JP2001201833A - Dye-fixing element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-fixing element which enhances the light fastness of a dye formed by a diffusion transfer system and reduces stain. SOLUTION: The dye-fixing element is used in a color image-forming method in which a photosensitive element with a photosensitive layer, containing at least photosensitive silver halide and a binder is developed, an image-forming dye or its precursor is released or formed in parallel or with silver development by the development and it is diffused or diffusion-transferred to form an image in the dye-fixing element. The dye fixing element has a base and a dye fixing layer on the base and the base has an L* value of 91 or larger, 90% or higher opacity, an apparent specific gravity of 0.85-1.25, an oxygen permeability of 50 ml or lower oxygen per (24 hr.m2.atm) and a steam permeability of 20 g or lower water per (24 hr.m2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye fixing element used in combination with a photosensitive element containing photosensitive silver halide in a diffusion transfer type image forming system.

[0002]

2. Description of the Related Art As a method for forming or releasing and diffusing an image-forming dye by exposing and developing a photosensitive silver halide and transferring the dye, a photographic material of a color diffusion transfer system (a so-called photographic material). Instant photography) and a method using a heat development color diffusion transfer system are known. Images obtained by these methods are generally inferior in light fastness to conventional photographic images, and various methods for improving light fastness have been studied. Further, in the image forming method of the diffusion transfer method, there is a problem of stain, and various improvements have been studied.
One of the methods for improving the light resistance and the method for reducing the stain includes the use of an ultraviolet absorber. Also, the use of various anti-fading agents used in so-called conventional photographic systems in diffusion-transfer photographic materials has been studied. However, the anti-fading agents useful in conventional photographic systems are oil-soluble, whereas the dyes used in the photographic method of forming an image by transferring the dyes are mainly water-soluble. In addition, since it is difficult to contain the discoloration inhibitor in a positional relationship that can sufficiently act on the dye, a sufficient effect cannot be obtained. In addition, Japanese Patent Publication No. 49-20974 proposes to add hindered piperidines and / or their radicals to a photosensitive element, and discloses that it is effective also in a dye diffusion transfer type image forming method. Have been. However, when these additives are added directly to the dye-fixing element, color mixing occurs and photographic properties change, and a good color image cannot be obtained.

A dye fixing element used in an image forming method of a dye diffusion transfer system generally contains a mordant, and an image is formed by fixing a dye to be diffused and transferred to the mordant by ionic interaction. . Conventionally, this dye immobilization method mordantes not only the dye transferred and diffused, but also ionic substances and water-soluble ionic substances existing in the air,
It has the disadvantage of fixing and coloring. Vanillin, 2,6-ditert-butyl-para-nitrophenol (hereinafter abbreviated as BNP), and the like are known as substances that fly from the air to the dye fixing element and mordant and color.
BNP is 2,6-di-t-butylparamethylphenol (also known as 2,6-di-t-butylhydroxytoluene, hereinafter abbreviated as BHT), which is generally used as an antioxidant in the production of various polymer materials. , And is produced by oxidation and nitration of BHT. BNP present in the air mordantes the stored dye-fixing element,
It develops yellow and forms stain on the dye-fixing element.

[0004] The dye fixing element is composed of BNP existing in the atmosphere.
For example, JP-A-9-31427 proposes a method of preventing the yellowing of the dye-fixing element by disposing a layer having a barrier property against a substance such as BNP. In addition, there is known a method of laminating a transparent film on output paper for the purpose of physically protecting the image surface, improving the surface properties, or preventing light fading due to oxygen blocking. However, these methods are difficult to implement in terms of material cost, user labor, hardware cost, and the like.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and to provide a dye fixing element capable of improving light fastness of an image formed by a diffusion transfer system and reducing stain. Aim.

[0006]

Means for solving the above problems are as follows. <1> After developing a photosensitive element having a photosensitive layer containing at least a photosensitive silver halide and a binder, release or generate an image-forming dye or a dye precursor corresponding to or inversely to silver development by the development. A dye-fixing element used in a color image forming method for forming an image on a dye-fixing element by diffusing or diffusion-transferring the dye or dye precursor, wherein the dye-fixing element comprises a support, Having a dye-fixing layer thereon, and L * of the support
The value is 91 or more, the opacity is 90% or more, the apparent specific gravity is 0.85 to 1.25, and the oxygen permeability of the support is 50 ml / 24 h · m ² · atm or less,
A dye-fixing element having a water vapor permeability of 20 g / 24 h · m ² or less. <2> The dye-fixing element according to <1>, wherein the support has a paper substrate and a shielding layer formed on the paper substrate and capable of shielding oxygen and water. <3> The dye-fixing element according to <2>, wherein the paper substrate has a natural pulp content of 60% by weight or more. <4> The dye-fixing element according to <2> or <3>, further including a polyethylene layer formed by applying a melt containing polyethylene between the blocking layer and the dye-fixing layer.

