JPH06266082A - Heat-developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the heat-developable photosensitive material small in fluctuation of sensitivity even if temperature varies at the time of exposure by forming a photosensitive silver halide emulsion layer containing silver halide grains formed in the presence of a selenium compound on a support. CONSTITUTION:The heat-developable photosensitive material has one of the photosensitive silver halide emulsion layers containing the silver halide grains formed in the presence of the selenium compound on a support and this layer has maximum spectral sensitivity in the wavelength region of >=700nm. The silver halide grains formed in the presence of the selenium compound is formed usually by adding an instable type selenium compound, such as isoselenocyanates, selenoureas, selenoketones, selenoamides, selenocarboxylic acids, phosphine selenides, and colloidal metallic selenium, and/or a non instable selenium compound at a high temperature, preferably, >=40 deg.C, and stirring the emulsion for a prescribed time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material which has little sensitivity variation even when the temperature during exposure varies.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver salt photograph edition (1982, published by Corona Publishing Co., Ltd.), pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
18443, 61-238056, and U.S. Pat. No. 47.
No. 83396, No. 4740445 and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the dye is diffused by being oxidized and reduced by the reducing agent remaining without being oxidized. US Pat. No. 4,783,396 discloses a diffusible dye as a compound that releases a diffusible dye by a similar mechanism by reductive cleavage of an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom). A photothermographic color light-sensitive material using a releasing compound is described.

[0006]

Since such a photothermographic material requires a short processing time and has a simple developing apparatus, it has been used in various applications in recent years. With the spread thereof, when it is used in various places, there arises a problem that the sensitivity changes due to a change in temperature of the place where it is used. In particular, when a photothermographic material having a spectral sensitivity peak in the infrared region is created, the sensitivity of the sensitizing dye in the infrared region generally fluctuates due to changes in electron injection efficiency into the silver halide grains due to temperature changes. Resulting in. To solve this problem, Japanese Patent Application No. 3-31521
No. 9 reported a photothermographic material containing iron ions in silver halide grains, but it was still insufficient. Therefore, it is an object of the present invention to provide a photothermographic material that has little sensitivity variation even if the temperature varies during exposure.

[0007]

Such an object is achieved by the following constitution (1) or (2).

(1) A photothermographic material comprising a support and at least one photosensitive silver halide emulsion layer containing silver halide grains formed in the presence of a selenium compound. (2) A photosensitive silver halide emulsion layer containing silver halide grains formed in the presence of a selenium compound is 700 n
The photothermographic material according to (1) above, which has a maximum spectral sensitivity in a region of m or more.

The present invention will be described in more detail below. As the selenium compound used in the present invention, a selenium compound disclosed in a conventionally known patent can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, European Patent Publication No. 458287, and US Pat. No. 5,158,892 are preferably used. Specific unstable selenium compounds include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenium ketones, selenoamides, selenocarboxylic acids (eg, 2-selenopropione). Acid, 2-
(Selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like.

Although the preferred types of labile selenium compounds have been described above, these are not limiting. Stable selenium compounds as additives for photographic emulsions are known to those skilled in the art as far as selenium is unstable, the structure of the compounds is not so important, and the organic part of the selenium compound molecule is selenium. It is generally understood that they have no role other than to support and allow them to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

The non-labile selenium compounds used in the present invention include Japanese Examined Patent Publication Nos. 46-4553 and 52-344.
The compounds described in JP-B No. 91 and JP-B-52-34491 are used. Examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, and 2-selenazolidinediones. , 2-selenooxazolidinethione and derivatives thereof and the like.

Of these selenium compounds, compounds represented by the following general formula (I) and general formula (II) are preferable. General formula (I)

[0013]

[Chemical 1]

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, , Vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoyl) Phenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR
₁ (R _2), - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group,
It represents an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group benzoyl group, pentafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethyl group). Benzoyl group).

In the general formula (I), Z ₁ preferably represents an alkyl group, an aryl group or --NR ₁ (R ₂ ) and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different, a hydrogen atom,
It represents an alkyl group, an aryl group or an acyl group.

In the general formula (I), more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide.

