JPH06289556A - Heat developable diffusion transfer type color photosensitive material - Google Patents

Abstract

PURPOSE:To provide the heat developable diffusion transfer type color photosensitive material which is excellent in discrimination without adversely affecting other photographic characteristics. CONSTITUTION:The heat developable diffusion transfer type color photosensitive material having a photosensitive silver halide, binder, reducible dyestuff donative compd. and reducing agent on a substrate further contains)the compd. expressed by the following formula: ([A]-[B]m-[C]n-[D])p-[E]. In the formula, [A] denotes an alkyl mnp group or aryl group; [B] denotes a repeating unit of an ethylene oxide group; [C] denotes a combination group; [D] denotes a dissociatable substituent; [E] denotes a hydrogen ion or mono- to tervalent cations; m denotes >=1 integer; n denotes 0 or 1; p denotes an integer from 1 to 3 corresponding to the valence of [E].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat development diffusion transfer type color light-sensitive material, and more particularly to a heat development diffusion transfer type color light-sensitive material excellent in image discrimination.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity and gradation control. Has been. In particular, since the best image quality is obtained for color hard copy, it has been studied more vigorously these days.

In recent years, the image forming processing method of a light-sensitive material using silver halide has been simplified by a conventional wet processing, an instinct photographic system containing a developing solution, and a dry heat development processing such as heating. Systems have been developed that can quickly obtain images. The simple and rapid processing method described above often employs a method of forming an image by a diffusion transfer method in order to prevent image contamination due to printout of silver halide after the image is formed.

The diffusion transfer method is a method of forming or releasing a diffusible dye imagewise and transferring the diffusible dye to an image-receiving material having a mordant with a solvent such as water. The details are Angew. .Chem.Int.Ed.Engl.22 (1983) 19
It is described in detail in 1. In a system in which an image is formed by a diffusion transfer method, a dye-donor compound is contained in a light-sensitive material, and an image is formed by transferring a dye derived from the compound to an image-receiving material in a developing process. In such a system, even if a small amount of the dye generated in the white background is transferred to the image receiving material, the white background is significantly contaminated. Therefore, Japanese Patent Laid-Open No. 4-2
As described in No. 0956 and the like, attempts have been made to improve a white background by adding a compound having a function of adsorbing a dye to a light-sensitive material (hereinafter referred to as a dye trap method).

[0005]

The inventors have continued to develop the above-mentioned heat development diffusion transfer type color light-sensitive material, and have also examined the dye trap method. However, it has been found that in the conventional method, a large decrease in Dmax causes a remarkable decrease in Dmax in order to obtain a sufficient white background density.

(Object of the Invention) An object of the present invention is to provide a heat-development diffusion transfer type color photographic material excellent in image discrimination.

[0007]

The objects of the present invention are as follows.
This is achieved by the heat development diffusion transfer type color light-sensitive material shown in the section. 1) At least a light-sensitive silver halide, a binder, and a non-diffusible dye-donor compound which releases or forms a diffusible dye on a support in correspondence or inversely to the reaction in which silver halide is reduced to silver. A heat development diffusion transfer type color light-sensitive material having the following general formula [I]
A heat development diffusion transfer type color photosensitive material comprising a compound represented by: General formula [I] ([A]-[B] _m- [C] _n- [D]) _p- [E] In the formula, [A] represents a substituted or unsubstituted alkyl group or aryl group. [B] represents a repeating unit of an ethylene oxide group. [C] represents a linking group.
[D] represents an anionic dissociative substituent. [E]
Represents a hydrogen ion or a trivalent cation. m represents an integer of 1 or more. n represents 0 or 1. p represents an integer of 1 to 3 corresponding to the valence of [E]. 2) The heat-development diffusion transfer type color light-sensitive material as described in (1), which further comprises a polymer compound represented by the following general formula [II]. General formula [II] [X]-[Y] _k [Z] In the formula, [X] represents a repeating unit of a monomer having a quaternary ammonium group. [Y] represents a repeating unit of a monomer having no quaternary ammonium group. [Z]
Is a counter anion of [X]. k is an integer of 0 or more. 3) One of the quaternary ammonium group counter anions contained in the polymer compound represented by the general formula [II].
0% or more is an anion obtained by removing [E] from the general formula [I], (1) or (2)
The heat development diffusion transfer type color photosensitive material described.

The present invention will be described in detail below.

