JPH04333845A - Photosensitive thermosensitive transfer type image forming material and image forming method - Google Patents

Abstract

PURPOSE:To provide an image forming material and an image forming method by which a distinct color image with high resolution is obtained with easy drying processing and in which digital image recording with high resolution is also accomplished. CONSTITUTION:After image-exposure is performed to a photosensitive thermosensitive transfer type image forming material obtained by containing at least silver salt oxidant, reducer, binder and thermal diffusion dyestuff on the same surface of a supporting body, and a transfer type image forming material having a layer consisting of at least the silver salt oxidant, the reducer, the binder and the thermal diffusion dyestuff on the same surface of the supporting body, heat development is performed to form a silver image in an image state. Then, they are superposed on an image receiving material and uniformly exposed, so that the deystuff is transferred in the image state on the image receiving material.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel image-forming material and image-forming method using a heat-developable photosensitive material.

0002

2. Description of the Related Art As a method for easily obtaining images, particularly high-quality color images, by dry processing, methods using heat-developable photosensitive materials or heat-sensitive transfer materials are known.

[0003] An image forming method using a heat-developable photosensitive material is described, for example, in Research Disclosure (RD) No. 299
63 and the Journal of the Photographic Society of Japan, Vol. 51, No. 4 (1988), p. 269, and after exposure, it is thermally developed to form monochrome or color images of silver or pigments, or it is formed or released by development. A monochrome or color image is formed on an image-receiving sheet by transferring the dye. Transferring dyes is an excellent method for obtaining clear color images, but the composition of the photosensitive material and the structure of the dye-forming compound become complicated. Therefore, material costs tend to increase.

On the other hand, thermal transfer materials are known as a method for forming images by transferring dyes, such as RD.
No. 32019. Although thermal transfer materials are excellent in that images can be formed in a simple manner, they have a problem in that high-resolution images cannot be recorded at high speed due to low resolution and sensitivity.

Furthermore, in US Pat. No. 3,767,394, a heat-developable photosensitive layer is provided on one side of a transparent support, a heat-diffusible dye layer is provided on the opposite side, and after exposure, heat development is performed. conduct,
An image forming method is described using a material that combines a heat-developable photosensitive material and a heat-diffusible dye, in which the dye is transferred and an image is formed by overlapping the image-receiving material and uniform exposure. However, in the above method, since the dye-containing layer and the silver image forming layer are separated via the support, the efficiency of utilizing the heat converted from light to heat in the silver image area due to uniform exposure is low, making it difficult to obtain a high density image. It is necessary to increase the exposure energy. Furthermore, since heat is transmitted through the binder, the sharpness of the image is reduced due to heat diffusion. Furthermore, it has the disadvantage that it is difficult to apply to laser writing for obtaining high-resolution digital image recording, which has been rapidly developed in recent years.

[0006]Therefore, there is a need for the development of a new image forming method that can record high-quality images at high speed through dry processing, and can also record high-resolution digital images.

[0007]

OBJECTS OF THE INVENTION An object of the present invention is to provide a novel image-forming material and image-forming method that can easily produce high-resolution, clear color images through dry processing. Another object of the present invention is to provide a new image forming material and image forming method that also allows high resolution digital image recording.

[0008]

[Structure of the Invention] The above object of the present invention is to provide a light and heat sensitive transfer type image forming material containing at least a silver salt oxidizing agent, a reducing agent, a binder and a heat diffusible dye on the same side of a support; A transfer type image forming material having a layer consisting of at least a silver salt oxidizing agent, a reducing agent, a binder and a heat diffusible dye on the same side was subjected to imagewise exposure and heat development to form an imagewise silver image. This is achieved by an image forming method in which the dye is then overlapped with an image-receiving material and exposed uniformly to imagewise transfer the dye to the image-receiving material.

The present invention will be explained in more detail below.

