JPH0473772B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a heat-developable color light-sensitive material, and more particularly to a multi-layer heat-developable color diffusion transfer light-sensitive material which has improved color turbidity and improved dye transferability from the bottom layer. [Prior Art] The conventionally known color photography method using photosensitive silver halide is superior to other color photography methods in terms of photosensitivity, gradation, and image preservation, and is the most widely used color photography method. It has been put into practical use. However, in this method, wet processing is used for steps such as development, bleaching, fixing, and water washing, which takes time and effort, and there are concerns that the processing chemicals may cause pollution to the human body, or the processing room and There are many problems, such as concerns about contamination of workers by treatment chemicals, and furthermore, the labor and cost of waste liquid treatment. Therefore, there has been a demand for the development of a method for forming color images that allows dry processing. Heat-developable black-and-white photosensitive materials characterized in that the development process is carried out by heat treatment have been known for a long time. A photosensitive material comprising silver oxide and a developer is disclosed. Furthermore, many heat-developable color photosensitive materials are also known, which are based on this heat-developable black-and-white photosensitive material. For example, US Patent No. 3531286, US Patent No. 3761270, US Patent No.
No. 3764328, Research Disclosure No.
No. 15108, No. 15127, No. 12044, No. 16479, etc. are U.S. patents for heat-developable photosensitive materials containing photographic couplers and color developing agents.
No. 3180731, Research Disclosure No. 13443
and No. 14347, etc., regarding those using leuco dyes, U.S. Patent No. 4235957, Research
Disclosure No.14433, No.14448, No.
15227, No. 15776, No. 18137, and No. 19419, etc., which apply the silver dye bleaching method, include U.S. Patent Nos. 4124398, 4124387, and
No. 4123273 describes methods for thermally bleaching photothermographic materials. However, these proposals regarding heat-developable color photosensitive materials are difficult or impossible to bleach or fix the simultaneously formed black, white, and silver images, or even if it is possible, wet processing etc. are not required. It is what you need. Therefore, these proposals are not found to be desirable as it is difficult to obtain fresh color images or requires complicated post-processing. On the other hand, heat-developable color photosensitive materials that obtain color images by transferring diffusible dyes released by heat development are disclosed in JP-A-57-179840, JP-A-57-186744, and JP-A-57.
-No. 198458, No. 57-207250, No. 58-40551,
It is disclosed in each publication No. 58-58543, and the patent application No. 57-122596 and No. 57-57 filed by the present inventors.
It is also shown in the specifications of No. 229649. In these proposals, a dye-providing substance having a diffusible dye in the same molecule releases the diffusible dye through a heat development reaction of an organic silver salt, and transfers the diffusible dye to an image-receiving layer to obtain a color image. In this specification, this is referred to as a "dye-releasing type." On the other hand, patent application No. 57-229671 by the present inventors
No. 58-33363 and No. 58-33364, the proposal is that a colorless or light-colored dye-providing substance reacts with an oxidized color developing agent produced by a thermal development reaction of an organic silver salt. A color image is obtained by forming a heat-diffusible dye and transferring it to an image-receiving layer.
It is called. Regardless of the dye-releasing type or dye-forming type, when it is desired to diffusely transfer dyes using heat without requiring wet processing to obtain a multicolor image on the image-receiving layer, generally It is convenient to use a photosensitive material with a multilayer structure. It is well known that a multilayer structure is used even in the case of general color sensitive materials that require normal wet processing. For example, in the case of a printed photosensitive material, in the case of color paper, a blue-sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler, and a red-sensitive layer containing a cyan coupler are usually formed in order from the bottom layer. In the case of Ectaflex, the lowest layer is a red-sensitive layer that provides a cyan dye, followed by a green-sensitive layer that provides a magenta dye, and a blue-sensitive layer that provides a yellow dye. An intermediate layer is coated between each layer to prevent color turbidity, and in many cases, a yellow filter layer is coated between the blue-sensitive layer and the green-sensitive layer. On the other hand, in order to produce full color in heat-developable color photosensitive materials, it is important to prevent color turbidity between each layer as described above, and an intermediate layer is usually provided between the blue-sensitive layer, green-sensitive layer, and red-sensitive layer. By providing this, it is possible to suppress color turbidity. However, in order to suppress color turbidity, an intermediate layer is provided, in particular, the film thickness is increased, and a binder (such as gelatin) that acts non-diffusively with respect to the dye-providing substance and the oxidized product (DP') of the developing agent is added. If the amount is increased, there is a problem that the transferability