In the present invention, the compound represented by the general formula [I] belongs to the category of compounds used as a surfactant in the field. In the general formula [I],
The group represented by [A] represents a substituted or unsubstituted alkyl group or aryl group, and is preferably a group having 8 or more carbon atoms. Examples of such groups include n-octyl group, t-octyl group, dodecyl group, cetyl group, lauryl group, stearyl group, phenyl group, naphthyl group, tosyl group, xylyl group, cumyl group, mesityl group, isopropylnaphthyl group. Group, nonylphenyl group, octylphenyl group,
There are a dibutylphenyl group, a t-octylphenyl group and the like. Of these, a substituted aryl group is particularly preferable.

Next, the group represented by [B] represents a repeating unit of an ethylene oxide group. This group is widely known in the art as a water-soluble group of nonionic surfactants. The number m representing this repeating unit may be any number as long as it is an integer of 1 or more, but preferably 1 to 10
It is 0, more preferably 2 to 30.

Next, the group represented by [C] represents a linking group, preferably an oxygen atom, an alkylene group, an alkoxy group, an alkylenedioxide group and the like.
The number n representing the type of the linking group may be any number as long as it is an integer of 0 or more, but is preferably 0 to 2.

Further, the group represented by [D] represents an anionic dissociative substituent and has a function of imparting water solubility to the present compound. Such groups include O ^- groups,
Examples thereof include S ⁻ group, COO ⁻ group, and SO ₃ ⁻ group, with COO ⁻ group or SO ₃ ⁻ group being preferred.
This group requires a counter cation represented by [E], and examples thereof include a hydrogen ion, a metal ion having a valence of 1 to 3 (for example, lithium ion, sodium ion,
Potassium ion, rubidium ion, calcium ion, magnesium ion, zinc ion, aluminum ion, etc.). Among these, hydrogen ion, sodium ion, and potassium ion are particularly preferable.

In the following "Chemical formula 1" to "Chemical formula 4", the general formula [I]
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

Next, the compound represented by the general formula [II] will be described. The compound is a compound used as a quaternary salt polymer in the art as a mordant or a dye trapping agent. In the present invention, this is used as a dye trap agent. The use examples and compounds are described in JP-A-2-44356, JP-A-4-20956 and the like, and the compounds represented by the general formula [II] in the present invention are equivalent thereto. Further, in the present invention, when this compound is used, the compound represented by the general formula [I] may be used as the counter anion of the quaternary salt in exchange for 10% or more of the counter anion.
Specific examples of the compound represented by the general formula [II] are shown below, but the present invention is not limited thereto. Further, in the chemical formula of the embodiment, the counter anion of the quaternary ammonium salts Cl ^- are expressed in, which for convenience Cl ^- and to have, other p- toluenesulfonic acid ion, no problem even ions such as sulfate ions . This anion can be converted into the compound represented by the general formula [I] by a known method, for example, the method described in JP-A-4-20956.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

When the compounds represented by the general formulas [I] and [II] are added to the light-sensitive material, any of a light-sensitive emulsion layer, an intermediate layer and a protective layer can be selected as the addition layer. However, it is preferably an intermediate layer. The addition amount of the compound represented by the general formula [I] is 0.001 to 10 g /
m ² is preferably 0.01 to 1 g / m ² . Further, the addition amount of the compound represented by the general formula [II] is 0.00
1 to 10 g / m ^2, preferably from 0.01 to 1 g / m ^2.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a dye-donor compound (which may also serve as a reducing agent as described later) and a binder on a support. Furthermore, if necessary, an organic metal salt oxidizing agent and the like can be added. These components are often added to the same layer, but if they can react, they can be added separately to separate layers. For example, when a colored dye-donating 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 light-sensitive material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

As an example of the dye-donor compound used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. This coupler may be a 4-equivalent coupler or a 2-equivalent coupler, but has a diffusion resistant group as a leaving group,
Two equivalent couplers that form diffusible dyes by oxidative coupling reactions are preferred. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers are described in Theory of the Photographic Process (4th. Ed. TH James, edited by Mac.
Millan, 1977) pages 291 to 334, and pages 354 to 361, JP-A-58-12353, 5
8-149046, 58-149047, 59
-11111, 59-124399, 59-1
74835, 59-231539, 59-23
No. 1540, No. 60-2951, No. 60-14242
No. 60-234474, 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, Y represents a simple bond or linking group, and Z represents a photosensitive silver salt having an imagewise latent image or Conversely, it causes a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releases Dye, and the difference between the released 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 Dyes may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (5). The following (1) to (3) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and (4) and (5) are for silver halide. A diffusible dye image (negative dye image) is formed in correspondence with the development of No. 1.

