JP2003202655A - Dye fixing element for color diffusion transfer process and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color image forming method in which the physical strength of a film is not deteriorated and a color image excellent in light resistance is formed in a method by which an image forming dye or a precursor thereof is released or generated in proportion or inverse proportion to silver development and an image is formed by diffusion transfer of the dye. <P>SOLUTION: A dye fixing element for a color diffusion transfer process is provided which has a UV absorbing layer containing ≥0.2 g/m<SP>2</SP>coating weight of a UV absorbent above a mordanting layer, wherein a compound of formula (1) (where x and y show the mole fractions of repeating units, x+y=1 and y=0.85-0.95) is contained as at least one of dispersion media for the UV absorbent by 25-200 mass% of the UV absorbent and the total of the UV absorbent and the dispersion media for the UV absorbent is ≤1.0 g/m<SP>2</SP>coating weight. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for improving the light fastness of dye-fixing elements in imaging systems using light-sensitive elements and dye-fixing elements. More specifically, in an image forming method for forming an image, an image forming dye is produced and released by exposure and development of a photosensitive silver halide, and the image is formed by diffusively transferring the image forming dye from a photosensitive layer to an image receiving layer. The present invention relates to an image forming method having improved fastness. Also, an image forming dye is produced by exposing and developing a photosensitive silver halide,
It relates to a dye fixing element used in a method of forming an image by releasing and diffusively transferring the image forming dye from a photosensitive layer to an image receiving layer.

[0002]

2. Description of the Related Art A photographic material of a color diffusion transfer system (so-called a so-called photographic material is known as a method for forming an image by exposing or developing a photosensitive silver halide to generate or release an image forming dye, and further transferring the dye. Instant photography), heat development color diffusion transfer method, and method using photosensitive microcapsules are known.

Images obtained by these methods are generally inferior in light resistance to conventional photographic images,
Conventionally, various methods have been considered for improving light resistance. There have been many studies such as the use of anti-fading agents, devising the layer structure, installation of an oxygen barrier layer, and among these, a method of using an ultraviolet absorber as one of the anti-fading agents has been reported (for example, , Patent Documents 1 to 3).

This method is effective for improving the light resistance, but in order to exert a sufficient effect, it is necessary to sufficiently block harmful ultraviolet rays, and the coating amount of the ultraviolet absorber to be added is increased. There is a need. However, on the other hand, in principle, the addition of the ultraviolet absorber needs to be added to the layer in which the dye is mordanted or to the side of the observation surface from which the dye is mordanted, which inevitably hinders the diffusion of this dye. Therefore, in order to achieve a sufficient UV blocking effect while minimizing the adverse effect on the diffusion of the dye, the UV absorber ratio of the layer to which the UV absorber is added must be high, and the physical strength of that layer There was a demerit that it would become weak. In particular, in the heat development color diffusion transfer system utilizing heat for image formation, a movable substance such as a salt, an oil, a base or a precursor thereof added to a light-sensitive material and a dye fixing element diffuses by heating, Since the physical strength of the film tends to be weakened, the demerit of adding the ultraviolet absorber to the physical strength is more remarkable.

[0005]

[Patent Document 1] JP-A-46-3335

[Patent Document 2] JP-A-57-157245

[Patent Document 3] Japanese Patent Laid-Open No. 61-153638

[0006]

It is an object of the present invention to release or produce an image-forming dye or precursor thereof in response to silver development, or vice versa, to form an image by diffusion transfer of the dye. A dye-fixing element suitable for use in the method, a method for forming a color image excellent in light resistance without deteriorating the physical strength of a film using the same, and a color image formation using the dye-fixing element To provide the material.