General formula (II)

[0019]

[Chemical 2]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, --OR ₇ , --NR ₈ (R ₉ ) , -SR ₁₀ , -S
eR ₁₁ , X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (II), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group). Group, n-propyl group, isopropyl group, t-
Butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, Benzyl group,
Phenethyl group).

In the general formula (II), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3 -Sulfophenyl group, α-naphthyl group, 4-methylphenyl group).

In the general formula (II), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (for example, pyridine group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula (II), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (II), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or --OR ₇ ,
R ₇ represents an aliphatic group or an aromatic group. General formula (II)
And more preferably trialkylphosphine selenide,
Represents triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

In the present invention, the selenium compound is allowed to be present in the grain forming reaction system during the formation of silver halide grains.
Here, the term "during the formation of silver halide grains" refers to the step before the silver halide grains become the final size or shape, and specifically, the mixing step of the water-soluble halide and the water-soluble silver salt and the subsequent physical step. Refers to the aging process. In order to allow the selenium compound to be present in the reaction system for silver halide grain formation, in the emulsion grain formation step, in a dispersion medium (gelatin or polymer having a protective colloid) solution, in an aqueous halide solution,
It is carried out by allowing a selenium compound to coexist in the silver salt aqueous solution or another aqueous solution. The selenium compound is dissolved in water or an organic solvent such as methanol and ethanol, alone or in a mixed solvent, or disclosed in JP-A-4-140738.
No. 4-140739, it is used by dissolving it in a gelatin solution. The selenium compound used is 1
The selenium compound may be used in combination of two or more kinds without being limited to the kind. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

In the present invention, the amount of the selenium compound used in the silver halide grain forming step is preferably 1 × 10 ^-8 mol or more and 1 × 10 ^-3 mol or less per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-4 mol or less. Unlike the case where the selenium compound of the present invention is added during chemical sensitization, it is introduced (doped) inside the silver halide grains. And by that,
It is considered that the sensitivity is prevented from changing due to the temperature change during the exposure.

The silver halide used in the present invention is the same as the silver halide conventionally used in photothermographic materials, except that it is formed in the presence of a selenium compound. Is. That is, the halogen composition may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral, 1
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (197).
8 years), and any of the silver halide emulsions described in JP-A No. 62-253159 can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The heat-developable light-sensitive material of the present invention basically has a photosensitive silver halide and a binder on a support and, if necessary, further contains an organic metal salt oxidizing agent, a reducing agent and a dye-donating property. A compound (which may also serve as a reducing agent as described later) can be contained. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, there are combinations of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. In this case, the silver halide formed into grains in the presence of the selenium compound of the present invention may be used in at least one of the above photosensitive layers.
The photothermographic material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the superabsorbent polymer described above. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of reducing agents used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,483,914 No. 30
~ Column 31, ibid. 4,330,617, ibid. 4,590,1
52, JP-A-60-140335 (17)-
(18), No. 57-40245, No. 56-1387.
No. 36, No. 59-178458, No. 59-53831.
No. 59-182449 and 59-182450.
Nos. 60-119555, 60-128436 to 60-128439, 60-19854.
No. 0, No. 60-181742, No. 61-259253.
Nos. 62-244044, 62-131253 to 62-131256, European Patent No. 220,
There are reducing agents and reducing agent precursors described on pages 78 to 96 of 746A2. US Pat. No. 3,039,869
Combinations of various reducing agents such as those disclosed in US Pat.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent is optionally added to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Examples thereof include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later. In the present invention, the reducing agent is added in an amount of 0.
The amount is 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, silver can be used as the image forming substance. Further, when the silver ion is reduced to silver under a high temperature condition, a compound that generates or releases a mobile dye in response to this reaction or vice versa, that is, a dye-donating compound may be contained. it can. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
Specific examples of color developing agents and couplers can be found in T.W. H. Jam
es "The Theory of the Pho"
"graphical Process" 4th edition 291 ~
Pp. 334 and 354-361, JP-A-58-123
No. 533, No. 58-149046, No. 58-1490.
47, 59-11148, and 59-12439.
9, No. 59-174835, No. 59-231539.
No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2.
No. 3474, No. 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) n-Z represents a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different. General formula [LI]
Specific examples of the dye-donating compound represented by are the following compounds (1) to (4). In addition, the following ~
Is to form a diffusible dye image (positive dye image) corresponding to the development of silver halide, and is a diffusible dye image (negative dye image) to correspond to the development of silver halide.
Is formed.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, and 3,482,972 are described. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used.
Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379, JP-A-59-185333,
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107, JP-A-59-84453.
No. 101649, No. 61-88257, RD240
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
No. 142530, U.S. Pat. Nos. 4,343,893 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction, U.S. Pat. Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610, which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,783,3.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64) and (70), and compounds (11) to (23) described in Kokai Giho 6-6199.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, and U.S. Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like. Reducible to silver halide or organic silver salt,
A compound that releases a diffusible dye when the other party is reduced (DR
R compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381.
9, 51-104343, RD17465, U.S. Pat. Nos. 3,725,062 and 3,728,113.
No. 3,443,939, JP-A-58-11653.
7, 57-179840, U.S. Pat. No. 4,50.
0,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626 in columns 22 to 44. Among them, the compounds (1) to
(3), (10) to (13), (16) to (19),
(28)-(30), (33)-(35), (38)-
(40) and (42) to (64) are preferable. The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful. In addition, as a dye-donor compound other than the coupler and the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure May 1978 issue, pages 54 to 58, etc.), Azo dyes used in the heat developable silver dye bleaching method (US Pat.
35,957, Research Disclosure, 1
976, No. 4, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617, etc.) and the like can also be used.