(1) US Pat. Nos. 3,134,764, 3,362,819, 3,597,200 and 3,
Dye developers in which a hydroquinone-based developer and a dye component are linked, as described in JP-A Nos. 544,545 and 3,482,972. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

(2) As described in US Pat. No. 4,503,137, a non-diffusible compound that releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide Can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, US Pat.
Examples thereof include compounds that release a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring described in JP-A No. 199,354.

(3) US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,39
As described in No. 6, Kokai Giho No. 87-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example, US Pat. No. 4,139,3
89, 4,139,379, JP-A-59-185.
333, 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat. No. 4,232,107, JP-A-59-101649. , 61-88257, RD
24025 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-5-58
6-142530, U.S. Pat. No. 4,343,893,
Compounds that cleave a single bond after reduction to release a diffusible dye described in U.S. Pat. No. 4,619,884, and diffusible dyes after electron acceptance described in U.S. Pat. No. 4,450,223. Releasing nitro compounds, US Pat.
Examples thereof include compounds that release a diffusible dye after electron acceptance as described in JP 609,610.

Further, more preferable ones are US Pat. No. 4,783,396 and European Patent 220,746A2.
No. 87-6199, US Pat. No. 4,783,3
96, JP-A-63-201653, JP-A-63-2
No. 01654 and the like, the N—X bond (X
Represents an oxygen, sulfur or nitrogen atom) and a compound having an electron-withdrawing group, a SO2-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106885. Compounds having a PO-X bond (where X is as defined above) and an electron-withdrawing group in one molecule, as described in JP-A-63-27134.
No. 1341 describes a C—X ′ bond (X ′ in one molecule).
Represents the same as X or represents --SO2-) and a compound having an electron withdrawing group. Also, JP-A-63-27
Π conjugated with an electron-accepting group described in 1341
A compound that releases a diffusible dye by cleaving a single bond after reduction by the bond 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 European Patent 220,746A2 or US Patent 4,78.
Compounds (1) to (3), (7) to (1
0), (12), (13), (15), (23) ~ (26), (31), (32), (35), (36),
(40), (41), (53) ~ (59), (64), (70), Open Technical Report 87-6
199 compounds (11) to (23) and the like.

(4) A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and which 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 US Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like.

(5) A compound (DRR compound) which is reducing to a silver halide or an organic silver salt and releases a diffusible dye when the other is reduced. Since this compound does not need to use any other reducing agent, it is preferable because the image is not contaminated by oxidative decomposition of the reducing agent. A typical example thereof is US Pat.
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.
No. 7, 57-179840, U.S. Pat. No. 4,500,
No. 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, columns 22 to 44, and among them, the compounds (1) to (3 ), (10) ~ (1
3), (16) ~ (19), (28) ~ (30), (33) ~ (35), (38) ~ (40),
(42) to (64) are preferable. US Pat. No. 4,639,4
No. 08. The compounds described in columns 37 to 39 are also useful.

Other than the above-mentioned couplers and dye-providing compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pp. 54-58, etc.) ), An azo dye used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, April 1976.
Monthly issue, pages 30-32, etc.), leuco dyes (US Pat. No. 3,9,9)
85,565, 4,022,617, etc.) can also be used.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a dye-donating compound and a binder on a support. These components are often added to the same layer, but if they can react, they can be added separately to separate layers. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.

In order to obtain a wide range of colors on the chromaticity diagram 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 a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, 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 ordinary color light-sensitive materials. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes may be added to improve the color separation property.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either 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 any other shape.

A specific example is US Pat. No. 4,500,62.
No. 6, Column 50, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029
(1978), any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.
The silver halide emulsion may be used in an unripened state, but is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination in 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-62-253159).

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 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, US Pat. No. 4,617,25
7, JP-A-59-180550 and JP-A-60-1403.
No. 35, RD17029 (1978), 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 (Patent No. 3,615,641) those described in JP-A-63-23145). 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.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. The use of an organic metal salt is particularly preferable in the photothermographic element. 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 agent include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in 500,626, columns 52 to 53. Further, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and silver acetylene described in JP-A-61-249044 are also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. 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.
As an example, RD17643 (1978) 24-
Azoles and azaindenes described on page 25, JP-A-5
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-9-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-8.
The acetylene compounds described in 7957 are 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. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52. As in the present invention, in a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photosensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the photosensitive material and the dye fixing material, 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 material 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. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (32)-
The mordant described on page (41), JP-A-62-244043,
Examples thereof include those described in JP-A No. 62-244036. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

If necessary, the dye fixing material may 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. A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing material. An example thereof is Japanese Patent Laid-Open No. 62-25315.
Examples thereof include those described in No. 9, pages (26) to (28).
Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein such as a gelatin derivative or a cellulose derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan,
Examples thereof include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M
Homopolymers of vinyl monomers having (M is hydrogen atom or alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel manufactured by Sumitomo Chemical Co., Ltd.) L-5H) 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 is possible to quickly absorb water by using the above superabsorbent polymer. 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.