The silver salt oxidizing agent of the present invention is disclosed in Japanese Patent Publication No. 43-492.
No. 1, No. 44-26582, No. 45-12700,
No. 45-18416, No. 45-22815, JP-A-52-137321, No. 53-36224, No. 53
-37626, 58-118635, 58-1
18639, U.S. Patent No. 3,330,633,
No. 342,599, No. 3,719,492, No. 3,7
No. 61,270, No. 3,764,328, No. 3,79
Organic silver salt compounds described in No. 4,496, No. 4,105,451, etc. can be used. Especially long-chain fatty acids (
Silver salts of behenic acid (behenic acid) or silver salts of benzotriazole and its derivatives are preferred because of their developability and separation of exposed and unexposed areas, that is, high-quality images can be obtained with short development times. In particular, JP-A-58-118635 and JP-A No. 60-1
Silver salts of benzotriazole and its derivatives as described in No. 94449 are preferred when a water-soluble binder is used. The amount of silver salt oxidizing agent added is 0.01 to 1 m2 of support.
20g is preferred.

As a reducing agent, US Pat. No. 3,342,59
No. 9, No. 3,351,280, No. 3,719,492
No. 3,761,270, No. 3,764,328 and RD No. Compounds described in No. 29963 and the like can be used. The amount of reducing agent added is 0.0 per m2 of support.
1 to 15 g is preferred.

As a binder, RD No. 32019
Although the polymer binder described on page 929 of , can be used, water-soluble polymers are preferred for the productivity of the material of the present invention and for adding the dye in a dispersed state. As the water-soluble polymer, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol, and gelatin are preferably used. These polymers may be used alone or in combination of two or more. The amount of binder added is 0.0 per m2 of support.
3 to 20 g is preferred.

[0013] As a thermodiffusible dye, JP-A-60-27
No. 594, No. 60-31563, No. 60-53564
No. 60-131293, No. 60-239289, No. 61-35994, No. 61-227091, No. 61-227092, No. 61-268494, No. 6
No. 1-268495, No. 62-87393, No. 62-
No. 99195, No. 62-294593, No. 63-15
No. 790, No. 63-74685, No. 63-14206
No. 2, No. 63-182163, No. 63-205288
No. 64-63194, JP 1-263092, JP 2-3450, JP 2-155693 and RDN
o. The dyes described in 32019932, page 939 can be used. In addition, in order to improve image stability, especially fixing properties, please refer to JP-A-59-78893, page 3, JP-A-6
It is preferable to use the chelatable dyes described in No. 0-2398, pages 2 to 5. Particularly preferred chelatable dyes are tridentate chelatable dyes, and dyes represented by the following general formula are preferably used.

[0014]

[Chemical formula 1]

In the formula, X1 has at least one ring of 5 to 7
represents a group of atoms necessary to complete an aromatic carbocyclic or heterocyclic ring composed of atoms, and at least one adjacent position of the carbon atom bonded to the azo bond is substituted with a nitrogen atom or a chelating group. X2 represents an aromatic heterocycle or aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms, and G represents a chelating group.

The dyes of the invention are added to the binder in solution or in dispersion. The dispersed state is a state in which it is incompatible with the binder, and it is preferably added in the form of solid fine particles. In order to add the dye in the form of solid fine particles, a method of mechanically dispersing the dye into solid fine particles using a ball mill, sand mill, etc. can be used.

The dyes of the present invention may be used alone or in combination of two or more, and the amount used is 0.05 to 1 per m2 of support.
0g is preferred.

Even if all of these compounds constituting the present invention are added in the same layer, the photosensitive and thermosensitive layer containing these compounds constituting the present invention may be composed of, for example, a layer consisting of a silver salt oxidizing agent, a reducing agent, and a binder, and a layer consisting of a heat-diffusible dye and a binder. The layer may be composed of two separate layers, but at least the heat-diffusible dye may be added to the same layer as the silver salt oxidizing agent-containing layer or to the upper layer (the layer farthest from the support) of the silver salt oxidizing agent-containing layer. In order to increase the light-to-heat conversion efficiency in full-surface exposure and obtain a high-resolution image, it is more preferable that all the components are added in the same layer.

In addition to the compound-containing layer of the present invention, a subbing layer may be provided for the purpose of improving the adhesion between the layer and the support and for preventing the dye from diffusing toward the support.

[0020] As the support used in the present invention, a transparent plastic film support can be used.
A specific example is RDNo. 32019, page 929 can be used. The thickness of the support is preferably 3 to 200 μm.

