number of the cutouts is not limited to one, but may be plural.

In the present invention, the portion where the photosensitive material and the processing material do not completely match is the width direction or the front-back direction,
The sieve exists in both the width direction and the front-back direction, and may have a cutout in at least one of the photosensitive material and the processing material.

Hereinafter, specific examples of the superposed state of the light-sensitive material and the processing material in the present invention will be described. The vertical relation, the front-rear relation, the width relation, and the like can be freely changed. It is not limited to this.

FIGS. 1 to 6 show claims 1 to 4 and 6 of the present invention.
A specific example of a state where the photosensitive material and the processing material described in (1) are superimposed is shown. 7 to 11 show specific examples of a state in which the photosensitive material and the processing material according to the first to fourth aspects of the present invention are superposed. 12 to 16 show claims 1 to 4, 6 and 6 of the present invention.
7 shows a specific example of a state in which the photosensitive material and the processing material described in No. 7 are superimposed. 17 to 19 show claims 1 to 5 of the present invention.
Specific examples of the state where the photosensitive material described in Nos. 4 and 7 and the processing material are superimposed are shown. 20 and 21 show specific examples of a state in which the photosensitive material and the processing material according to the first to fourth, sixth, and seventh aspects of the present invention are overlaid. FIGS. 22 and 23 show specific examples of a state in which the photosensitive material and the processing material according to the first to fourth aspects of the present invention are superimposed. FIG. 24 shows a specific example of a state in which the photosensitive material and the processing material according to claim 5 of the present invention are overlaid. FIGS. 25 and 26 show a specific example of a state where the photosensitive material and the processing material according to the fifth and seventh aspects of the present invention are superposed.

In each figure, reference numeral 10 denotes a photosensitive material, reference numeral 20 denotes a processing material, reference numeral 30 denotes a notch, and reference numeral A denotes a transport direction.

[0094]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. Example 1 <Preparation of seed emulsion T-1> Seed emulsion T-1 having two parallel twin planes was prepared by the following method. (A-1 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g Finished with water to 34.0 liters. (Solution B-1) Finish to 3815 ml with 810.0 g of silver nitrate water. (C-1 solution) Potassium bromide 567.3 g Finished to 3815 ml with water. (D-1 solution) Ossein gelatin 163.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) % Methanol solution 5.5 ml Make up to 3961 ml with water. (E-1 solution) Nitric acid (10%) 91.1 ml (F-1 solution) 56% acetic acid aqueous solution Required amount (G-1 solution) Ammonia water (28%) 105.7 ml (H-1 solution) Potassium hydroxide Aqueous solution (10%) required amount

Solution E-1 was added to solution A-1 which was vigorously stirred at 30 ° C. using a stirrer described in JP-A-62-160128, and then solution B-1 and solution C-1 were double-jetted. According to the method, 279 ml of each was added at a low speed for 1 minute to produce silver halide nuclei.

Thereafter, the solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-1 was further added, the pH was adjusted to 9.3 with the solution H-1, and 6.5 minutes. Aging was performed. Thereafter, the pH was adjusted to 5.8 with the F-1 solution, and then the remaining B-1 solution and the C-1 solution were subjected to a double jet method to obtain a pH of 37.
Min, and desalted immediately by a conventional method. When this seed emulsion was observed with an electron microscope, two parallel
This was a monodispersed tabular seed emulsion having an ECD of 0.72 μm having twin planes and a coefficient of variation in particle size distribution of 16%.

<Preparation of Tabular Grain Emulsion Em-1> Emulsion Em-1 was prepared using seed emulsion T-1 and the following solutions. (A-2 solution) Ossein gelatin 519.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) % Methanol solution 4.5 ml Seed emulsion T-1 5.3 mol equivalent Make up to 18.0 liters with water. (Solution B-2) 3.5N silver nitrate aqueous solution 2787 ml (Solution C-2) Potassium bromide 1020 g Potassium iodide 29.1 g Finished to 2500 ml with water. (D-2 solution) Potassium bromide 618.5 g Potassium iodide 8.7 g Make up to 1500 ml with water. (E-2 solution) Potassium bromide 208.3 g Make up to 1000 ml with water. (F-2 solution) 56% acetic acid aqueous solution Required amount (G-2 solution) Potassium bromide 624.8 g Finish up to 1500 ml with water. (H-2 solution) Fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (ECD = 0.05 μm) equivalent to 0.672 mol