The present inventor has paid attention to the fact that oxygen is a factor that promotes fading of a formed image, and has examined the provision of a blocking element for preventing diffusion of oxygen into a dye fixing element. Was not seen. However, when a blocking element for preventing the diffusion of water vapor simultaneously with the diffusion of oxygen was provided, a remarkable effect was recognized. In addition, as for the stain, an examination was made to provide a blocking element for preventing the diffusion of BNP and BHT, but no sufficient effect was found. However, when a blocking element for preventing the diffusion of water vapor at the same time as the diffusion of BNP and BHT was provided, a remarkable effect was recognized. Based on this finding, the present invention has been completed. The mechanism of the effect of moisture on the photobleaching of the image formed by the diffusion transfer method is unknown, but the dye is present at high density in oil droplets in a conventional photographic system, whereas in the diffusion transfer method, It is considered that moisture in the photoreaction is more likely to be affected because of a more dilute dispersion state. The synergistic effect of shielding oxygen and water is more remarkable as the diffusible dye is more soluble in the hydrophilic solvent, and is more significant as the equilibrium water content of the dye fixing element membrane is higher.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The dye-fixing element of the present invention has a support and a dye-fixing layer thereon. The support is L *
Value is 91 or more, opacity is 90% or more, apparent specific gravity is 0.85 to 1.25, and oxygen permeability is oxygen 5
0 ml / 24 h · m ² · atm or less, and water vapor permeability is 20 g / 24 h · m ² or less. In the dye-fixing element of the present invention, since the support has the whiteness (L * value), opacity, and apparent specific gravity in the above ranges, the image formed on the dye-fixing element by the diffusion transfer method has a good texture. And maintain image quality. Further, in the present invention, by reducing the oxygen permeability and the water vapor permeability of the support, discoloration of an image caused by light irradiation and generation of stain due to a substance existing in the air are prevented. Therefore, when the dye-fixing element of the present invention is used, the formed image can maintain good texture and image quality, can have high light fastness, and can reduce the occurrence of stain.

In the present invention, the L * value is defined as CIE 19
It shows whiteness in a 76 (L * a * b *) color space. CIE 1976 (L * a * b) of the support
*) The L * value in the color space is 91 or more, preferably 93 or more, more preferably 96 or more. Also,
(A *) ² + in 1976 (L * a * b *) color space
The white color represented by (b *) ² is preferably as neutral as possible. The value of (a *) ² + (b *) ² is more preferably 4 or less, further preferably 2 or less. The value a in the color space is preferably -1 or more and 2 or less. The b value is preferably -4 or more and 1 or less. More preferably, a value is -1 or more and 2 or less,
And b value is -4 or more and 1 or less. Still more preferably, the a value is -0.5 or more and 1 or less, and the b value is -2.
It is 0 or less.

Regarding whiteness, JIS P 8123
Can also be specified. In that case, it is preferably at least 80%, more preferably at least 85% according to the method specified in the JIS. Furthermore, 440-640n
It is preferable that the spectral reflectance in the wavelength range of m is 85% or more, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength range is 5% or less. More preferably, the spectral reflectance is 85% or more in the wavelength range of 400 to 700 nm, and the difference between the maximum spectral reflectance and the minimum spectral reflectance in the same wavelength range is within 5%.

In order to adjust the whiteness and keep the L * value of the support within the above range, fine white particles, a dye, a pigment and the like can be added to the support. Examples of the white fine particles include barium sulfate, titanium oxide, calcium carbonate, calcium sulfate, zinc oxide, silica, kaolin, talc,
Clay, diatomaceous earth, magnesium silicate, calcium silicate and the like. These may be used alone or in combination of two or more. Among these,
Barium sulfate, titanium oxide and calcium carbonate are preferred, and it is preferred to use at least one of these.

The opacity of the support is at least 90%. Preferably it is at least 92%. Opacity is JIS
It can be measured by the method specified in the standard (P8138). A support having 100% opacity is a completely opaque paper. The higher the opacity, the better the image with less noise from the back side. The opacity of the support can be adjusted to the above range by adding the white fine particles to the support. In addition, the opacity can be increased by including air bubbles in the support.

The apparent specific gravity of the support is 0.85 to 1.
25. Preferably it is 0.90 to 1.20. If the apparent specific gravity is less than 0.85, knicks may easily occur, and if it exceeds 1.25, the texture of the print is impaired. The “apparent specific gravity” is a so-called “unit apparent volume” including a void portion included in the support.
Weight.

The support has an oxygen permeability of 50 ml of oxygen.
/ 24h · m ² · atm or less and water vapor permeability of water 2
0 g / 24 h · m ² or less. The dye-fixing element of the present invention may use, as the material of the support itself, a material exhibiting the oxygen permeability in the above range and the water vapor permeability in the above range, or the oxygen permeability or the water vapor permeability of a pulp material or the like. On a substrate having a high level, a shielding layer made of a material that shields oxygen and water vapor may be formed to constitute a support, and the oxygen permeability in the above range and the water vapor permeability in the above range may be imparted to the support. .