Hydrophobic additives such as dye-donating compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donor compound used.
It is the following. Also, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,50.
0,626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat.
00,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages (32) to (41), mordants described in JP-A-6-61
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256, pages (27) to (29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. . The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. As an example, K. Venkataraman edition “Th
e Chemistry of Synthetic
Dyes ", Vol. V, Chapter 8, compounds described in JP-A-61-143752 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As a hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye fixing element in order to enhance the storability of the light-sensitive material. In addition to the above, European Patent Publication 210,660 and US Pat. No. 4,740,445.
Combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound) described in JP-A-61-
Compounds that generate a base by electrolysis as described in No. 232451 can also be used as the base precursor.
The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive material and the dye fixing element.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal created by using a computer represented by Signal, CG and CAD can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of a dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 70 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower. Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

Further, in order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. is contacted. And passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0076]

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

Example 1

A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant,
0.5 g of the anionic surfactant (1) was added to a 5% gelatin aqueous solution, and the mixture was pulverized with a mill for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain an electron transfer agent dispersion having an average particle size of 0.35 μm.

[0082]

[Chemical 11]

[0083]

[Chemical 12]

Next, a method for preparing a dispersion of the dye trapping agent will be described.

Polymer latex (1) (solid content 13
%) 108 ml, surfactant (1) 20 g, and water 1232 ml with stirring, while stirring anionic surfactant (1) 5
% Aqueous solution 600 ml was added over 10 minutes. Using an ultrafiltration module, the dispersion thus prepared was
It was concentrated to 0 ml and desalted. Next, 1500 ml of water was added, and the same operation was repeated once more to disperse the dye trapping agent dispersion 5
00g was obtained.

[0086]

[Chemical 13]

[0087]

[Chemical 14]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

Gelatin dispersions of yellow, magenta, cyan and electron donor were prepared according to the formulations shown in Table 1, respectively. That is, each oil phase component was dissolved by heating at about 60 ° C to form a uniform solution, this solution and the water phase component heated at about 60 ° C were added, and the mixture was stirred and mixed, and then mixed with a homogenizer for 13 minutes for 120 minutes.
Dispersed at 00 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0090]

[Table 1]

[0091]

[Chemical 15]

[0092]

[Chemical 16]

[0093]

[Chemical 17]

[0094]

[Chemical 18]

[0095]

[Chemical 19]

[0096]

[Chemical 20]

[0097]

[Chemical 21]

[0098]

[Chemical formula 22]

[0099]

[Chemical formula 23]

[0100]

[Chemical formula 24]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride)
g and 30 mg of the compound (4) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were further added simultaneously at an equal flow rate for 25 minutes. Also (III), (I
V) 10 minutes after the addition of the liquid was started, an aqueous solution of a gelatin dispersion of the dye (1 g of gelatin in 105 ml of water, 70 g of the dye (a)) was added.
mg, pigment (b) 139 mg, pigment (c) 5 mg at 45 ° C
Which was kept warm) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7 to adjust sodium thiosulfate and 4-hydroxy-.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then the antifoggant (1) was added, followed by cooling. Thus, 657 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0104]