[0007]

As a result of repeated studies to solve the above problems, the inventor
Dispersion using a water-insoluble copolymer of a certain kind as at least one of the dispersion media, and by introducing it into the dye fixing element, the light fastness of the image can be remarkably improved without deteriorating the physical strength of the film. The present invention has been completed based on this finding. That is, the object of the present invention was achieved by the following dye fixing element. (1) An ultraviolet absorbing layer containing an ultraviolet absorbing agent at a coating amount of 0.2 g / m ² or more is provided above the mordant layer (on the image observing side), and at least one dispersion medium of the ultraviolet absorbing agent. Containing the compound represented by the general formula (1) as a ratio (mass ratio) of 25% to 200% of the ultraviolet absorber, and the total amount of the ultraviolet absorber and the dispersion medium of the ultraviolet absorber is the coating amount. Is 1.0 g / m ² or less, a dye fixing element for a color diffusion transfer method. General formula (1)

[0008]

[Chemical 2]

In the formula, x and y represent the mole fractions of the repeating units and are 1 in total. y is in the range of 0.85 to 0.95. In the present specification, the above formula represents the mole fraction of the repeating unit of the copolymer, and the binding mode (block copolymer, random copolymer) is not particularly limited. (2) The dye fixing element according to (1), wherein the ultraviolet absorbing layer uses 50% to 200% of the total mass of the ultraviolet absorber and the dispersion medium as a water-soluble polymer as a binder. (3) Gelatin accounts for 50% to 100% of the water-soluble polymer used as the binder of the ultraviolet absorbing layer (2)
The dye-fixing element described in 1. (4) Used in heat development color diffusion transfer method (1),
The dye fixing element according to (2) or (3). (5) An image forming method comprising using the dye-fixing element according to any one of (1) to (4) and a light-sensitive element in combination.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The ultraviolet absorbing layer of the present invention refers to a layer which absorbs at least a part of the ultraviolet rays reaching the next layer by absorbing the ultraviolet rays reaching the layer in the layer, and the ultraviolet absorbing layer of the present invention is At least 0.2 g / m ² or more of an ultraviolet absorber is added as a coating amount. The upper limit of the coating amount of the ultraviolet absorber is 1.0 g / m ² or less in combination with the dispersion medium used for dispersing the ultraviolet absorber in the ultraviolet absorbing layer described later.

In the present invention, the ultraviolet absorbing layer is provided in the dye fixing element in the protective layer or between the protective layer and the dye fixing layer. Further, the layer may be formed as a single layer or may be divided into a plurality of layers.

In the present invention, the ultraviolet absorber added to the ultraviolet absorbing layer may be selected from known organic compounds having appropriate absorption characteristics, and is generally used for ultraviolet absorption. Even a compound that is not used as an agent can be used as long as it has an absorption in the ultraviolet region of 320 nm or more and 400 nm or less, which strongly affects the light resistance of the dye fixing element. From the viewpoint of the effect of the invention, the material added to the ultraviolet absorbing layer is preferably an organic ultraviolet absorber, and more preferably, a normal organic ultraviolet absorber and / or its It is preferably selected from similar compounds.

Specific examples of organic UV absorbers include, for example, benzotriazole compounds (for example, those described in US Pat. No. 3,533,794), 4-thiazolidone compounds, and benzophenone compounds (for example, Japanese Unexamined Patent Publication (Kokai) No.
No. 2784), cinnamic acid ester compounds (for example, US Pat. Nos. 3,705,805 and 3,70).
No. 7,375), benzoxazole compounds (for example, US Pat. No. 3,700,455), butadiene compounds (for example, US Pat. No. 4,04).
No. 5,229), and US Pat.
The compounds described in JP-A-54-48535 and the like can be mentioned. In addition, compounds introduced as typical UV absorbers in the review articles such as "Characteristics and Applications of Ultraviolet Rays (UV Cut) Materials" (Technical Information Society) are also mentioned as specific examples. For example, cyanoacrylate compounds,
Examples thereof include triazine compounds.

The organic UV absorbers used in the present invention may be used alone or in combination of two or more of the above known UV absorbers.

In the method of introducing the ultraviolet absorber into the ultraviolet absorbing layer in the present invention, the dispersion medium is used in combination to introduce it as an emulsion. As the dispersion medium, at least the above-mentioned general formula (1) is used.
The compound represented by 25% to 20% by mass of the ultraviolet absorber
It is characterized by using 0%. Preferably 25% to 10
It is 0%. If this condition is satisfied, it is possible to jointly use another generally known dispersion medium as the dispersion medium used for emulsifying and dispersing the ultraviolet absorber. For example, a water-soluble polymer (typically gelatin) can be used in combination. Further, examples of the water-soluble polymer used as the binder of the ultraviolet absorbing layer include polyacrylic acid, polyvinyl alcohol, modified polyvinyl alcohol, acrylic acid-vinyl alcohol copolymer, dextran and the like.