The oxygen permeability of the support is measured as an oxygen permeation volume per unit area after the support is placed in an environment under 1 atm of oxygen for 24 hours. The oxygen permeability of the support is more preferably not more than 30 ml / 24 h · m ² · atm of oxygen. The water vapor permeability of the support was determined by placing the support in an environment of 38 ° C. and 90% RH.
It is measured as the water vapor permeation weight per unit area after lapse of 4 hours. The water vapor permeability of the support is 15 g of water.
/ 24 h · m ² or less.

The fixing element of the present invention can be produced by incorporating a material for shielding oxygen and water vapor into a support or a shielding layer formed on the support. The material for shielding oxygen and water vapor is not particularly limited as long as it is a material capable of adjusting oxygen permeability and water vapor permeability to the above range, and various materials such as an organic material, an inorganic material, and a composite material are used. Can be used. Examples are shown below, but the materials used in the present invention are not limited to the following examples. For example, polymer materials such as polypropylene, polyvinylidene chloride, nylon 6, polyethylene terephthalate, cellophane, polyvinyl alcohol, eval, and polyacrylonitrile, and inorganic materials such as aluminum oxide and silicon oxide can be used. The constituent material may be used alone for the support, or a plurality of materials may be used in combination for the support to impart the above properties to the support. For example, the above properties may be imparted to the support by combining a material having a high oxygen barrier property and a material having a high water vapor barrier property.

Among the above constituent materials, a laminated film in which EVAL is sandwiched up and down with polypropylene or nylon 6 or a material obtained by depositing silicon oxide or aluminum oxide on polyethylene terephthalate can be preferably used.

Some examples of the constituent materials which are commercially available as laminated films are shown below. "Taiko" series manufactured by Nimura Chemical Co., Ltd. with moisture-proof treatment on cellophane surface, "Saran-UB" manufactured by Asahi Kasei Kogyo Co., Ltd. of biaxially stretched polyvinylidene chloride film, Daicel Chemical Co., Ltd. K-Celsi "," Celci KET "manufactured by Daicel Chemical Co., Ltd. coated with polyvinylidene chloride on biaxially stretched polyester," Celci KON "manufactured by Daicel Chemical Co., Ltd. coated with polyvinylidene chloride on biaxially stretched nylon, and biaxially stretched polypropylene "Celsi KOP" manufactured by Daicel Chemical Industries coated with polyvinylidene chloride, "BARRILO" manufactured by Toyo Metallizing Co., Ltd.
X ", polyester or polypropylene film, and" Tech Barrier "manufactured by Mitsubishi Kagaku Kojin Bax, which is obtained by depositing silicon oxide, and can be used as a constituent material of the support of the dye-fixing element of the present invention.

The support of the dye-fixing element of the present invention or the shielding layer of the support can be prepared by the following method. For example, when the material to be used can be used as a solution or dispersion such as water or an organic solvent, the solution and the dispersion are prepared using various coating methods such as bar coating and gravure coating. Can be. In the case of using a material having heat fusibility, it can be manufactured by using a melt extrusion method or a melt stretching method. When a material that vaporizes, such as aluminum oxide or silicon oxide, is used, it can be manufactured by a vapor deposition method. A metal such as aluminum can be used as a thinly stretched metal foil. In addition, the manufacturing methods exemplified above can be used alone, or can be used in combination when manufacturing a laminated support or a shielding layer.

When a support or a shielding layer is formed by laminating and laminating previously formed film materials, a thin (for example, several microns) adhesive layer is applied to one film surface, and then laminated. A method is used in which the other film is laminated. Also, several μm
It can be used as an adhesive layer by providing a thin undercoat of about m. When a laminated support or a shielding layer is manufactured, a surface treatment may be performed in advance to improve the surface activity of each layer and to provide adhesion. Examples of the surface treatment include a surface activation treatment such as corona discharge, glow discharge, flame treatment, and surface etching with a solvent, depending on the material to be laminated.

When the support is formed by forming the shielding layer on a substrate, the substrate may be permeable to oxygen or water vapor or may be shielding. As the substrate, "Basics of photographic engineering-silver halide photography-" edited by the Photographic Society of Japan
Published by Corona Co., Ltd. (1979) (223)-(24)
0) Papers described on page 0, and photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, film-processed synthetic paper made of polypropylene or the like, or synthetic resin pulp such as polyethylene and natural pulp. Mixed paper, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, ceramic and the like are used.

As the base material, a paper base material is preferably used. In addition to 100% natural pulp paper, mixed paper made from synthetic resin pulp and natural pulp, Yankee paper, baryta paper, coated paper, Cast coated paper can also be used preferably. When a paper base is used, it is preferable to use a paper base having 60% by weight or more of natural pulp because unevenness in treatment can be reduced.