[Chemical 25]

[0105]

[Table 2]

[0106]

[Chemical formula 26]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 783 ml of water, 0.5 g of potassium bromide, 6 g of sodium chloride).
Then, to the compound (4) (30 mg added and kept at 65 ° C.), the solutions (I) and (II) in Table 3 were simultaneously added at an equal flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were further added simultaneously at an equal flow rate for 15 minutes. Also, (III) solution, (I
V) 2 minutes after the start of the addition of the solution, an aqueous solution of a gelatin dispersion of the dye (0.9 g of gelatin in 95 ml of water, 61 of the dye (a)) was added.
50 mg, containing 121 mg of pigment (b) and 4 mg of pigment (c)
Which was kept warm) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added, followed by cooling. Thus, 671 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0109]

[Chemical 27]

[0110]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride in 690 ml of water).
g and the compound (4) (15 mg, which was kept warm at 47 ° C.), the solutions (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 32 minutes. Also, (III) solution,
One minute after the addition of the liquid (IV) was completed, an aqueous solution of a gelatin dispersion of the dye (2.5 g of gelatin in 100 ml of water, dye (d) 2
(Containing 50 mg and kept at 40 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene was added for optimum chemical sensitization at 68 ° C, and then an antifoggant
After adding (2), it was cooled. Thus, 658 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm
Got

[0113]

[Table 4]

[0114]

[Chemical 28]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride).
Then, the solution (I) and the solution (II) shown in Table 5 were simultaneously added to the compound (4) (15 mg added and kept at 60 ° C.) at an equal flow rate for 20 minutes. After 10 minutes, solution (III) and solution (IV) in Table 5 were simultaneously added at the same flow rate for 20 minutes. Also, (III) solution,
One minute after the addition of the liquid (IV) was completed, an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 72 ml of water, 18 of the dye (d)) was added.
(Containing 0 mg and kept at 40 ° C.) was added all at once.

After washing with water and desalting in a conventional manner, 32 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added, followed by cooling. Thus, 655 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0117]

[Table 5]

Photosensitive silver halide emulsion (5) [for blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 5 g of sodium chloride).
Then, the solution (I) and the solution (II) shown in Table 6 were simultaneously added to the compound (4) (15 mg added and kept at 51 ° C.) at an equal flow rate for 8 minutes. After 10 minutes, the solutions (III) and (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes. Also, (III) solution, (I
One minute after the addition of the solution V), an aqueous solution of the dye (in 95 ml of water and 5 ml of methanol, 220 mg of the dye (e) and 1 of the dye (f)) was added.
10 mg and kept at 31 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and then sodium thiosulfate and 4-hydroxy-6-methyl- 1,3,3a, 7-Tetrazaindene was added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.32 μm
5 g was obtained.

[0120]

[Table 6]

[0121]

[Chemical 29]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (water 695 ml, gelatin 20 g, potassium bromide 0.3 g, sodium chloride 9 g).
Then, to the compound (4) which was added with 15 mg of the chemical A and kept at 63 ° C.), the solutions (I) and (II) in Table 7 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, the solutions (III) and (IV) in Table 7 were further added simultaneously at an equal flow rate for 30 minutes. Also, (II
One minute after the addition of the solutions (I) and (IV) was completed, an aqueous solution of the dye (water 6) was added.
Into 6 ml and 4 ml of methanol, 150 mg of dye (e) and 75 mg of dye (f), which were kept at 45 ° C., were added all at once.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and then sodium thiosulfate and 4-hydroxy-6-methyl- 1,3,3a, 7-Tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added and then cooled. Thus, 645 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0124]

[Table 7]

A coating solution was prepared as follows using the above dispersion and emulsion.