The compound represented by the general formula (1) is not particularly limited by the molecular weight, but a low molecular weight compound is preferable, and a mass average molecular weight of 300 to 5000 is preferable. As the compound represented by the general formula (1), a commercially available compound can be used, and for example, Crystalrex 1120 (manufactured by Hercules Co.) can be used.

The image fixing material used in the present invention has at least a layer for fixing an image forming dye on a support, and a mordant is added to the dye fixing layer. If necessary, a surface protective layer, a timing layer, and an acid neutralization layer are provided, and a binder, a base generator, a thermal solvent, an antifoggant, a stabilizer, a hardener, a plasticizer, a high-boiling organic solvent, a coating aid. Agents, surfactants, antistatic agents, matting agents, slip agents, antioxidants and the like can be contained. Specifically, the dye fixing element described in JP-A-8-304982 and JP-A-9-59.
68, a dye image receiving material described in JP-A-9-34081, an image receiving element described in JP-A-10-142765,
Additives, materials and layer structures used in the image receiving element (dye fixing element) described in JP-A-9-152705 are applied, and more preferable embodiments are also described therein.

The light-sensitive material used in the present invention basically has a light-sensitive silver halide, a binder and a dye-donating compound on a support, and if necessary, a chemical sensitizer and a sensitivity-enhancing agent. , Spectral sensitizer, supersensitizer, whitening agent,
Antifoggants, stabilizers, light absorbers, filter dyes, hardeners, base generators, plasticizers, high boiling organic solvents, coating aids, surfactants, antistatic agents, matting agents, etc. may be contained. it can. Specifically, JP-A-9-1580
5, a heat-developable color light-sensitive material described in JP-A-9-15270.
Diffusion transfer silver halide photosensitive material described in JP-A-9-9
Color light-sensitive material described in 0582, JP-A-9-34081.
Heat-developable color light-sensitive material described in JP-A-10-14276.
The color diffusion transfer light-sensitive material described in 5 is mentioned, and more preferable embodiments are also described in these.

In the present invention, an alkali treatment composition can be used if necessary. The alkaline processing composition is evenly spread between the light-sensitive element and the image-receiving element after exposure of the light-sensitive element,
It develops the photosensitive layer, contains alkali and developer,
Further, it contains a thickener, a development accelerator, a development inhibitor, an antioxidant and the like, if necessary. Specifically, JP-A-10-142
This is the case for the treatment composition described in 765, and more preferable embodiments are also described therein.

In the present invention, as a support for a light-sensitive material or an image-fixing material, "Basics of Photographic Engineering-Silver Salt Photo-" edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) (22)
3) to (240) pages, synthetic polymers (films)
And other photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (such as triacetyl cellulose) or those films containing a pigment such as titanium oxide, Film method synthetic paper made from polypropylene etc., 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, Ceramic or the like is used. These can be used alone, or a support having one or both sides laminated with a synthetic polymer such as polyethylene, PET, polyester, polystyrene can be used.

In addition, JP-A-62-253,159 (29) to (31), JP-A-1-161,236 (14) to (17), JP-A-63-316,848.
No. 2, JP-A-2-22651, and JP-A-3-56,955.
No. 5,001,033 and the like 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. Further, for the purpose of improving the wettability of the coating solution and improving the adhesion between the coating film and the support, it is also preferable to preliminarily coat a polymer such as gelatin or PVA on the surface of these supports.

The thickness of the support varies depending on the purpose for which it is used, but is usually 40 μm or more and 400 μm or less. However, in the case of a method of forming an image using an element coated on two or more separate supports, the support on the non-image side of the element finally has a support thinner than the above range. The body (5 μm or more and 250 μm or less) is preferably used. As such a thin support, for example, PET
A film having aluminum vapor-deposited thereon is used.

Particularly when heat resistance and curl characteristics are severely demanded, it is used as a support for a light-sensitive material.
No. 6, No. 6-43581, No. 6-51426, No. 6-
No. 51437, No. 51442, No. 6-82961,
6-82960, 6-82959, 6-67
No. 346, No. 6-202277, No. 6-175282.
The supports described in No. 6, No. 6-118561, No. 7-219129, and No. 7-219144 can be preferably used.