In the present invention, the support may have a polyethylene layer formed by applying a melt containing polyethylene. It is preferable to have the polyethylene layer (laminate layer) in that the unevenness of the treatment can be reduced because the smoothness of the support is improved. As the polyethylene contained in the melt, various polyethylenes having a low density to a high density can be used. The melt may contain additives other than polyethylene.
It is preferable to include titanium oxide in the melt because whiteness can be improved. Polyethylene can be used as a binder into which titanium oxide can be kneaded. Therefore, when the whiteness of the support is improved, it is preferable to form the polyethylene layer and to include titanium oxide in the polyethylene layer. In the melt, it is preferable that titanium oxide is contained in an amount of 5 to 15% by weight based on polyethylene.

The above-mentioned melt may contain other additives as necessary, one of various additives may be used alone, or two or more of them may be used in combination. May be. For example, the white fine particles, the dye, and the pigment may be contained for adjusting the whiteness. Further, a light fastness improver, a fluorescent brightener, a stabilizer and the like can be contained. Examples of the light resistance improver include, for example, zinc sulfate, zinc oxide, hindered amine-based antioxidants, and benzotriazole-based ultraviolet absorbers such as benzophenone, and these may be used alone. Two or more kinds may be used in combination.

The thickness of the polyethylene-containing layer is 5 to 5
It is preferably 0 μm, more preferably 10 to 40 μm. The polyethylene-containing layer is preferably formed between the dye-fixing layer and the support. When the support has the shielding layer, it is preferably formed between the shielding layer and the dye-fixing layer.

The surface of the support may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. It is also preferable to coat a polymer such as gelatin or PVA on the surface of the support in advance for the purpose of improving the wettability of the coating solution and the adhesion between the coated film and the support.

In order to adjust the curl characteristics of the support, a resin layer containing polyethylene, a hydrophilic binder layer, or the like may be provided on the back surface of the support. The curl characteristics of the support can be adjusted using other known methods.

The support may have a concave and convex shape on the back surface. When the back surface has the uneven shape, it is possible to prevent the dye fixing elements from adhering to each other and the dye fixing element from adhering to another member. When the support or the back surface of the support is a polyethylene-containing layer formed by melt extrusion, the surface of the chill roll may be matted to form a mold, and the back surface of the support may be provided with an uneven shape. it can.

In the present invention, the thickness of the support is 5
It is preferably from 0 to 500 μm. More preferably, 70 to 3
00 μm. When the support comprises a paper substrate and a shielding layer, the thickness of the shielding layer is preferably a thickness that does not impair the texture of the paper substrate, and is generally 1 to 70.
μm, and more preferably 2 to 50 μm.

[0030] The support has transportability and print handling properties.
Surface resistance is 10 ⁶Ω or more 10¹³Ω or less
Preferably below 10.⁸Ω or more 10¹²Ω or less
More preferably. The stiffness is 0.3mN ・ m or more
It is preferably 3 mN · m or less, and 0.6 mN · m or less.
More preferably, it is not more than 2 mN · m. Front and back
The ratio of static friction coefficient (front / back) is 0.2 or more and 3 or less
It is preferably 0.5 or more and 2 or less.
New The moisture content of the support was 3% from the viewpoint of uneven processing.
Preferably not less than 10% and not more than 4% and not more than 8%
Is more preferable.

The dye fixing element of the present invention has a dye fixing layer on the support. The dye fixing layer preferably contains a mordant for mordant and fixing the dye released from the photosensitive element. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88256, pages (32) to (41) and JP-A-1-16
No. 1,236, pages (4) to (7), mordants described in U.S. Pat. Nos. 4,774,162 and 4,619,883;
Nos. 4,594,308 and the like can be mentioned. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

The dye fixing element may further have a surface protective layer, a timing layer, and an acid neutralizing layer, if necessary. In each of the layers, a binder, a base generator, a hot solvent,
It may contain whitening agents, antifoggants, stabilizers, hardeners, plasticizers, high-boiling organic solvents, coating aids, surfactants, antistatic agents, matting agents, slip agents, antioxidants, etc. it can. Various materials used for the dye-fixing layer and the other layers of the dye-fixing element are described in JP-A-8-30.
No. 4982, a dye-fixing element described in JP-A-9-59.
No. 68, JP-A-9-3408.
JP-A-10-142765
Patent Application Publication No. JP-A-9-152
Materials used for the dye-fixing element (dye-fixing element) described in JP-A-705 can be used. Preferred examples of the materials described in the above-mentioned respective publications are used as preferred examples of the present invention. Can be.

The dye fixing element of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of the dye. As the heat generating element in this case, those described in JP-A-61-145544 can be used.