First layer (red-sensitive emulsion layer) 648.5 g of the photosensitive silver halide emulsion (1), 351.5 g of the photosensitive silver halide emulsion (2), and 1050 g of a 16% aqueous solution of lime-processed gelatin, 40 g each. Melted at ℃ and mixed. Further, 4563 g of a gelatin dispersion of a cyan dye-providing compound was dissolved at 45 ° C and added. Next, 83.6 ml of a 5% aqueous solution of the water-soluble polymer (1) was added to prepare a coating solution for the first layer. Viscosity is 85 at 40 ℃
The centipoise and pH were 6.3.

[0127]

[Chemical 30]

Second Layer and Sixth Layer (Intermediate Layer) A solution prepared by dissolving 1845 g of a zinc hydroxide dispersion at 45 ° C. in 1000 g of a 16% aqueous solution of lime-processed gelatin was added,
41 ml of 25% aqueous solution of dextran, 748 g of gelatin dispersion of electron donor dissolved at 45 ° C., 527 ml of dye trapping agent dispersion, and 20 ml of 5% aqueous solution of water-soluble polymer (1) were added to the second layer and This was the coating liquid for the sixth layer. At 40 ° C, the viscosity was 80 centipoise and the pH was 7.9.

Third Layer (Green Sensitive Emulsion Layer) 710 g of the photosensitive silver halide emulsion (3) and 290 g of the photosensitive silver halide emulsion (4) were dissolved and mixed at 40 ° C. Further, 2511 g of a gelatin dispersion of a magenta dye-donor compound was dissolved at 45 ° C and added. Next, 9.6 ml of a 9.8% aqueous solution of sulfuric acid, 5% of the water-soluble polymer (1)
70.5 ml of the aqueous solution was added to obtain a coating solution for the third layer. Four
At 0 ° C, the viscosity was 75 centipoise and the pH was 5.4.

Fourth layer (intermediate layer) A solution prepared by dissolving 317 g of the dispersion of the electron transfer agent at 45 ° C. in 1000 g of a 16% aqueous solution of lime-processed gelatin was added, and 3777 ml of ion-exchanged water and a gelatin dispersion 7 of the electron donor.
Dissolved 48g at 45 ℃, 25% of dextran
61 ml of an aqueous solution, 426 ml of a dye trapping agent dispersion, 19.1 ml of a 9.8% aqueous solution of sulfuric acid, 5 parts of a water-soluble polymer (1).
% Aqueous solution was added to prepare a coating solution for the fourth layer. Four
At 0 ° C, the viscosity was 85 centipoise and the pH was 5.3.

Fifth Layer (Blue Sensitive Emulsion Layer) 765.2 g of the photosensitive silver halide emulsion (5) and 234.8 g of the photosensitive silver halide emulsion (6) were dissolved and mixed at 40 ° C. Further, 2064 g of a gelatin dispersion of a yellow dye-donor compound was dissolved at 45 ° C and added. Next, 11.4 ml of a 9.8% aqueous solution of sulfuric acid, a water-soluble polymer
51.1 ml of the 5% aqueous solution of (1) was added to prepare a coating solution for the fifth layer. Viscosity is 75 centipoise at 40 ℃, pH
Was 5.3.

Seventh Layer (Protective Layer) A gelatin dispersion of a matting agent (18 g of polymethyl methacrylate having an average particle diameter of 3.5 μm dispersed in a 5% aqueous solution of acid-treated gelatin) in 1000 g of a 16% aqueous solution of acid-treated gelatin. ) 38 g, deionized water 1640 ml, 70% methanol solution 1 of the following anionic surfactant (1)
0.6 ml, 20.6 ml of a 5% methanol solution of the following surfactant (3), and 2.5 ml of a 32% aqueous solution of NaOH were added,
This was the coating liquid for the seventh layer. At 40 ° C., the viscosity was 14 centipoise and the pH was 8.7.

[0133]

[Chemical 31]

[0134]

[Chemical 32]

Using the above coating solution, a wet film thickness of Table 9 was formed on the support having the constitution shown in Table 8 below.
The coating solution for the seventh layer was applied from the layer to prepare a light-sensitive material 101.

[0136]

[Table 8]

[0137]

[Table 9]

While the coating solution was being sent to the fourth layer, a 1.6% aqueous solution of the following hardener (1) was added by a mixing system immediately before the coating so that the coating amount was 2.39 ml / m ² . That is, a mixed layer provided with stirring blades was provided at a position immediately before the coating of the liquid feeding system for the fourth layer, and the coating liquid and the aqueous solution of the hardener were combined on the upstream side of the mixed layer for coating.