As a hardener used for the constituent layers of the light-sensitive material and the dye-fixing material, 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 present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye-fixing material. The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as formation of a dye from a dye-donor compound or 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, it is 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. For details of these, see U.S. Pat. No. 4,678,739 No. 38-
It is described in column 40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,51.
No. 1,493 and JP-A No. 62-65038. In a system in which heat development and dye transfer are performed 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 material in order to enhance the storage stability of the light-sensitive material.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a 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), The compounds that generate a base by electrolysis as described in JP-A No. 61-232451 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
It is advantageous to add the light-sensitive material and the dye-fixing material separately.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing material for the purpose of always obtaining a constant image with respect to 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 after proper development to lower the concentration of the base in the film to stop the development or to interact with silver and a silver salt to suppress development. 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. More specifically, JP-A-62-2
No. 53159 (31) to (32).

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material 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. .

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive material and the dye-fixing material. Specifically, (25) of JP-A-62-253159
Page, 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 include “modified silicone oil” technical data published by Shin-Etsu Silicone Co., Ltd. p. Various modified silicone oils described in 6-18B, especially carboxy-modified silicone (trade name X-
22-3710) and the like are effective.

Further, JP-A-62-215953 and 63
The silicone oil described in No. 46449 is also effective. An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. 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. In addition, JP-A-61
The compounds described in No. 159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (U.S. Pat. No. 3,352,6
No. 81), benzophenone compounds (JP-A-46-
2784) and others, JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
No. 1,155, No. 4,245,018, columns 3 to 36,
No. 4,254,195, columns 3 to 8, JP-A-62-17.
4741, 61-88256 (27)-(29), 6
3-199248, JP-A-1-75568, 1-
There are compounds described in No. 74272 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272, pages 125-137. An anti-fading agent for preventing fading of the dye transferred to the dye fixing material may be contained in the dye fixing material in advance,
The dye fixing material may be supplied from the outside such as a photosensitive material.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. An example of this is K. Veenkataraman's edition, The 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,
Examples thereof include biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazolidone compounds, and carbostyryl compounds.

The fluorescent whitening agent can be used in combination with an anti-fading agent. In the constituent layers of the light-sensitive material and the dye-fixing material, coating aids, improvement of peelability, improvement of sliding property, antistatic,
Various surfactants can be used for the purpose of promoting development and the like. Specific examples of the surfactant are disclosed in JP-A-62-17346.
No. 3 and No. 62-183457.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444, JP-A-62-135826 and the like, oil-like fluorinated compounds such as fluorinated oil, or solid fluorinated compound resins such as tetrafluoroethylene resin Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used for the light-sensitive material and the dye-fixing material. 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, A
Japanese Patent Laid-Open Nos. 63-274944 and 6-96, such as S resin beads.
There are compounds described in 3-274952.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A No. 61-88256, pages (26) to (32). In the present invention, a support that can withstand the processing temperature is used as the support for the light-sensitive material and the dye-fixing material. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and film-type synthetic paper made from polypropylene or the like. 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 or
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 semiconductor metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

The light source used for exposing the color light-sensitive material of the present invention is a light emitting diode or a semiconductor laser. As the light emitting diode in the present invention,
GaAsP (red), GaP (red, green), GaAsP: N
(Red, yellow), GaAs (infrared), GaAlAs (infrared,
Various materials such as red), GaP: N (red, green, yellow), QaAsSi (infrared), GaN (blue), and SiC (blue) can be used.