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 using a camera, a method of exposing through a reversal film or a negative film using 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, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., US Pat. No. 4,500,626, column 56, JP-A-2-53,37.
The light sources and exposure methods described in No. 8 and No. 2-54,672 can be used. Further, a blue light emitting diode, which has made remarkable progress recently, can be used, and a light source combined with a green light emitting diode and a red light emitting diode can be used.
In particular, JP-A-7-140567 and JP-A-7-248549.
No. 7, No. 7-248541, No. 7-295115, No. 7-290760, No. 7-301868, No. 7-3.
01869, 7-306481, 8-1578.
The exposure apparatus described in No. 8 can be preferably 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 non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KD).
P), lithium iodate, inorganic compounds typified by BaB ₂ O ₄ , urea derivatives, nitroaniline derivatives, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM). -Oxide derivatives, JP-A-61-53462 and JP-A-62-210432
The compounds described in No. 10 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. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera, or the like, Nippon Television Signal Standard (NTS
A television signal represented by C), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG or CAD can be used.

The light-sensitive material and / or dye fixing element used in the present invention can be used for various purposes.
For example, the dye-fixing element after heat development transfer can be used as a positive or negative color print material.
Further, by using a photosensitive material which is a mixture of a black dye-donor substance and each of yellow, magenta and cyan dye-donor substances, a black-and-white positive or negative print material or a printing material such as a squirrel sensitive material is used. Or it can be used as a radiographic material. When the dye-fixing element of the present invention is used as a material for printing from a photographic material, a photographic material having an information recording ability as described in JP-A-6-163450 and 4-338944 is used to expose a light-sensitive material to heat development. It is preferred to make a print on the dye-fixing element of the invention by transfer. As this printing method, Japanese Patent Laid-Open No.
-241251, No. 5-19364, No. 5-193
The method described in No. 63 can be used. Further, it can be used as a photographing material by appropriately desilvering the light-sensitive material after the heat development transfer. In that case, as the support, for example, JP-A-4-124645 and JP-A-5-4032
It is preferable to record photographing information and the like using a support having a magnetic layer described in No. 1, No. 6-35092 and No. 6-317875. The light-sensitive material and / or the dye fixing element may be in a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of the dye. The heat generating element in this case is disclosed in JP-A-61-145,5.
Those described in No. 44 etc. can be used. The heating temperature in the heat development step is about 50 ° C to 250 ° C, and particularly about 6 ° C.
0 ° C to 180 ° C 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 process is
Transfer is possible in the temperature range from the temperature in the heat development step to room temperature.
Temperatures as low as 0 ° C are preferred.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056 and the like, 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. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent, for example, 50 ° C. to 100 when the solvent is water.
° C is preferred. Examples of the solvent used for accelerating the development and / or for the diffusion transfer of the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the above-mentioned JP-A-61). No. 238,056, page 4, upper right column, line 9 to page 6, upper left column, line 8) is used, a low boiling point solvent or a low boiling point solvent and water or the basic aqueous solution. A mixed solution may be mentioned. Further, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, an antifungal agent, and an antibacterial agent may be contained in the solvent. Water is preferably used as the solvent used in the steps of heat development and diffusion transfer, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water or the like can be used. Further, in a heat developing device using a light-sensitive material and an image receiving element, water may be used up or used up, or may be circulated for repeated use. In the latter case, water containing the components eluted from the material will be used. Further, JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
You may use the apparatus and water described in No. 5, etc.

These solvents can be applied to the light-sensitive material, the dye-fixing element or both of them. The amount used may be not more than the mass of the solvent corresponding to the maximum swelling volume of the entire coated film. As a method of applying this water, for example, JP-A-62-253,159, page (5), JP-A-63-
The method described in No. 85,544 is preferably used.
Further, the solvent may be enclosed in microcapsules, or may be incorporated in the light-sensitive material or the dye fixing element or both in the form of a hydrate in advance. The temperature of the applied water is 3 as described in JP-A-63-85,544.
It may be 0 ° to 60 ° C.