[0139]

[Chemical 33]

The photosensitive silver halides (3) and (4) of the light-sensitive material 101 were prepared by using emulsions which differed only in that the compound of the present invention was added to solution IV as shown in Table-12. I made 111. Next, how to make the image receiving material will be described.

Image-receiving material R101 having a constitution as shown in Table 10
made.

[0142]

[Table 10]

[0143]

[Table 11]

[0144]

[Chemical 34]

[0145]

[Chemical 35]

[0146]

[Chemical 36]

[0147]

[Chemical 37]

[0148]

[Chemical 38]

[0149]

[Chemical Formula 39]

[0150]

[Chemical 40]

Using the above-mentioned photosensitive materials 101 to 111 and image receiving paper material R101, processing was carried out using an image recording apparatus described in JP-A-2-84634. That is, the original image (a test chart in which Y, M, Cy, and gray wedges whose densities are continuously changed is recorded) is passed through a slit to obtain a table 12
Scanning exposure was carried out at the temperature shown in (1), and the exposed light-sensitive material was immersed in water kept at 40 ° C. for 4 seconds, squeezed with a roller, and immediately superposed so that the image-receiving material and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface becomes 80 ° C., the photosensitive material is peeled from the image receiving material by heating for 15 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. It was

Table 12 shows the results of measuring the sensitivity of magenta in the gray image thus obtained by the self-recording densitometer. The sensitivity is indicated by the relative value of the reciprocal of the exposure amount required for the magenta density to reach 0.7, and the sensitivity when the comparative photosensitive material 101 was exposed at 25 ° C. was expressed as 100.

[0153]

[Table 12]

As is clear from the results shown in Table 12, the sensitivity of the photosensitive material of the present invention is small even if the temperature during exposure changes.

Example 2

A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (7) [Emulsion for Fifth Layer] Solution (I) and solution (II) having the composition shown in Table 16 were added to an aqueous solution having the composition shown in Table 15 and stirred well for 15 minutes. And added at the same time, and thereafter, (III) solution and (I
Solution V) was added over 35 minutes.

[0158]

[Table 13]

[0159]

[Table 14]

In addition, 18 minutes after the start of the addition of the solution III, the 0.5% methanol solution of the sensitizing dye (a) 75 minutes was added for 25 minutes.
cc was added.

[0161]

[Chemical 41]

After washing with water and desalting (the precipitation agent a was used at a pH of 4.1) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 17. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.31 μm.

[0163]

[Chemical 42]

[0164]

[Table 15]

Photosensitive Silver Halide Emulsion (8) [Emulsion for Third Layer] Solution (I) and solution (II) having the composition shown in Table 19 are added to an aqueous solution having the composition shown in Table 18 and stirred for 10 minutes. And added at the same time, and then (III) solution and (I
Solution V) was added over 45 minutes.

[0166]

[Table 16]

[0167]

[Table 17]

After washing with water and desalting (pH was set to 3.9 using the precipitating agent a) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 5.9 and pAg to 7.8. After adjustment, chemical sensitization was performed at 70 ° C. At the end of the chemical sensitization, 42 of a gelatin dispersion of sensitizing dye (b) (5% gelatin, 0.5% sensitizing dye) was added. The compounds used for the chemical sensitization are shown in Table 20. The yield of the obtained emulsion was 645 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.32 μm.

[0169]

[Chemical 43]

[0170]

[Table 18]

Photosensitive Silver Halide Emulsion (9) [Emulsion for First Layer] Solution (I) and solution (II) having the composition shown in Table 22 are added to an aqueous solution having the composition shown in Table 21 for 15 minutes with good stirring. And added at the same time, and thereafter, (III) solution and (I
Solution V) was added over 25 minutes.

[0172]

[Table 19]

[0173]

[Table 20]

After washing with water and desalting (the precipitation agent a was used at a pH of 3.8) by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.6 and pAg to 8.0. After adjustment, chemical sensitization was performed at 58 ° C. At the end of the chemical sensitization, 42 of a gelatin dispersion of sensitizing dye (c) (gelatin 5%, sensitizing dye 1%) was added. The compounds used for the chemical sensitization are shown in Table 23. The yield of the obtained emulsion is 6
It was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7% at 50 g and an average grain size of 0.22 μm.