Examples of the constitution of the dye-fixing element of the present invention are shown below, but the dye-fixing element of the present invention is not limited to the following constitution examples. It is preferable that the interface between the layers has been subjected to the above-described surface treatment. Here, the description of the surface treatment is omitted. In Structural Examples 1 to 3, the part from the back layer to the polyethylene-containing layer below the dye-fixing element constituent layer corresponds to the support. Further, the structural examples 4 and 5 are examples in which the support itself is made of a synthetic resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or a derivative thereof exhibiting the above characteristics. Configuration Examples 3 and 5 are configuration examples in which the dye fixing element also functions as a photosensitive element. Configuration example 1. Back layer (1 μm) / polyethylene-containing layer (26 μm) / base paper layer (160 μm) / blocking layer (20 μm)
m) / polyethylene-containing layer (20 μm) / dye-fixing layer (10 μm) Back layer (1 μm) / polyethylene-containing layer (26 μm) / base paper layer (160 μm) / polyethylene-containing layer (35 μm) / blocking layer (3 μm) / dye solid layer (10
μm) Configuration example 3. Back layer (1 μm) / polyethylene-containing layer (26 μm) / base paper layer (160 μm) / blocking layer (20 μm)
m) / polyethylene-containing layer (20 μm) / dye fixing layer (10 μm) / photosensitive element constituent layer (7 μm) Support / Dye fixing layer Configuration example 5 Support / dye fixing layer / photosensitive element constituting layer

The dye fixing element of the present invention is used together with a photosensitive element in an image forming system of a diffusion transfer system. The photosensitive element corresponds to silver development or reverse,
It releases or produces an imaging dye or dye precursor. The photosensitive element basically has a photosensitive silver halide, a binder, and a dye-providing compound on a support, and further, if necessary, a chemical sensitizer, a sensitivity enhancer, a spectral sensitizer, Supersensitizers, brighteners, antifoggants, stabilizers, light absorbers, filter dyes, hardeners, base generators, plasticizers, high-boiling organic solvents, coating aids, surfactants, antistatic Agents, matting agents and the like. Specifically, a heat-developable color photosensitive element described in JP-A-9-15805, a diffusion transfer silver halide photosensitive element described in JP-A-9-152705,
Japanese Patent Application Laid-Open No. 9-34
No. 081, a heat-developable color photosensitive element disclosed in
And a color diffusion transfer photosensitive element described in JP-A-142765, and those described in these can be applied to more preferred embodiments. The photosensitive element may have a conductive heating element layer as a heating means for heat development and diffusion transfer of the dye. As the heat generating element in this case, those described in JP-A-61-145544 can be used.

The photosensitive element may be coated on the same support as the dye-fixing element, even if it is coated separately on a support separate from the dye-fixing element. Is also good. Regarding the mutual relationship between the photosensitive element and the dye fixing element, the relationship described in column 57 of U.S. Pat. No. 4,500,626 can be applied to the present invention. When the support has a separate support, examples of the support of the photosensitive element include those listed as the base of the support of the dye-fixing element. In addition, JP-A-62-253,159 (29) to (31)
Page, JP-A-1-161,236 (14)-(17)
Page, JP-A-63-316,848, JP-A-2-22,
No. 651, No. 3-56,955, U.S. Pat.
The support described in No. 1,033 or the like can be used.
Particularly when heat resistance and curling characteristics are strictly demanded, JP-A-6-41281 and JP-A-6-43 are used as supports for photosensitive elements.
No. 581, No. 6-51426, No. 6-51437,
Nos. 6-51442, 6-82961, 6-82
No. 960, No. 6-82959, No. 6-67346,
6-202277, 6-175282, 6-
118561, 7-219129, 7-219
The support described in No. 144 can be preferably used.

The dye fixing element of the present invention is used in combination with a photosensitive element in an image forming system of a diffusion transfer system. In the image forming system, the photosensitive element is first exposed imagewise. Examples of the method of exposing the photosensitive element include, 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 negative film using a printer or a enlarger, an exposure apparatus of a copying machine, and the like. A method of scanning and exposing an original image through a slit or the like, a method of exposing image information by emitting a light emitting diode or various lasers via an electric signal, exposing a CRT, a liquid crystal display,
There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system. The exposure may be performed in a state where the photosensitive element and the dye fixing element are in contact with each other,
Only the photosensitive element may be exposed.

Light sources used for the exposure include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, and the like, US Pat. No. 4,500,626, column 56, JP-A-2-53,378, and the like. 2-54, 6
The light source and the exposure method described in No. 72 can be used. Further, a light source using a blue light emitting diode, which has been remarkably developed recently, and a green light emitting diode in combination with a red light emitting diode can be used. In particular, JP-A-7-140
No. 567, No. 7-248549, No. 7-248541
Nos. 7-295115, 7-290760, 7-301868, 7-301869, and 7-3
Exposure apparatuses described in JP-A Nos. 06481 and 8-15788 can be preferably used.

Further, image exposure can 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 nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (KD)
P), inorganic compounds represented by lithium iodate, BaB2O4, etc., urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM) JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are preferably used. As a 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 image information includes an image signal obtained from a video camera, an electronic still camera, etc.
A television signal represented by C), an image signal obtained by dividing an original image into a number of pixels such as a scanner, and an image signal created by using a computer represented by CG and CAD can be used.