Further, as described above, an infrared-visible conversion element for converting the infrared light of the infrared light emitting diode into visible light with a phosphor can be used. As such a phosphor, a phosphor activated with a rare earth is preferably used, and as the rare earth, Er ³⁺ , Tm ³⁺ , Yb ³⁺ or the like can be used. Specific examples of the semiconductor laser that can be used in the present invention include In _1-x Ga _x P as a light emitting material.
(-700 nm), GaAs _1-x P _x (610-900 n)
m), Ga _1-x Al _x As (690 to 900 nm), In
GaAsP (100 to 1670 nm), AlGaAsSb
A semiconductor laser using a material such as (1250 to 1400 nm) can be given. Irradiation of light to the color light-sensitive material in the present invention is performed by N
It may be a YAG laser (1064 nm) in which a d: YAG crystal is excited by a GaAs _x P _(1-x) light emitting diode.

Further, in the present invention, the second harmonic generation element (SHG element) is an element for converting the wavelength of the laser light into one half by applying the non-linear optical effect. For example, the non-linear optical crystal. Examples include those using CD ^* A and KD ^* P (Laser Handbook, edited by Laser Society, published December 15, 1982, pages 122 to 1).
(See page 39). Also, Li ⁺ is added to H ⁺ in the LiNbO ₃ crystal.
A LiNbO ₃ optical waveguide device having an optical waveguide ion-exchanged with can be used [NIKKEI ELECTRONICS,
1986.7.14. (No. 399) pages 89-90].

As the other light source, a light source such as natural light, a tungsten lamp or a CRT light source can be used. Depending on the case, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a color negative film using a printer, an enlarger, or the like may be used.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal operated by using a computer represented by CG and CAD can be used. When the present invention is used as a heat-developable color light-sensitive material and is subjected to heat-development, the heating temperature in the heat-development step is from about 50 ° C. to about 250 ° C. and development is possible. It is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. 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. In such a heat-developable color light-sensitive material, the total film thickness of each layer coated on the support is 15 μm or less in dry film thickness. With such a film thickness, dye transfer can be promoted and an effect of forming an image with excellent sharpness can be obtained. However, with such a light-sensitive material, on the other hand, problems such as color separation are remarkable. Become. The present invention solves this.

In the present invention, a solvent may be used to promote color transfer. Also, JP-A-59-21844
As described in detail in No. 3, No. 61-238056, etc.,
For the photothermographic material, it is also useful to carry out development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water). 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, the temperature 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 (these bases). Examples thereof include those described in the section of the image formation accelerator). 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 material, the photosensitive 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 coated film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coated film less the weight of the entire coated film). As a method of applying a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
There is a method described on page 6). Alternatively, the solvent may be contained in a microcapsule and previously incorporated in the light-sensitive material or the dye-fixing material or both.

In order to promote dye transfer, a method of incorporating a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature into the light-sensitive material or the dye-fixing material can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, 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. Also,
A high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing material in order to accelerate dye transfer. As a heating method in the developing and / or transferring step,
Contact heated blocks and plates, heat plates,
It includes contact with hot pressers, heat rollers, halogen lamp heaters, infrared and far-infrared lamp heaters, and passage through high-temperature atmospheres. Further, a resistance heating element layer may be provided on the photosensitive material or the dye fixing material, and the resistance heating element layer may be energized and heated. As the heating element layer, Japanese Patent Laid-Open No. Sho 6
Those described in 1-147244 can be used.

Superimposing the light-sensitive element and the dye fixing material,
The pressure condition and the method for applying the pressure when closely contacting each other are disclosed in Japanese Patent Laid-Open Publication No.
The method described in page 1-147244 (27) can be applied.
Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For processing a heat-developable color light-sensitive material, for example, JP-A-59-75147 and JP-A-59-17754.
No. 7, No. 59-181353, No. 60-18951.
The devices described in Japanese Utility Model Publication No. 62-25944 and the like are preferably used.

[0080]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 A method for preparing the fifth layer silver halide emulsion (I) will be described.

To the well-stirred aqueous solution having the composition shown in Table 1, the solutions I and II having the compositions shown in Table 2 were added over 10 minutes, and then the solutions III and IV having the compositions shown in Table 2 were added. Add over 25 minutes.

[0083]

[Table 1]

[0084]

[Table 2]

Immediately before the chemical sensitization, 1% of the sensitizing dye a was used.
50 cc of solution (mixed solvent of methanol: water = 1: 1) was added.

Washing with water, pH = 4.1 using desalting precipitant a
Then, 22 grams of gelatin was added and pH = 6.
After adjusting to 0 and pAg = 7.9, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are shown in Table 3.

[0087]

[Chemical 9]

[0088]

[Chemical 10]

[0089]

[Chemical 11]

The yield of the obtained emulsion was 630 g, and it was a monodisperse cubic emulsion having a variation coefficient of 10.3%, and the average grain size was 0.21 μm.