The preparation method is shown below. 9942 ml of a 5.0% gelatin solution containing 0.254 mol of potassium iodide
Then, 3092 ml of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. Temperature during particle formation is 4
The temperature was controlled at 0 ° C., and the pH and EAg were established. (I-2 solution) 10 ml of an aqueous solution containing 1.4 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide (Liquid J-2) 2.3 × 10 ⁶ mol of sodium ethylthiosulfonate per mol of silver halide Aqueous solution containing ^-5 mol 100ml (K-2 solution) 10% potassium hydroxide aqueous solution

Solution A-2 was added to the reaction vessel, and while stirring vigorously at 75 ° C., solution I-2 was added.
Solution, Solution C-2 and Solution D-2 were added by a double jet method according to the combination shown in Table 2, and a seed crystal was grown.
Em-1 was prepared. Here, B-2 solution, C-2 solution, D
-2 The addition rate of the liquid is changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the generation of small particles other than the seed particles growing and the particle size distribution due to Ostwald ripening between the growing particles. To prevent deterioration.

First, the crystal growth was performed by controlling the solution temperature in the first addition reaction vessel to 75 ° C., the pAg to 8.9, and the pH to 5.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all of the remaining solution B-2. For controlling pAg and pH, Solution E-2, Solution F-2 and Solution K-2 were added as necessary.

After the formation of the particles, desalting was performed according to the method described in JP-A-5-72658. Thereafter, gelatin is added and dispersed, and at 40 ° C., pAg 8.06, pH
An emulsion of 5.8 was obtained. The silver iodide content of this emulsion was 5.3.
When the silver halide grains in this emulsion were observed with an electron microscope, the average aspect ratio of the ECD (grain size in terms of projected area circle) = 1.50 μm and the variation coefficient of the grain size distribution of 14% was 7. 0 hexagonal tabular monodispersed silver halide grains.

[0102]

[Table 1]

<Chemical Sensitization and Spectral Sensitization> Em-1 was divided into small portions, and the following spectral sensitizing dyes were added to each of them. Further, optimal amounts of sodium thiocyanate, sodium thiosulfate, triethylthiourea, chloroauric acid, 1- (3-acetamidophenyl) -5-mercaptotetrazole (AF-
5) was added and heated to 50 ° C. After ripening for each of the optimum reaction times, the mixture was cooled, and a stabilizing agent ST-1 and an antifoggant AF-5 were added thereto to obtain a red-sensitive silver halide emulsion.
1, green-sensitive silver halide emulsion-1 and blue-sensitive silver halide emulsion-1 were obtained. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-sensitive silver halide emulsion-1 Sensitizing dye (SD-1) 0.04 mmol Sensitizing dye (SD-2) 0.07 mmol Sensitizing dye (SD-3) 0.04 mmol Sensitizing dye (SD-4) 0.13 mmol green-sensitive silver halide emulsion-1 sensitizing dye (SD-5) 0.04 mmol sensitizing dye (SD-6) 0.03 mmol sensitizing dye (SD-7) 0 .17 mmol sensitizing dye (SD-8) 0.02 mmol sensitizing dye (SD-9) 0.02 mmol sensitizing dye (SD-10) 0.02 mmol blue-sensitive silver halide emulsion-1 sensitizing dye (SD-11) 0.19 mmol Sensitizing dye (SD-12) 0.06 mmol

Further, according to a method basically similar to that of the above Preparation Example, the silver iodide content was 3 mol%, the ECD (particle diameter in terms of projected area circle) = 0.59, the average aspect ratio was 3.4, and the particle diameter distribution was as follows. A silver halide emulsion containing monodispersed silver iodobromide tabular grains having a variation coefficient of 16% was compared with a red-sensitive silver halide emulsion-1, a green-sensitive silver halide emulsion-1, and a blue-sensitive silver halide emulsion-1. Similarly, spectral sensitization and chemical sensitization were performed to obtain a red-sensitive silver halide emulsion-2, a green-sensitive silver halide emulsion-2, and a blue-sensitive silver halide emulsion-2. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-sensitive silver halide emulsion-2 Sensitizing dye (SD-1) 0.08 mmol Sensitizing dye (SD-3) 0.08 mmol Sensitizing dye (SD-4) 0.42 mmol Green-sensitive halogen Silver halide emulsion-2 Sensitizing dye (SD-5) 0.04 mmol Sensitizing dye (SD-6) 0.15 mmol Sensitizing dye (SD-7) 0.35 mmol Sensitizing dye (SD-9) 0 0.05 mmol Blue-sensitive silver halide emulsion-2 Sensitizing dye (SD-11) 0.38 mmol Sensitizing dye (SD-12) 0.11 mmol The sensitizing dyes used here are shown below.