In order to accelerate dye transfer, a method in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material and / or the dye-fixing element can also be adopted. The layer to be incorporated may be any of a photosensitive silver halide layer, an intermediate layer, a protective layer and a dye fixing layer, but a dye fixing layer and / or a layer adjacent thereto is preferable. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere. A method of superimposing a light-sensitive material and a dye fixing element is disclosed in JP-A-62-253,159 and JP-A-6-26.
The method described in pages 1-147, 244 (27) can be applied.

Any of a variety of developing devices can be used in processing the photographic element, if desired. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
44, JP-A-6-130509, and JP-A-6-95338.
No. 6, No. 6-95267, No. 8-29955, No. 8-
The devices described in No. 29954 and the like are preferably used. As commercially available devices, Fuji Photo Film Pictrostat 100 and Pictrostat 200,
Same pictrostat 300, same pictrostat 33
0, the same Pictrography 3000, the same Pictrography 4000 (both are trade names) and the like can be used.

[0033]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1 First, a method for producing a dye fixing element will be described. The support shown in Table 1 was coated with the layer constitution shown in Table 2 to prepare a dye fixing element 100. This dye fixing element is a comparative example of the present invention having no ultraviolet absorbing layer.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

Ultraviolet absorber (1) was dispersed in the fifth layer of this dye fixing element with the dispersion medium shown in Table 3 and this dispersion was added to prepare ultraviolet absorption layers 101 to 110. Of these, 108 to 109 are dye fixing elements of the present invention, and the others are comparative examples for confirming the effects of the present invention. 108-1
The compound (4) used in 10 is a dispersion medium used in the present invention, and is a crystallized compound commercially available from Hercules Co., Ltd. as a compound represented by the general formula (1).
20 was used.

[0042]

[Table 3]

Next, a method for producing the heat-developable color light-sensitive material will be described. First, a method for preparing a photosensitive silver halide emulsion will be described. Photosensitive silver halide (1) [fifth layer (680 nm photosensitive layer)
Emulsion] A solution (I) and a solution (II) having the composition shown in Table 5 were simultaneously added to an aqueous solution having a composition shown in Table 4 for 13 minutes, and 10 minutes after the addition, Solution (III) and solution (IV) having the composition shown in (3) were added over 33 minutes.

[0044]

[Table 4]

[0045]

[Chemical 7]

[0046]

[Table 5]

From 13 minutes after the addition of the liquid (III) is started, 27
Aqueous solution containing 0.350% of sensitizing dye over 1 minute 1
50 cc was added.

[0048]

[Chemical 8]

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. Then, the chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 6. 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 0.20 μm.

[0050]

[Chemical 9]

[0051]

[Table 6]

[0052]

[Chemical 10]

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] An aqueous solution having the composition shown in Table 7 and a solution (I) having the composition shown in Table 8 and ( Solution II) was added simultaneously over 18 minutes, and 10 minutes after that, solutions (III) and (IV) having the compositions shown in Table 8 were added over 24 minutes.

[0054]

[Table 7]

[0055]

[Table 8]

Washing with water and desalting (the above-mentioned sedimentation agent b
Was used to adjust the pH to 3.9), and then decalcified lime-treated ossein gelatin (calcium content 15
22 g (0 ppm or less) and redispersed at 40 ° C.,
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (0.39 g) was added to adjust the pH to 5.9 and pAg to 7.8. Then, it was chemically sensitized at 70 ° C. The compounds used for the chemical sensitization are shown in Table 9. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (solution having the composition shown in Table 10). After chemical sensitization, the temperature was lowered to 40 ° C., 200 g of a gelatin dispersion of a stabilizer described later was added, and the mixture was sufficiently stirred and then stored.
The obtained emulsion had a yield of 938 g and was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6% and an average grain size of 0.2.
It was 5 μm.

[0057]

[Table 9]

[0058]

[Table 10]

[0059]

[Chemical 11]

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Table 12 was added to an aqueous solution having a composition shown in Table 11 which was sufficiently stirred.
Solution (I) and solution (II) having the composition shown in Table 1 were simultaneously added over 18 minutes, and 10 minutes later, the solution (II) having the composition shown in Table 12 was added.
Solution I and solution IV were added over 24 minutes.