Silver halide is preferably added to the silver salt oxidizing agent-containing layer of the image forming material of the present invention for the purpose of increasing the sensitivity of the light-sensitive material. As the silver halide, silver halide prepared in advance may be used, or silver halide prepared by reacting a silver salt oxidizing agent with a halide may be used. As a specific example of silver halide, RDNo.
．． 29963, page 211 can be used.

Silver halide is spectrally sensitized so that it is sensitive to light in the visible to near-infrared region, depending on the exposure method used. Specific examples of spectral sensitizers used for spectral sensitization include RD No. Examples include compounds described in No. 29953.

For the purpose of improving developability and dye transferability, the image forming material of the present invention has RD No. 29963, U.S. Patent No. 4,983,502, U.S. Patent No. 4,770,889,
It is preferable to add the thermal solvents described in JP-A-62-139549 and JP-A-63-53548.

In addition to the above compounds, antifoggants (such as RD No. 29963 and US Pat. No. 4,837,1) may also be used.
Additives such as the compound described in No. 41) are added.

Next, the image forming method of the present invention will be explained.

The light and heat sensitive transfer type image forming material of the present invention (hereinafter referred to as the material of the present invention) is exposed to light in accordance with image information. The exposure light sources used include tungsten lamps, halogen lamps, xenon lamps, CRT light sources,
FO-CRT light sources, light emitting diodes, laser light sources (gas lasers, dye lasers, YAG lasers, semiconductor lasers), etc. can be used, but in order to obtain high-resolution digital images, scanning exposure with a laser light source is recommended. preferable.

The exposed material of the invention is thermally developed to form a silver image. Heat development is usually heated at a temperature of 80 to 150°C for 1 to 120 seconds, but in order to prevent the heat-diffusible dye from diffusing during heat development, heat development is performed at a temperature of 80 to 150°C.
Preferably, it is heated at a temperature of 120° C. for 1 second to 30 seconds.

When the thermally developed heat-diffusible dye-containing layer of the material of the present invention and the image-receiving layer of the image-receiving sheet are overlapped and uniformly exposed to light from the support side of the material of the present invention, the area on which the silver image has been formed is exposed. The heat-diffusible dye-containing layer absorbs light and is heated in accordance with the silver image, and the dye is transferred to the image-receiving layer in accordance with the image information to form an image.

In order to form a full-color image in the present invention, a light and heat sensitive transfer type image forming material having a yellow light and heat sensitive layer containing a heat diffusible yellow dye and a magenta light and heat sensitive layer containing a heat diffusable magenta dye are used. It is sufficient to use a light and heat sensitive transfer type image forming material having a light and heat sensitive transfer type image forming material having a cyan dye and a light and heat sensitive transfer type image forming material having a light and heat sensitive layer containing a cyan dye. A light and heat sensitive transfer type image forming material can be used. Furthermore, a material capable of forming a monochrome image can be obtained by adding three heat-diffusible dyes, yellow, magenta and cyan, to the same light- and heat-sensitive layer.

In the present invention, the yellow, magenta, and cyan heat-transferable dyes may be used as long as they give yellow, magenta, or cyan images during image formation. Included in magenta pigments.

The image-receiving material that can be used in the image formation of the present invention has an image-receiving layer provided on a support. The material constituting the support of the image-receiving material and the image-receiving layer is RD No. 3201
The materials described on page 9,930 can be used. When the aforementioned chelatable dye is used as the dye,
A metal source for donating metal ions to the dye is contained in the image receiving layer. As the metal source, organic or inorganic metal salts and metal complexes can be used, and preferred metal sources include metal complex compounds described in US Pat. No. 4,987,049.

Preferred embodiments of the present invention are as follows.

(1) A layer containing at least a silver salt oxidizing agent, a reducing agent, a binder, and a yellow heat-diffusible dye on the same surface of the support; A light- and heat-sensitive transfer type image-forming material comprising, in plane sequential order, a layer containing a dye, and a layer containing at least a silver salt oxidizing agent, a reducing agent, a binder, and a cyan heat-diffusible dye.