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<Preparation of Photosensitive Material 101> Using the emulsion thus obtained and a compound described below, a subbed transparent PEN
Photosensitive layers having the following composition were sequentially applied on a base (thickness: 85 μm) to prepare a photosensitive material 101 having a multilayer structure. Amount of each material added mg of coating amount per 1 m ²
/ M ² . However, silver halide was expressed in terms of silver.

First layer: Antihalation layer Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling solvent (Oil-2) 200 Zinc oxide 410 Dye (AI-1) 280 Dye (AI-2) 240 Dye (AI) -3) 400

Second layer: Cyan coloring layer Gelatin 1000 Red-sensitive silver halide emulsion-1 350 Red-sensitive silver halide emulsion-2 290 Color developing agent (D-24) 520 Cyan coupler (C-1) 360 High boiling solvent (Oil-1) 460 High boiling point solvent (Oil-2) 130 Antifoggant (AF-6) 1

Third layer: Intermediate layer Gelatin 800 Dye (AI-2) 160 Additive (HQ-2) 20 High boiling solvent (Oil-2) 60 Water-soluble polymer (PS-1) 60 Zinc oxide 410

Fourth layer: Magenta color-forming layer Gelatin 1800 Green-sensitive silver halide emulsion-1 350 Green-sensitive silver halide emulsion-2 290 Color developing agent (D-24) 520 Magenta coupler (M-1) 400 High boiling solvent (Oil-1) 460 High boiling point solvent (Oil-2) 90 Antifoggant (AF-6) 1 Water-soluble polymer (PS-1) 20

Fifth layer: Intermediate layer Gelatin 800 Dye (AI-1) 320 Additive (HQ-1) 6 Additive (HQ-2) 20 High boiling solvent (Oil-1) 75 Zinc oxide 240

Sixth layer: Yellow color-forming layer Gelatin 3200 Blue-sensitive silver halide emulsion-1 670 Blue-sensitive silver halide emulsion-2 550 Color developing agent (D-24) 520 Yellow coupler (Y-1) 1060 High boiling solvent (Oil-1) 450 High boiling point solvent (Oil-2) 300 Antifoggant (AF-6) 2 Water-soluble polymer (PS-1) 40

Seventh layer: Intermediate layer Gelatin 1500 Water-soluble polymer (PS-1) 60 Zinc oxide 1380

Eighth layer: protective layer Gelatin 1000 Matting agent (WAX-1) 200 Water-soluble polymer (PS-1) 120

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersion aid SU-4, stabilizer S
T-1, ST-2, antifoggants AF-1, AF-2,
AF-3, AF-4, AF-5, hardeners H-1, H-
2, H-3 and H-4 were added. Also, F-2, F-
3, F-4 and F-5 each in a total amount of 15.0 mg /
m ^Two, 60.01mg / m^Two, 50.0mg / m^TwoAnd 1
0.0mg / m^TwoAnd add to each layer so that
Was. The materials used above are as follows.

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<Preparation of processing sheet P-1>
A layer having the following composition was sequentially applied on an EN base (thickness: 85 μm) to prepare a treated sheet P-1. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2. The materials used were as described above, and those not present were shown below.

First layer Addition amount (mg / m ² ) Gelatin 460 Water-soluble polymer (PS-2) 20 Surfactant (SU-3) 23 Hardener (H-5) 360

Second layer Gelatin 2400 Water-soluble polymer (PS-3) 360 Water-soluble polymer (PS-1) 700 Water-soluble polymer (PS-4) 600 High boiling point solvent (Oil-3) 2000 Guanidine picolinate 2730 Quinolic acid Potassium 225 Sodium quinolinate 180 Surfactant (SU-3) 24

Third layer Gelatin 2400 Water-soluble polymer (PS-1) 24 Surfactant (SU-3) 700 Guanidine picolinate 2370 Water-soluble polymer (PS-3) 360 Water-soluble polymer (PS-4) 600

Fourth layer Gelatin 220 Water-soluble polymer (PS-2) 60 Water-soluble polymer (PS-3) 200 Potassium nitrate 12 Matting agent (PM-2) 10 Surfactant (SU-3) 7 Surfactant (SU) -5) 7 Surfactant (SU-6) 10 Hardener (H-5) 370

[0131]

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<Preparation of photosensitive materials 102 to 103> Photosensitive materials 102 and 103 were prepared in the same manner as in preparation of photosensitive material 101 except that the amount of zinc oxide in the seventh layer was changed to 730 and 240. .

<Preparation of Processing Sheets P-2 and P-3> Processing of the processing sheet P-1 was performed in the same manner except that the addition amount of guanidine picolinate of the third layer was changed to 910 and 0. Sheets P-2 and P-3 were prepared.