[0175]

[Chemical 44]

[0176]

[Table 21]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Gelatin dispersions of yellow, magenta, cyan and electron donor were prepared according to the formulations shown in Table 1. That is, each oil phase component was dissolved by heating at about 60 ° C to form a uniform solution, this solution and the water phase component heated at about 60 ° C were added, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes for 100 minutes.
It was dispersed at 00 rpm. Water was added to this and stirred to obtain a uniform dispersion.

By these, a photothermographic material 201 as shown in Table 24 was constructed.

[0180]

[Table 22]

[0181]

[Table 23]

[0182]

[Chemical formula 45]

[0183]

[Chemical formula 46]

[0184]

[Chemical 47]

[0185]

[Chemical 48]

[0186]

[Chemical 49]

[0187]

[Chemical 50]

[0188]

[Chemical 51]

[0189]

[Chemical 52]

[0190]

[Chemical 53]

[0191]

[Chemical 54]

The high-boiling organic solvent (1) is triisononyl phosphate, and the high-boiling organic solvent (2) is
It is trihexyl phosphate.

The photosensitive silver halides (8) and (9) of the light-sensitive material 201 were prepared by using emulsions except that the compound of the present invention was added to solution IV as shown in Table 27. Made 211.

[0194]

[Table 24]

Next, a method for preparing the dye fixing material will be described.

R201 was prepared as a dye-fixing material by coating the composition on Table 25 on a polyethylene-laminated paper support.

[0197]

[Table 25]

[0198]

[Chemical 55]

[0199]

[Chemical 56]

[0200]

[Chemical 57]

[0201]

[Chemical 58]

Polymers, high-boiling organic solvents and matting agents are shown below. Polymer * 5 Sodium vinyl alcohol copolymer (75/25 molar ratio) Polymer * 7 Dextran (molecular weight 70,000) High boiling organic solvent * 8 Reofos 95 (Ajinomoto Co., Inc.)
Matting agent * 10 Benzoanamin resin (ratio of particles exceeding 10μ: 18 vol%)

Next, evaluation was performed by the following exposure and processing.

The above-mentioned light-sensitive materials 201 to 211 are described in Japanese Patent Application No.
Exposure was carried out under the conditions shown in Table 26 using the laser exposure apparatus described in Japanese Patent Application No. 3-81418 and Japanese Patent Application No. 63-204805. 11m on the emulsion side of exposed photosensitive materials 201-211
1 / m ² of water was supplied by a wire bar, and then the dye fixing material R201 and the dye fixing material R201 were superposed so as to be in contact with the film surface. Using a heat roller whose temperature was adjusted so that the water-absorbed film temperature was 85 ° C., the dye fixing material was peeled from the photosensitive material after heating for 25 seconds, and an image was obtained on the dye fixing material.

[0205]

[Table 26]

With respect to the image thus obtained,
Table 27 shows the results obtained by measuring the sensitivities of cyan and yellow using a self-recording densitometer. The sensitivity is represented by the ratio of the reciprocal of the exposure amount at which a density of 0.7 is obtained, and the sensitivity of the comparative photosensitive material 201 is represented as 100.

[0207]

[Table 27]

As is clear from the results in Table 27, the photosensitive material of the present invention shows little change in sensitivity even if the temperature during exposure changes.

[0209]

As described above, according to the present invention,
It is possible to provide that the fluctuation of the sensitivity is small even if the temperature at the time of exposure changes.

[Procedure amendment]

[Submission date] April 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0149

[Correction method] Change

[Correction content]

[0149]

[Chemical Formula 39]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0200

[Correction method] Change

[Correction content]

[0200]

[Chemical 57]

Claims (2)

[Claims] 1. At least one silver halide grain which is grain-formed on a support in the presence of a selenium compound.
A photothermographic material having a layer of a photosensitive silver halide emulsion layer. 2. The photosensitive silver halide emulsion layer containing silver halide grains formed in the presence of a selenium compound has a maximum spectral sensitivity in a region of 700 nm or more. Photothermographic material.