of the released or formed diffusible dye to the image-receiving layer decreases. In particular, the transferability of the diffusible dye from the photosensitive layer closest to the support (lowermost photosensitive layer) is significantly reduced. In addition, in conventional photographic methods using comparative photographic materials, techniques using hydroquinones, catechols, etc. are known to prevent color turbidity, but when these techniques are applied to heat-developable color photosensitive materials, the following problems occur. There are problems like this. That is, for example, alkylhydroquinones, such as those used in conventional silver halide emulsions, are effective reducing agents, and because they have diffusivity in heat-developable color photosensitive materials, they act as developers. There is a problem in that it is unfavorable in terms of photographic characteristics. Therefore, it is necessary to prevent color turbidity without using these compounds in heat-developable color photosensitive materials, but no effective method is known yet. [Object of the Invention] An object of the present invention is to provide a heat-developable color photosensitive material that can prevent color turbidity and has improved transferability of diffusible dyes from the lowermost photosensitive layer. [Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have developed a photosensitive silver halide, an organic silver salt, a dye donor substance capable of releasing or forming a diffusible dye upon thermal development, and a reducing agent. and a binder, the heat-developable color photosensitive material having at least two photosensitive layers on a support, the sensitivity of the photosensitive silver halide and the hue of the dye being different from each other; Couplers that can react with the oxidized form of a developing agent to form an immobile compound during the process, and which have an alkyl group having 8 or more carbon atoms and/or an alkyl group having 4 or more carbon atoms at a site other than the active site substituent. It has been found that the above object can be achieved by having a substantially non-photosensitive intermediate layer containing at least one selected from those having an aryl group and a hydrophilic group, and the present invention completed. The present invention will be explained in detail below. In the present invention, the coupler that can react with the oxidized form of a developing agent to form an immobile compound (hereinafter referred to as the coupler of the present invention) is an internal compound used in the conventional conventional color silver salt method. Yellow, magenta and cyan couplers for color development are used, such as active methylene compounds such as open-chain ketomethine compounds, pyrazolone compounds and pyrazolone triazole compounds, active methylene compounds such as phenol or naphthol derivatives, or leaving groups in the active sites of these compounds. A so-called 2-equivalent coupler having . The above coupler is an aryl compound having an alkyl group having 8 or more carbon atoms and/or an alkyl group having 4 or more carbon atoms at a site other than the active site substituent because it can react with the oxidized product of the developing agent to form an immobile compound. In addition to the group, it has a hydrophilic group such as a sulfo group, a carboxyl group, or a sulfamoyl group. The above coupler can be represented by the following general formula. In the formula, R ₁ , R ₂ , R ₃ and R ₆ are hydrogen atoms, halogen atoms (preferably fluorine atoms, chlorine atoms or bromine atoms), alkyl groups having 1 to 22 carbon atoms, alkoxy groups, aryl groups, amino group, alkylamino group, arylamino group, alkylamido group, arylamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbamoyl group, arylcarbamoyl group, alkylcarbamoylamide group, arylcarbamoylamide group,
It represents a cyano group or a nitro group, and R ₂ and R ₃ may be combined to form a 5- to 6-membered carbocyclic or heterocyclic ring (preferably a naphthol ring formed by condensation with a phenol ring). . R ₄ represents an aryl group, preferably a phenyl group, such as an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, an alkoxy group, an alkyl group, an aryloxyalkyl group,
It represents an aryl group (preferably a phenyl group) substituted with a substituent selected from an N-substituted carbamoyl group, an alkylamino group, an arylamino group, a halogen atom, an acyloxy group, an acyloxyalkyl group, or a cyano group. R ₅ is a hydrogen atom, a halogen atom, an alkyl group,
Cycloalkyl group, aryl group, alkoxy group,
A substituent selected from an aryloxy group, an aralkyl group, an acylamino group, an alkoxyalkyl group, an aryloxyalkyl group, an N-substituted carbamoyl group, an alkylamino group, an arylamino group, an acyloxy group, an acylamino group, or a cyano group. represents, and these substituents further include a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a sulfamoyl group, an N-substituted carbamoyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkyl group,
Aryl group, alkoxy group, aryloxy group,
It may be substituted with an aralkyl group or an acyl group. Note that at least one of R ₁ to _{R 6} needs to be substituted with a sulfo group or a carboxyl group. X is a hydrogen atom, a halogen atom, or a group that couples with and leaves the oxidized form of a developing agent, such as a sulfo group, an alkoxy group, an aryloxy group,
Acylamino group, alkyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group,
Alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group,
arylazo group, heterocyclic residue,