<Evaluation of Samples> The photosensitive materials 101 to 103 produced as described above were cut into a size of 60 mm × 90 mm and processed as described below. That is, 1/600 Lux is applied to each photosensitive material via an optical wedge.
After exposure for 100 seconds, the exposed surface of the photosensitive material is exposed to 40
15 ml / m ² of hot water of 10 ° C., and treated sheets P-1 to P-1
After overlapping the film surfaces of P-3 and each other, heat development was performed at 85 ° C. for 40 seconds using a heat block. At this time, the processing sheet has the same size as the photosensitive material, and as shown in FIG.
Both were shifted and superimposed. When the photosensitive material and the processing sheet were peeled off within 5 seconds from the completion of the heat development, a gray wedge-shaped image was obtained on the photosensitive material. The transmission density of each sample was measured with blue light, green light and red light, and a characteristic curve was obtained. Table 2 shows the difference (ΔD) between the maximum density and the minimum density obtained by the combination of each photosensitive material and each processing sheet. (The larger the ΔD, the better.)

[0135]

[Table 2]

As is apparent from Table 2, a sufficient △ D in the "photographic light-sensitive material containing a layer containing a compound which forms a dye by a coupling reaction with a developing agent and an oxidized form of the developing agent" according to the present invention is sufficient. In order to obtain an aqueous solution, it is preferable to carry out thermal development in the presence of a large amount of a poorly water-soluble metal salt compound (here, zinc oxide) and / or a large amount of a base precursor (here, picolinic acid, quinolinic acid). That is, it is clear that it is preferable to use the photosensitive materials 101 and 102 and the processing sheets P-1 and P-2 in order to obtain a sufficient ΔD.

Example 2 The photosensitive materials 101 to 103 prepared in Example 1 had a thickness of 50 μm.
A stripe image having a pitch was exposed, and the same heat development processing as in Example 1 was performed. However, the time from the end of the heat development to the peeling of the photosensitive material and the processing sheet was changed in the range of 5 seconds to 120 seconds. While observing the surface condition of the photosensitive material after peeling, the image was read by a scanner, and the quality was evaluated. Table 3 shows the results. The evaluation is expressed in five grades, each of which is based on the following scale.

A: No defect is observed on the surface of the photosensitive material, and scanning can be performed without any problem. ○ ・ ・ Small scratches and defects are observed on the photosensitive material surface,
There is almost no hindrance to scanner reading. Δ: The surface of the photosensitive material is damaged or defective, and the quality of the image read by the scanner is deteriorated. X: The influence of scratches and defects generated on the surface of the photosensitive material is large, and the quality of the image read by the scanner is significantly reduced. XX: Cannot be peeled. Alternatively, the photosensitive material after peeling is so damaged that it is almost impossible to read by a scanner.

[0139]

[Table 3]

As is evident from Table 3, the photosensitive material according to the present invention has an adverse effect on scanner reading unless it is immediately peeled off after thermal development. This tendency is remarkable in a combination of a photosensitive material and a processing sheet capable of obtaining a large ΔD. Therefore, in order to achieve both ΔD and scanner reading quality, it is necessary to use means capable of promptly performing the peeling step.

Example 3 The same processing and evaluation as in Example 2 were performed, except that the photosensitive material and the processing sheet were overlapped without shifting each other. In this case, the peeling operation is difficult to perform, and it is difficult to complete the peeling within 5 seconds. It took 10 seconds or more. Table 4 shows the evaluation results after 10 seconds. The five-point scale is the same as in Table 3.

[0142]

[Table 4]

It can be seen that, since excessive stress is applied at the time of peeling, defects on the surface of the photosensitive material are more likely to occur than in the case of Example 2, and the influence on scanner reading is increased.

(Comparative Example) As a photosensitive material, a donor "PG donor PG-S" for pictography manufactured by FUJIFILM Corporation was used.
G ", and the same processing and evaluation as in Example 3 were performed using PG paper PG-SG, an image receiving paper for pictography manufactured by FUJIFILM Corporation as a processing sheet. Also in this case 5
The peeling could not be completed within seconds, but even after 120 seconds from the heat development, the peeling could not be performed and no defect occurred on the surface of the photosensitive material.

According to the second embodiment, it is preferable since the peeling is easy. However, even after exposure as in Example 2, almost no image was formed after development (not suitable as a photosensitive material for photography).

[0146]

According to the present invention, a method for forming an image by exposing a silver halide photographic material to an image, superimposing it on a processing material and subjecting it to heat development to form an image is also possible. The processing material can be easily and surely peeled off, so that digital image information with little noise can be created even if it is read by a scanner after image formation and converted into digital image information.