[0091]

[Table 3]

[0092]

[Chemical 12]

[0093]

[Chemical 13]

[0094]

[Chemical 14]

The method for preparing the silver halide emulsion (II) for the third layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 4, the solutions I and II having the composition shown in Table 5 were added over 18 minutes, and then the solutions III and IV having the composition shown in Table 5 were added. Added over 24 minutes.

[0097]

[Table 4]

[0098]

[Table 5]

Washing with water, desalting (using the precipitating agent b, pH = 3.
9) and then add 22 grams of gelatin to obtain a pH =
After adjusting to 5.9 and pAg = 7.8, chemical sensitization was performed at 70 ° C. Further, during the chemical sensitization, sensitizing dyes b and c
In methanol (p-toluenesulfonic acid 0.2N)
Was added. The compounds used for the chemical sensitization are shown in Table 6.

[0100]

[Chemical 15]

The yield of the obtained emulsion was 645 g, and it was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.24 μm.

[0102]

[Table 6]

[0103]

[Chemical 16]

The method for preparing the silver halide emulsion (III) for the first layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 7, the solutions I and II having the compositions shown in Table 8 were added over 18 minutes, and then the solutions III and IV having the compositions shown in Table 8 were added. Add over 25 minutes.

[0106]

[Table 7]

[0107]

[Table 8]

After washing with water and desalting (performed at pH = 4.1 using the precipitating agent a shown in Chemical formula 11), 22 g of gelatin was added to adjust pH = 7.4 and pAg = 7.6. , 6
It was chemically sensitized at 0 ° C. In the middle of the chemical sensitization, a solution of the sensitizing dye d in methanol (p-toluenesulfonic acid 0.1
N) was added. The compounds used for the chemical sensitization are shown in Table 9.

[0109]

[Chemical 17]

The yield of the obtained emulsion was 650 g, a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0111]

[Table 9]

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described.

12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and the average particle size was 0.75 with a mill.
Milled for 30 minutes using mm glass beads. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. The oil phase components shown in Table 10 were each dissolved in 250 cc of ethyl acetate to obtain a uniform solution at 60 ° C. To this, add the water phase component heated to 60 ° C, and use a dissolver with a diameter of 8 cm for 30 minutes for 500 minutes.
Dispersed at 0 rpm. To this was added post-hydration and stirred to form a uniform dispersion. This is called a gelatin dispersion of hydrophobic additives.

[0115]

[Table 10]

Using these materials and the materials described in Chemical formulas 18 to 24, the heat-developable color light-sensitive material 101 having the multilayer structure shown in Tables 11 to 13 and the dye fixing material R-1 having the structure shown in Tables 14 to 15 were prepared. .

[0117]

[Table 11]

[0118]

[Table 12]

[0119]

[Table 13]

[0120]

[Table 14]

[0121]

[Table 15]

[0122]

[Chemical 18]

[0123]

[Chemical 19]

[0124]

[Chemical 20]

[0125]

[Chemical 21]

[0126]

[Chemical formula 22]

[0127]

[Chemical formula 23]

[0128]

[Chemical formula 24]

Next, with respect to the light-sensitive material 101, the light-sensitive material 102 which is exactly the same as the light-sensitive material 102 except that additives or trapping agents were added to the respective layers as shown in Table 16.
~ 110 were created respectively.

[0130]

[Table 16]

The color photosensitive material 101-1 having the above-mentioned multilayer structure.
No. 10 was exposed using a semiconductor ray exposure machine having the specifications shown in Table 17.

[0132]

[Table 17]

The exposed light-sensitive material was drawn at a linear velocity of 20 mm / s.
While feeding by ec, 15 ml / m ² of water was supplied to the emulsion surface with a wire bar, and immediately thereafter, the emulsion was superposed so that the image receiving material and the film surface were in contact with each other.

Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 83 ° C., it was heated for 30 seconds.

Next, when peeled off from the image receiving material, a clear transferred image was uniformly obtained on the image receiving material. The results of sensitometry of this transferred image with an X-lite densitometer are shown in Table 18.

[0136]

[Table 18]

From Table 18, Samples 106 to 1 of the present invention
It can be seen that in No. 10, an image excellent in discrimination having high Dmax and low Dmin is obtained.

Example 2 A method for preparing the photosensitive silver halide emulsions (IV) to (IX) will be described.