Next, the photosensitive element on which the latent image has been formed by exposure is thermally developed. The heating temperature in the thermal development step is
Generally, it is carried out at about 50 ° C to 250 ° C.
It is useful to work at ~ 180 ° C. The step of diffusing and transferring the dye released by heat development to the dye fixing element may be performed simultaneously with the heat development step, or may be performed after the heat development step. In the case of the latter, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is particularly 50 ° C. or higher and about 10 ° C.
Up to lower temperatures are preferred.

Although the movement of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases include the image forming accelerators). And a mixed solution of a low-boiling solvent and water or the above-mentioned basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photosensitive element and the dye fixing element of the present invention, water may be used up, or the water may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-
144,354, 63-144,355, 62
-38,460 and JP-A-3-210,555, etc., or water.

At the time of heat development, an alkali treatment composition can be used if necessary. The alkali treatment composition is developed uniformly between the photosensitive element and the dye-fixing element after exposure of the photosensitive element, and develops the photosensitive layer. It contains an alkali and a developing agent, and further includes a thickener and a development accelerator as necessary. Agents, development inhibitors, antioxidants and the like. More specifically,
-142765 corresponds to this,
What is described therein can be applied to more preferred embodiments.

The solvent can be applied to the light-sensitive element and / or the dye-fixing element. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method for applying water, for example, JP-A-62-2531,1
The method described in JP-A-59 (5), JP-A-63-85,544 and the like is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive element or the dye fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied is as described in
The temperature may be 30 ° C. to 60 ° C. as described in US Pat.

In order to promote the dye transfer, a system in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at a high temperature is incorporated in the photosensitive element and / or the dye fixing element can be adopted. The layer to be incorporated may be any of a light-sensitive silver halide layer, an intermediate layer, a protective layer and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. 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 heating block, a plate, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater, an infrared and far infrared lamp heater can be used. For example, or by passing through a high-temperature atmosphere. The heat development and transfer steps are preferably performed in a state where the photosensitive element and the dye fixing element are overlaid. As a method of superimposing, Japanese Patent Laid-Open No. 62-253
No. 159 and JP-A-61-147244 (27).
The method described on page can be applied.

In the image forming process in which the dye fixing element and the photosensitive element of the present invention are combined, any of various developing devices can be used if necessary. For example, see JP-A-59-752.
No. 47, 59-1777547, 59-18135
No. 3, No. 60-18951, Shokai 62-25944
JP-A-6-130509, JP-A-6-95338,
Nos. 6-95267, 8-29955, 8-29
Devices described in each gazette such as No. 954 are preferably used. Commercially available devices include Fuji Photo Film's Pictrostat 100 and Pictrostat 2
00, the same pictrostat 300, the same pictrostat 330, the same pictography 3000, the same pictography 4000 can be used.

The dye-fixing element of the present invention can be used in various applications in combination with a photosensitive element. For example, the dye fixing element after the heat development transfer can be used as a positive or negative color print material. Also, by using a photosensitive element using a black dye-donating substance or a mixture of yellow, magenta, and cyan dye-donating substances, a printing material such as a black-and-white positive-type or negative-type printing material or a lithographic material. Alternatively, it can be used as a radiographic material. In particular, when used as a material for printing from photographic materials, JP-A-6-163450 and JP-A-4-163450.
It is preferable to use a photographic material having information recording ability as described in JP-A-338944 to expose the photosensitive element of the present invention and produce a print on the dye-fixing element of the present invention by heat development transfer.
As this printing method, JP-A-5-241251,
The methods described in JP-A-5-19364 and JP-A-5-19363 can be used. Further, the photosensitive element after the heat development transfer is appropriately desilvered to be used as a photographing material. In this case, as a support for the photosensitive element and the fixing element, for example, JP-A-4-124645 and JP-A-5-4
0321, 6-35092, 6-317875
It is preferable to record photographic information and the like by using a support having a magnetic layer described in (1).

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Supports S-1 to S-13 having the configuration shown in Table 1 were produced. For any of the supports, high quality paper (L
BKP / NBSP = 6/4, density 1.053, natural pulp containing 160 g / m ² ). For any of the supports, on the back side of the base paper, the back side polyethylene-containing layer (27 μm) and the back layer (0.5
μm). The backside polyethylene-containing layer was a layer made of high-density polyethylene and having a density of 1.053. The back layer was a layer formed by applying a coating solution containing polyvinyl alcohol, colloidal silica, and alumina sol (each coating amount was 0.5 g.
/ M ² , 0.07 g / m ² , 0.14 g / m ² ).