[0061]

[Table 11]

[0062]

[Table 12]

After washing with water and desalting (the precipitation agent a was used at a pH of 3.8) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and pAg to 7.8. Adjusted to. Then, it was chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are shown in Table 13. The yield of the obtained emulsion was 683 g, which was a monodisperse cubic silver chlorobromide emulsion having a variation coefficient of 9.7%, and the average grain size was 0.32 μm.

[0064]

[Table 13]

Next, a method for preparing a fine grain silver chloride grain emulsion to be added to the first layer (810 nm photosensitive layer) will be described. Solution (I) and solution (II) having the composition shown in Table 15 were simultaneously added to an aqueous solution having the composition shown in Table 14 which had been sufficiently stirred for 4 minutes, and 3 minutes later, the composition shown in Table 15 (III) liquid
Solution (IV) was added over 8 minutes.

[0066]

[Table 14]

[0067]

[Table 15]

After washing with water and desalting (pH was set to 3.9 with the precipitating agent a) by a conventional method, lime-treated gelatin 132 was used.
g and redispersed at 35 ° C. to give 4-hydroxy-6-
The pH was adjusted to 5.7 by adding 4 g of methyl-1,3,3a, 7-tetrazaindene. The yield of the obtained silver chloride fine grain emulsion was 3200 g, and the average grain size was 0.10 μm.
It was m.

Next, a method for preparing a gelatin dispersion of colloidal silver will be described. The liquid having the composition shown in Table 17 was added over 24 minutes to the aqueous solution having the composition shown in Table 16 which was sufficiently stirred. After washing with water using the precipitating agent a, 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 51.
It was 2 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0070]

[Table 16]

[0071]

[Table 17]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. Gelatin dispersions of a yellow dye-donor compound, a magenta dye-donor compound and a cyan dye-donor compound were prepared according to the formulations shown in Table 18, respectively. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution, and the aqueous phase component heated at about 60 ° C. was added to the solution with stirring and mixing, and then a homogenizer was used for 10 minutes at 10,000.
Dispersed at rpm. Water was added to this and stirred to obtain a uniform dispersion. Further, using a ultrafiltration module (Asahi Kasei ultrafiltration module; ACV-3050), a gelatin dispersion of a cyan dye-donating compound was repeatedly diluted and concentrated with water to repeat the amount of ethyl acetate in Table 18 at 17.6 minutes. The amount of ethyl acetate was reduced so that it became 1.

[0073]

[Table 18]

A gelatin dispersion of the antifoggant is shown in Table 1.
Prepared according to the prescription of 9. That is, the oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then the mixture was stirred for 1 minute with a homogenizer for 1 minute.
Dispersion was carried out at 0000 rpm to obtain a uniform dispersion.

[0075]

[Table 19]

A gelatin dispersion of the high boiling point solvent is shown in Table 20.
Was prepared according to the prescription. That is, the oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then the mixture was stirred for 1 minute with a homogenizer for 1 minute.
Dispersion was carried out at 0000 rpm to obtain a uniform dispersion.

[0077]

[Table 20]

A gelatin dispersion of reducing agent was prepared according to the recipe in Table 21. That is, the oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, followed by 10 minutes with a homogenizer.
Dispersion was carried out at 000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0079]

[Table 21]

A dispersion of polymer latex a is shown in Table 22.
Was prepared according to the prescription. That is, an anionic surfactant was added over 10 minutes while stirring a mixed solution of the polymer latex (a), the surfactant and water in the amounts shown in Table 22 to obtain a uniform dispersion. Further, the obtained dispersion was prepared by using an ultrafiltration module (Asahi Kasei ultrafiltration module; ACV-3050) to repeatedly dilute and concentrate with water so that the salt concentration in the dispersion became 1/9. did.

[0081]

[Table 22]

A gelatin dispersion of stabilizer was prepared according to the recipe in Table 23. That is, the oil phase component is dissolved at room temperature,
To this solution was added the water phase component heated to approximately 40 ° C, and after mixing with stirring, use a homogenizer for 10 minutes at 10,000 rpm.
Dispersed in. Water was added thereto and stirred to obtain a uniform dispersion.