Light-sensitive silver halide emulsion (IV) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 cc of water, 0.5 g of potassium bromide, 3 parts of sodium chloride)
g and 30 mg of Compound 1 and kept at 45 ° C.), the solutions (I) and (II) in Table 19 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 19 were further added simultaneously at the same flow rate for 25 minutes. Also (II
Ten minutes after the start of addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of dye (1 g of gelatin in 67 ml of water, 67 mg of sensitizing dye (e), 133 mg of sensitizing dye (f), sensitizing dye (g ) Containing 4 mg and kept at 45 ° C.) 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, and sodium thiosulfate and 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene,
Chloroauric acid was added to perform optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0141]

[Table 19]

[0142]

[Chemical 25]

[0143]

[Chemical formula 26]

[0144]

[Chemical 27]

[0145]

[Chemical 28]

Light-sensitive silver halide emulsion (V) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 783 cc of water).
g and Compound 1 (30 mg) and the mixture was kept at 65 ° C.), the solutions (I) and (II) in Table 20 were simultaneously added at an equal flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 20 were added simultaneously at an equal flow rate for 15 minutes. Also (II
Two minutes after the start of addition of solutions I) and (IV), an aqueous solution of a gelatin dispersion of a sensitizing dye (0.9 g of gelatin in 95 ml of water, 61 mg of sensitizing dye (e), 121 mg of sensitizing dye (f), A dye containing 4 mg of the dye (g) and kept at 50 ° C.) 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 pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene,
Chloroauric acid was added to perform optimum chemical sensitization at 60 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0148]

[Table 20]

Photosensitive Silver Halide Emulsion (VI) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 675 cc of water, 0.5 g of potassium bromide, 4 parts of sodium chloride).
g and 15 mg of the chemical (A) and kept at 48 ° C.), solutions (I) and (II) in Table 21 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, solutions (III) and (IV) in Table 21 were further added simultaneously at an equal flow rate for 20 minutes. Also (II
One minute after the addition of the solutions I) and (IV), an aqueous solution of a gelatin dispersion of a sensitizing dye (3.0 g of gelatin in 120 ml of water and 300 mg of the sensitizing dye (h) and kept at 45 ° C) was packaged together. And added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, sodium thiosulfate and 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene,
Chloroauric acid was added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0151]

[Table 21]

[0152]

[Chemical 29]

Photosensitive Silver Halide Emulsion (VII) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride in 675 cc of water).
solution (I) and solution (II) shown in Table 22 were simultaneously added at an equal flow rate for 20 minutes. After 10 minutes, the solutions (III) and (IV) shown in Table 22 were added simultaneously at the same flow rate for 20 minutes. Also (II
One minute after the addition of solutions I) and (IV), an aqueous solution of a gelatin dispersion of a sensitizing dye (2.5 g of gelatin in 95 ml of water and 250 mg of sensitizing dye (h) and kept at 45 ° C) was packaged together. And added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene,
Chloroauric acid was added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.42 μm was obtained.

[0155]

[Table 22]

Photosensitive Silver Halide Emulsion (VIII) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 675 cc of water, 0.5 g of potassium bromide, 4 parts of sodium chloride).
g and 15 mg of the chemical (A) were added and kept at 50 ° C.), the solutions (I) and (II) in Table 23 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, the solutions (III) and (IV) in Table 23 were added simultaneously at the same flow rate for 32 minutes. Also (II
1 minute after the addition of the solutions (I) and (IV), an aqueous solution of the sensitizing dye (in 95 m1 of water and 5 m1 of methanol, 220 m of the sensitizing dye (i) was added.
g, containing 110 mg of sensitizing dye (j) and kept at 45 ° 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, sodium thiosulfate and 4-hydroxy-6-methyl-1, Optimum chemical sensitization was performed at 68 ° C. by adding 3,3a, 7-tetrazaindene. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0158]

[Table 23]

[0159]

[Chemical 30]

[0160]

[Chemical 31]

Photosensitive silver halide emulsion (IX) [for blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 675 cc of water, 0.3 g of potassium bromide and 9 g of sodium chloride).
solution (I) and solution (II) shown in Table 24 were simultaneously added at a constant flow rate for 10 minutes. After 10 minutes, solution (III) and solution (IV) in Table 24 were added simultaneously at the same flow rate for 30 minutes. Also (II
One minute after the addition of solutions I) and (IV) was completed, an aqueous solution of a sensitizing dye (66 m1 of water and 4 m1 of methanol,
g, containing 75 mg of sensitizing dye (j) and kept at 60 ° 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 the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene,
Chloroauric acid was added for optimum chemical sensitization at 68 ° C. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0163]

[Table 24]

A method for preparing a gelatin dispersion of a hydrophobic additive will be described. The oil phase components shown in Table 25 were dissolved to form a uniform solution at 60 ° C. To this, add the water phase ingredients heated to 60 ℃ and use a disperser with a dissolver of 8 cm in diameter to
Dispersed at 5000 rpm for minutes. To this was added post-hydration and stirred to form a uniform dispersion. This is called a gelatin dispersion of hydrophobic additives.