Next, with the composition shown in Table 1 below, the shielding layer was formed using various materials in various arrangements, and the support S-1 was formed.
To S-13. In the table, the left column shows constituent layers closer to the base paper. In all the supports, the composition of the surface polyethylene-containing layer was such that low-density polyethylene (density 0.923) 90.2 parts by weight, surface-treated titanium oxide (9.8 parts by weight), and ultramarine (0.001 parts by weight). Parts by weight) and the thickness was 36 μm.

[0050]

[Table 1]

Table 2 below shows the physical properties of the supports S-1 to S-13.

[0052]

[Table 2]

Next, on the surfaces of the produced supports S-1 to S-13, a number of layers shown in Table 3 below were formed by a multi-layer coating method, and image receiving materials (dye fixing elements) 101 to 11 were formed.
3 was produced.

[0054]

[Table 3]

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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Next, a heat-developable color photosensitive material (photosensitive element)
A method for manufacturing the device will be described. First, a method for producing a photosensitive silver halide emulsion will be described. Photosensitive silver halide (1) [5th layer (680 nm photosensitive layer)
Emulsion for use] Solution (I) and solution (II) having the composition shown in Table 5 were simultaneously attached to a sufficiently stirred aqueous solution having the composition shown in Table 4 over 19 minutes. The solution (III) having the composition shown in (1) was added over 33 minutes, and the solution (IV) was added over 33 minutes and 30 seconds.

[0062]

[Table 4]

[0063]

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[0064]

[Table 5]

Also, 15 minutes after the start of the addition of the solution (III), 27
Aqueous solution containing 0.350% of sensitizing dye over 1 minute
50 cc was added.

[0066]

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After washing with water and desalting (using a precipitant a at a pH of 3.7 to 4.1) according to a conventional method, 22 g of lime-treated ossein gelatin was added, and the pH was adjusted to 6.0 and pAg. Was adjusted to 7.9 and then chemically sensitized at 60 ° C. The compounds used for chemical sensitization are as shown in Table 6. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0068]

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[0069]

[Table 6]

[0070]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] A solution (I) of the composition shown in Table 8 was added to an aqueous solution of the composition shown in Table 7 which was sufficiently stirred. Solution II) was added simultaneously over 18 minutes, and 5 minutes later, solution (III) having the composition shown in Table 8 was added over 24 minutes, and solution (IV) was added over 24 minutes and 30 seconds.

[0072]

[Table 7]

[0073]

[Table 8]

Lime-treated ossein gelatin (calcium content: 150 ppm) after washing with water, desalting (pH was set to 3.9 using the sedimentation agent b) and decalcification according to a conventional method.
22 g), redisperse at 40 ° C., add 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, adjust the pH to 5.9 and the pAg to 7.8. Was adjusted to Then, it was chemically sensitized at 70 ° C. The compounds used for chemical sensitization are as shown in Table 9. During the chemical sensitization, the sensitizing dye was converted to a methanol solution (Table 10).
(A solution having the composition shown in Table 1). In addition, 40 after chemical sensitization
The temperature was lowered to 0 ° C., and a gelatin dispersion 20 of a stabilizer described later was prepared.
0 g was added, stirred sufficiently, and then stored. The yield of the obtained emulsion was 938 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0075]

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[0076]

[Table 9]

[0077]

[Table 10]

[0078]

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Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Sensitive Layer)]
Solution (I) and Solution (II) having the composition shown in Table 12 were simultaneously added over 18 minutes, and 5 minutes later, (III) having the composition shown in Table 12
The solution was added over 24 minutes, and the solution (IV) was added over 24 minutes and 30 seconds.

[0080]

[Table 11]

[0081]

[Table 12]

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

[0083]

[Table 13]

Next, a method for preparing fine silver chloride particles 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 the well-stirred aqueous solution having the composition shown in Table 14 over 4 minutes, and 3 minutes later, the solution having the composition shown in Table 15 was added. Solution (III) and solution (IV) were added over 8 minutes.

[0085]

[Table 14]

[0086]

[Table 15]

After washing with water and desalting (using a precipitant a at a pH of 3.9), 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.
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 to the sufficiently stirred aqueous solution having the composition shown in Table 16 over 24 minutes. Thereafter, the resultant was washed with a settling agent a and then added with 43 g of lime-treated ossein gelatin to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 51
2 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0089]

[Table 16]

[0090]

[Table 17]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Gelatin dispersions of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound were each prepared as prescribed in Table 18. That is, each oil phase component is heated and dissolved at about 70 ° C. to form a uniform solution, and the aqueous phase component heated to about 60 ° C. is added to this solution, and the mixture is stirred and mixed.
Dispersed at rpm. Water was added thereto and stirred to obtain a uniform dispersion. Further, the gelatin dispersion of the cyan dye-donating compound was repeatedly diluted and concentrated with water using an ultrafiltration module (Asahi Kasei ultrafiltration module; ACV-3050), and the amount of ethyl acetate in Table 18 was 17.6 minutes. The amount of ethyl acetate was reduced to become 1.