[0083]

[Table 23]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 24. That is, after mixing and dissolving each component,
30 using glass beads with an average particle size of 0.75 mm in a mill
Dispersed for minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.
The one having a thickness of 25 μm was used. )

[0085]

[Table 24]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. PM in methylene chloride
A liquid in which MA was dissolved was added to gelatin together with a small amount of a surfactant, and the mixture was stirred and dispersed at high speed. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain an average particle size of 4.
A uniform dispersion of 3 μm was obtained.

[0087]

[Chemical 12]

[0088]

[Chemical 13]

[0089]

[Chemical 14]

[0090]

[Chemical 15]

[0091]

[Chemical 16]

Heat-developable color photosensitive materials shown in Tables 25 to 28 were prepared using the above materials.

[0093]

[Table 25]

[0094]

[Table 26]

[0095]

[Table 27]

[0096]

[Table 28]

Image forming method The above dye fixing elements 100 to 110 were combined with the above light-sensitive material, and maximum exposure and development were carried out using a printer sold by Fuji Photo Film Co., Ltd. under the name of Pictrography 3000, and Y. A black solid image was obtained in which the M and C components were colored with maximum density.

Evaluation of Lightfastness A light-fading test of the dye fixing elements 100 to 110 was conducted under the following conditions. Discoloration tester: Weather-Omet manufactured by ATLAS
er 65WRC cycle: light (100000 Lux) /dark=3.8h
r / 1hr filter: None The reflection density of cyan in the solid black portion before the fading test and after 2 weeks of the fading test was measured by X-rite3 manufactured by X-rite.
Measurement was carried out using 10TR to obtain the dye residual rate after the fading test. This value is shown in Table 29. Those that are substantially unusable are marked with X in Table 29, and those that can be used are marked with ◯. (Dye residual ratio) = (reflection density after brown test) / (reflection density before brown test)

Evaluation of Film Strength Dye-fixing element 100-obtained by the above-mentioned image forming method
A scratch test was conducted on the surface of 110 under the following test conditions. The results are shown in Table 29. Those that are substantially unusable are marked with X in Table 29, and those that can be used are marked with ◯. Scratch tester: Shinto Scientific Co., Ltd. Continuous load type scratch tester TYPE18 Scratch condition: φ0.5mm sapphire needle 0-100g Load environment: 25 ℃ / 50% RH

[0100]

[Table 29]

From the above results, the use of the dye-fixing element of the present invention, compared to the dye-fixing element for comparison, has less adverse effect on the diffusion transfer, has a higher residual ratio of the dye in the fading test, and has a higher film strength. Is a strong dye fixing element.

[0102]

According to the dye-fixing element of the present invention, in the method of releasing or producing an image-forming dye or a precursor thereof by silver development and forming an image by diffusion transfer of the dye, the film strength is not lowered. An image having excellent light fastness can be formed, and an image forming method having excellent light fastness can be realized without lowering the film strength. Further, the thermal phenomenon color diffusion transfer photosensitive material using the above dye fixing element has an excellent effect of forming an image excellent in light fastness without lowering the film strength as described above.

Claims (5)

[Claims] 1. An ultraviolet absorbing layer containing an ultraviolet absorber at a coating amount of 0.2 g / m ² or more above the mordant layer, and having at least one of the general formula ( The compound described in 1) is added to the ultraviolet absorber of 25
% To 200% (mass ratio), and the total amount of the ultraviolet absorber and the dispersion medium of the ultraviolet absorber is 1.
A dye fixing element for a color diffusion transfer method, which has a content of 0 g / m ² or less. General formula (1) In the formula, x and y represent mole fractions of repeating units and are 1 in total.
Becomes y is in the range of 0.85 to 0.95. 2. The dye fixing element according to claim 1, wherein the ultraviolet absorbing layer uses, as a binder, 50% to 200% of a total of the mass of the ultraviolet absorber and the dispersion medium thereof as a water-soluble polymer. 3. The dye fixing element according to claim 2, wherein 50% to 100% of the water-soluble polymer used as the binder of the ultraviolet absorbing layer is gelatin. 4. The dye fixing element according to claim 1, 2 or 3, which is used in a heat development color diffusion transfer method. 5. An image forming method comprising using the dye fixing element according to claim 1 in combination with a photosensitive element.