[Brief description of the drawings]

FIG. 1 is a specific example of a state in which a photosensitive material and a processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 2 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 3 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 4 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 5 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 6 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 7 is a specific example of a state where the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 8 is a specific example of a state where the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 9 is a specific example of a state where the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 10 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 11 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 12 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superimposed.

FIG. 13 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superposed.

FIG. 14 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superimposed.

FIG. 15 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superimposed.

FIG. 16 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superimposed.

FIG. 17 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 18 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 19 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 20 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6 and 7 of the present invention are superposed.

FIG. 21 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4, 6, and 7 of the present invention are superimposed.

FIG. 22 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superposed.

FIG. 23 is a specific example of a state in which the photosensitive material and the processing material according to claims 1 to 4 of the present invention are superimposed.

FIG. 24 is a specific example of a state where the photosensitive material according to claim 5 and a processing material are superimposed.

FIG. 25 is a specific example of a state in which the photosensitive material according to claim 5 and the processing material are superimposed.

FIG. 26 is a specific example of a state in which the photosensitive material according to claim 5 and the processing material according to claim 7 are superimposed.

[Explanation of symbols]

 10: photosensitive material 20: processing material 30: notch A: transport direction

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H016 AC00 BA00 BC03 BD00 BE00 BK00 2H023 AA02 CD06 CD10 2H112 AA03 AA11 BA23 BC41

Claims (10)

[Claims] 1. A support comprising a plurality of photographic constituent layers including a layer containing a photosensitive silver halide emulsion, a developing agent, and a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent. A method of forming an image by superposing a silver halide photographic light-sensitive material on a processing material containing a base and / or a base precursor after image exposure and subjecting the silver halide photographic light-sensitive material to heat development to form an image. A heat development processing method, wherein the processing materials are overlapped in a state where they do not completely match. 2. The method according to claim 1, wherein said developing agent has the following general formula I-1 to I-
2. The thermal development method according to claim 1, which is at least one of the compounds represented by formula (5). Embedded image In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group.
Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. Embedded image In the formula, Z represents an atom group forming an aromatic ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. Embedded image In the formula, R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. R ₆ represents a substituted or unsubstituted alkyl group.
X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ ,
R _8, R _9, R ₁₀ represents a hydrogen atom or a substituent, R _7,
R ₈ , R ₉ and R ₁₀ may combine with each other to form a double bond or a ring. Embedded image In the formula, Z represents an atom group forming an aromatic ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. Embedded image In the formula, R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. R ₆ represents a substituted or unsubstituted alkyl group.
X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ ,
R _8, R _9, R ₁₀ represents a hydrogen atom or a substituent, R _7,
R ₈ , R ₉ and R ₁₀ may combine with each other to form a double bond or a ring. 3. A silver halide photographic light-sensitive material containing a poorly water-soluble metal salt compound.
3. The thermal development method according to 1. 4. A coupling reaction between a mosaic or striped filter layer having at least two regions having different spectral absorption characteristics on a support and at least one oxidized form of a silver halide emulsion and a developing agent. A method for forming an image by subjecting a silver halide photographic light-sensitive material having a layer containing a compound that forms a dye to image-exposure, superimposed with a processing material and subjected to heat development processing,
A heat development processing method comprising superposing the silver halide photographic material and the processing material in a state where they do not completely coincide with each other. 5. A silver halide photographic material having at least one layer containing a silver halide emulsion on both sides of a support, after imagewise exposure, is superposed on a processing material, and is subjected to heat development. Wherein the silver halide photographic light-sensitive material and the processing material are superimposed in a completely inconsistent state. 6. A method for forming an image by subjecting a roll-shaped silver halide photographic light-sensitive material to image processing, superimposing it on a processing material and subjecting it to heat development processing, wherein said silver halide photographic light-sensitive material and said processing A heat development method characterized in that the materials are overlapped in a state where they do not completely match. 7. The method according to claim 1, wherein at least one of the silver halide photographic material and the processing material has a cutout. 8. The thermal development processing method according to claim 1, wherein a processing material having a total amount of a base and a base precursor of 20 mmol / m ² or more is used. 9. A heat development processing method according to claim 1, wherein a light-sensitive material in which the hardly water-soluble metal salt compound contained on one side of the support is 20 mmol / m ² or more is used. . 10. An image formed on a silver halide photographic light-sensitive material by the heat development processing method according to claim 1 and converted into digital image information by reading with a scanner. Digital image information creation method.