[0165]

[Table 25]

A method for preparing a dispersion of the electron transfer agent (43) will be described. 10 g of the electron transfer agent (43) shown in Chemical formula 32,
Polyethylene glycol nonyl phenyl ether (g) 0.5 g as an dispersing agent, anionic surfactant (h)
0.5 g was added to a 5% lime-treated gelatin aqueous solution, and the mixture was milled for 60 minutes using a glass bead having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.3 μm.

[0167]

[Chemical 32]

A method for preparing a dispersion of the dye trap agent (44) will be described. Polymer latex (dye trap agent
(43)) (solid content 13.3%) 108 cc, nonionic surfactant (i) 20 g, while stirring a mixed solution of water 1232 cc, 5% aqueous solution of anionic surfactant (j) 600
cc was added over 10 minutes. The suspension thus obtained was concentrated to 500 cc using an ultrafiltration module (molecular weight cutoff of 10,000), desalted, 1500 cc of water was added, and the same operation was repeated once again. Thus, a dispersion of the dye trapping agent (44) was obtained.

[0169]

[Chemical 33]

A heat-development diffusion transfer type color photosensitive material 201 having a multilayer structure shown in Tables 26 to 29 was prepared.

[0171]

[Table 26]

[0172]

[Table 27]

[0173]

[Table 28]

[0174]

[Table 29]

[0175]

[Chemical 34]

[0176]

[Chemical 35]

[0177]

[Chemical 36]

[0178]

[Chemical 37]

Next, with respect to the light-sensitive material 201, a light-sensitive material 202 having exactly the same composition as 201 except that an additive was added or a trapping agent was changed as shown in Table 30.
~ 215 were prepared.

[0180]

[Table 30]

The color light-sensitive materials 201 and 2 having the above-mentioned multilayer structure.
No. 15 is exposed through B, G, R, and gray wedges whose densities are continuously changed, and the exposed photosensitive material is exposed to 45
After soaking in water kept at ℃, it was squeezed with a roller and immediately superposed so that the image receiving material R-1 and the film surface were in contact with each other. Then, using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 80 ° C., the photosensitive material was peeled from the image receiving material by heating for 15 seconds, and a clear positive color image was obtained on the image receiving material. .

Table 31 shows the results of sensitometry of the image of the gray portion thus obtained with an X-lite densitometer.

[0183]

[Table 31]

From the results shown in Table 31, it can be seen that the effects of the present invention are also apparent in the positive type photosensitive material.

Claims (3)

[Claims] 1. A non-diffusible dye that releases or forms a diffusible dye in response to or at least in response to a reaction of at least a photosensitive silver halide, a binder, and silver halide reduced to silver on a support. A heat development diffusion transfer type color light-sensitive material, which further comprises a compound represented by the following general formula [I] in the heat development diffusion transfer type color light-sensitive material having a donor compound. General formula [I] ([A]-[B] _m- [C] _n- [D]) _p- [E] In the formula, [A] represents a substituted or unsubstituted alkyl group or aryl group. [B] represents a repeating unit of an ethylene oxide group. [C] represents a linking group.
[D] represents an anionic dissociative substituent. [E]
Represents a hydrogen ion or a trivalent cation. m represents an integer of 1 or more. n represents 0 or 1. p represents an integer of 1 to 3 corresponding to the valence of [E]. 2. The heat development diffusion transfer type color photosensitive material according to claim 1, further comprising a polymer compound represented by the following general formula [II]. General formula [II] [X]-[Y] _k [Z] In the formula, [X] represents a repeating unit of a monomer having a quaternary ammonium group. [Y] represents a repeating unit of a monomer having no quaternary ammonium group. [Z]
Is a counter anion of [X]. k is an integer of 0 or more. 3. 10% or more of the counter anion of the quaternary ammonium group contained in the polymer compound represented by the general formula [II] is an anion obtained by removing [E] from the general formula [I]. The heat-development diffusion transfer type color photosensitive material according to claim 1 or 2, wherein