[0092]

[Table 18]

[0093]

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[0094]

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[0095]

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The gelatin dispersion of the antifoggant is shown in Table 1.
Prepared according to Formulation No. 9. That is, the oil phase component is heated and dissolved at about 60 ° C., the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed.
It was dispersed at 0000 rpm to obtain a uniform dispersion.

[0097]

[Table 19]

A gelatin dispersion of the reducing agent was prepared according to the recipe in Table 20. That is, the oil phase component is heated and dissolved at about 60 ° C., the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed.
The mixture was dispersed at 000 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0099]

[Table 20]

Table 21 shows the dispersion of the polymer latex a.
Prepared according to the formula That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 21 to obtain a uniform dispersion. Further, using an ultrafiltration module (Asahi Kasei ultrafiltration module; ACV-3050), the obtained dispersion was repeatedly diluted and concentrated with water so that the salt concentration in the dispersion became 1/9. did.

[0101]

[Table 21]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 22. That is, the oil phase component is dissolved at room temperature,
An aqueous phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed. Then, the mixture was homogenized for 10 minutes at 10,000 rpm.
Was dispersed. This was mixed with water and stirred to obtain a uniform dispersion.

[0103]

[Table 22]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 23. That is, after mixing and dissolving each component,
Using a glass bead with an average particle size of 0.75 mm,
Dispersed for minutes. Further, glass beads were separated and removed to obtain a uniform dispersion (zinc hydroxide had an average particle size of 0.2%).
The thing of 5 μm was used. ).

[0105]

[Table 23]

Next, a method for preparing a gelatin dispersion of a matting agent to be added to the protective layer will be described. PM in methylene chloride
The solution in which MA was dissolved was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus, and the average particle size was 4.
A uniform dispersion of 3 μm was obtained.

Using the above materials and the following materials, heat-developable color light-sensitive materials 100 shown in Tables 24 and 25 were prepared.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

[Table 24]

[0113]

[Table 25]

(Evaluation of Light Fastness) The Dye Fixing Material 10
1 to 113, respectively.
Exposure and thermal development were performed using a printer sold under the name of "Picrography 3000" by Fuji Photo Film Co., Ltd. in combination with the (photosensitive element) to obtain an image in which the monochromatic and gray densities were changed stepwise. Obtained. A light-fading test of this sample was performed under the following conditions. Discoloration tester: ATLAS-made Weather-Omet
er 65WRC cycle: bright (100,000 Lux) /dark=3.8 h
r / 1hr filter: Fuji Filter SC37 Before and after 3 weeks of the fading test, the reflection density of cyan in the solid black portion of the dye fixing element was measured using X-rite310TR manufactured by X + -rite, and after the fading test. The dye remaining rate was determined. This value is shown in Table 26.

(Evaluation of Stain) An image prepared in the same manner as described above and having the monochromatic and gray densities changed stepwise is stored at 25 ° C. for 6 months in a room free from light.
Table 26 shows the increase in yellow density in the fog area.

[0116]

[Table 26]

From the above results, the image receiving material 101 for comparison was used.
It has been demonstrated that the use of the image receiving materials 105 to 106 and 108 to 113 of the examples has a higher cyan residual rate and reduces the fading property as compared with the case of using Examples 104 to 107. Was. In addition, it was demonstrated that the image receiving materials of the examples showed less increase in stain concentration over time than the comparative image receiving materials.

Next, the photosensitive element to be used was changed to a Pictrostat Donor Film PS-DS sold by Fuji Photo Film Co., Ltd., and the printer was changed to a printer sold under the name of Pictrostat 330, in the same manner. As a result of forming an image and performing a similar test, it was found that the image receiving materials of the examples had similarly improved light fastness and reduced stain.

[0119]

According to the present invention, it is possible to provide a dye fixing element capable of improving the light fastness of an image formed by the diffusion transfer method and reducing stain.

Claims (4)

[Claims] Claims: 1. An image forming dye or dye precursor is released or developed corresponding to or inversely corresponding to silver development by developing a photosensitive element having a photosensitive layer containing at least photosensitive silver halide and a binder. A dye-fixing element used in a color image forming method of forming an image on the dye-fixing element by diffusing or diffusion-transferring the dye or the dye precursor, wherein the dye-fixing element comprises a support and A support having an L * value of at least 91, an opacity of at least 90%, an apparent specific gravity of 0.85 to 1.25,
The support has an oxygen permeability of 50 ml / 24 h · m ²
・ Atm or less and water vapor permeability is 20 g / 24 h of water
A dye-fixing element having a m ² or less. 2. The dye-fixing element according to claim 1, wherein the support has a paper substrate and a shielding layer formed thereon, which can shield oxygen and water. 3. The dye-fixing element according to claim 2, wherein the paper substrate has at least 60% by weight of natural pulp. 4. The dye-fixing element according to claim 2, further comprising a polyethylene layer formed by applying a melt containing polyethylene between the blocking layer and the dye-fixing layer.