[Formula] Motomata teeth

〔Example〕

Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Examples and Comparative Examples To 22.7 g of benzotriazole silver were added 400 ml of methyl alcohol and 500 ml of an 8% polyvinyl alcohol (Gohsenol AL-02, manufactured by Nippon Gohsei Kagaku) aqueous solution, and the mixture was dispersed in a ball mill for 24 hours. Next, while stirring this dispersion, a red sensitized silver iodobromide emulsion (silver iodide 5 mol%, gelatin in 1 kg of emulsion) was prepared.
60 g and 28 ml of cubic particles with an average particle size of 0.1 μm containing 0.353 mol of silver were added. Furthermore, p-amino-N,
8.3 g of N-diethylaniline and 30 g of exemplified dye-providing substance (1) as a cyan dye-forming coupler were mixed with 5 ml of a 5% aqueous solution of di(ethylhexyl)-sulfosuccinate and 100 ml of a 5% aqueous gelatin solution, and the mixture was ground and dispersed in a ball mill. added. Further, 9 ml of a 2% methanol solution of 3-amino-4-allyl-5-mercaptotriazole and 50 g of acetamide were added and stirred well. The coating solution prepared in this way was coated on a polyethylene terephthalate base coated with gelatin (dry film thickness 3 μm).
It was dried (silver content 5.2 mg/dm ² ). Next, an intermediate layer was applied on top of this with a 4% polyvinyl alcohol aqueous solution to a wet film thickness of 55 μm.
Dry. Then, green-sensitive silver halide of the same composition was added in place of the red-sensitive silver halide according to the recipe for the first layer, and a wet film was also formed with the same composition but using the exemplified dye-providing substance (12) as a coupler. Comparative sample 1 was prepared by coating and drying to a thickness of 55 μm. Next, 2-(N
-ethylcarbamoyl)-1-naphthol (1.03 g) with 10 ml of an aqueous solution of 4% polyvinyl alcohol 1 and 5% alkanol
Comparative Sample 2 is a sample that is exactly the same as Comparative Sample 1, except that the intermediate layer was coated to a wet film thickness of 55 μm after being ball-milled for 24 hours. Next, 2-, which was similarly used for the intermediate layer of Comparative Sample 2,
Comparative sample 3 was prepared by using 0.84 g of 1-phenyl-3-methyl-5-pyrazolone instead of (N-ethylcarbamoyl)-1-naphthol. Next, 2-, which was similarly used for the intermediate layer of Comparative Sample 2,
2-{4-(2,4-di-t-amylphenoxy)butylcarbamoyl}-1-naphthol instead of (N-ethylcarbamoyl)-1-naphthol
The one using 2.24g is called Comparative Sample 4, and similarly 1
-(2,4,6-trichlorophenyl)-3-
(2'-chloro-5'-palmitoylamidoanilino)
Comparative sample 5 using 3.1g of -5-pyrazolone
shall be. Next, 2-, which was similarly used for the intermediate layer of Comparative Sample 2,
(N-Ethylcarbamoyl)-1-naphthol was replaced with 3.46 g of the coupler exemplified compound (12) of the present invention, and the same sample as Comparative Sample 2 was used as the present invention sample 6, and similarly the exemplified compound (26) was used. The sample using 3.12g is designated as Invention Sample 7. Separately, 1 m ² of a 5% solution of polyvinyl chloride in tetrahydrofuran (containing 10% by weight of dibutyl phthalate based on the polymer) was placed on photographic baryta paper.
Apply so that the amount of polyvinyl chloride is 1.20g per coat,
Receiving paper was created. Comparative samples 1, 2, 3, 4, and 5 and inventive samples 6 and 7 were each exposed to red light through a step wedge. Next, place the receiving paper and the coated surface in close contact with each other.
Developed at 160°C for 1 minute. The density at the maximum density (Dm) part and the green density were measured. As a result, Comparative Samples 1, 2, and 3 had a muddy color tone, while Comparative Samples 4 and 5 had little color turbidity up to the middle tone area, but considerable color turbidity was observed in the Dm area. However, in samples 6 and 7 of the present invention, color turbidity was considerably reduced even in the Dm area. Table 1 shows the results of measuring the red density and green density in the Dm section.

[Table] Table 2 shows the results of similar development using green light through a step wedge.

【table】

[Table] As is clear from the above table, by having an intermediate layer containing the coupler of the present invention, color turbidity is improved and the transferability of the dye from the bottom layer is improved. In particular, when a coupler having both an alkyl group as a hydrophobic ballast group and a water-soluble group such as a sulfo group is used, it is found to be very effective against color turbidity in a thermal development system.

Claims (1)

[Claims] 1 Contains a photosensitive silver halide, an organic silver salt, a dye-providing substance capable of releasing or forming a diffusible dye by a thermal phenomenon, a reducing agent, and a binder, and the color sensitivity of the photosensitive silver halide and the dye In a heat-developable color photosensitive material having at least two photosensitive layers having different hues on a support, an immobile compound can be produced between the two photosensitive layers by reacting with an oxidized form of a developing agent. A coupler with an alkyl group having 8 or more carbon atoms at a site other than the active site substituent and/or
or a heat-developable color characterized by having a substantially non-photosensitive intermediate layer containing at least one selected from those having a hydrophilic group and an aryl group having an alkyl group having 4 or more carbon atoms. photosensitive material.