(2) A light- and heat-sensitive transfer image forming material in which the heat-diffusible dye is a black image-forming dye.

(3) A light- and heat-sensitive transfer type image forming material in which a heat-diffusible dye is added in a dispersed state and the binder is a water-soluble polymer.

(4) A light- and heat-sensitive transfer type image forming material having a photosensitive range of red light to near-infrared light.

(5) After imagewise exposing a transfer type image forming material having a layer consisting of a silver salt oxidizing agent, a reducing agent, a binder and a heat diffusive dye on the same side of a support with a laser beam, An image forming method in which a silver image is imagewise formed by heat development, and then overlaid on an image-receiving material and exposed uniformly to image-wise transfer the dye to the image-receiving material.

[0038]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 (Preparation of image forming material) A silver soap dispersion of silver behenate, which is a silver salt oxidizing agent, was prepared according to the method described in the examples on pages 5 and 6 of JP-A-57-158636. Obtained. In addition, near-infrared sensitizing dye IR-1 was used as a sensitizer, and R-1 was used as a reducing agent. The dispersion was applied to a 120 μm thick polyethylene terephthalate film base subbed with gelatin to a wet film thickness of 80 μm to provide a silver salt oxidizer-containing layer. After drying this film, a methyl ethyl ketone solution containing a heat-diffusible dye (dye-1, applied amount = 0.5 g/m2) and polyvinyl butyral (applied amount = 0.5 g/m2) was applied and dried, and the silver salt was oxidized. A heat-diffusible dye-containing layer was coated on top of the agent-containing layer to obtain Image Forming Material-1.

[0040]

[Case 2]

Example 2 (Preparation of image forming material) In Example 1, the silver salt oxidizing agent-containing layer and the heat-diffusible dye-containing layer were separate layers, but the silver salt oxidizing agent of Example 1 By coating a silver salt oxidizing agent dispersion with a heat diffusible dye added to the dispersion (applied amount = 0.5 g/m2), the silver salt oxidizing agent and the heat diffusive dye were contained in the same layer. Image forming material-2 was prepared.

Example-3 (Preparation of image-forming material) Each of the heat-diffusible dyes in image-forming material-2 of Example-2 was
2-6, mixture of dyes-1, 2, 3 and dyes-4, 5,
Image-forming materials-3 to 9 having the same composition as image-forming material-2 except that the mixture of image-forming material-6 was used instead were prepared.

[0043]

[Chemical formula 3]

[0044]

[C4]

Example 4 (Preparation of image forming material) In 50 ml of water in which 5 g of polyvinylpyrrolidone was dissolved (dye-
1) 5 g was added and dispersed in an alumina ball mill to obtain a pigment dispersion. Image forming material 10 was prepared by applying this dispersion liquid onto a layer containing a silver salt oxidizing agent prepared in the same manner as in Example 1 so that the pigmentation amount was 0.5 g/m<2>.

Example 5 (Preparation of image forming material) A benzotriazole silver dispersion was prepared by the method described in Example 1 of ``Dispersion of organic silver and thermal solvent'' of JP-A-3-15052. This dispersion was mixed with a silver iodobromide emulsion (infrared sensitized using near-infrared sensitizing dye IR-1) prepared by the method described in Example 1 of JP-A-3-15052, and a reducing agent (R-1). ), antifoggant (AF-1) was added, and 1 m2 of the image forming material
It was coated on the support used in Example-1 so that the coating amount was as follows.

Silver benzotriazole: 0.8g Polyvinyl butyral: 1.0g Heat solvent (S-1): 0.3g Silver iodobromide: 0.3gAg reducing agent (R-1): 0.8g Antifoggant: 0.08g The dye dispersion prepared in Example 4 was applied onto the above layer so that the amount of dye applied was 0.5g/m2 to obtain an image forming material.
11 was created.

[0048]

[C5]

Example-6 (Preparation of image-forming material) A dye (dye-1) dispersion was added to the benzotriazole silver-containing layer coating solution of Example-5, and the silver salt oxidizing agent and the heat-diffusible dye were dissolved. Image forming material-12 was obtained by coating in the same layer.

Example-7 (Preparation of image-forming material) Image similar to image-forming material-12 except that the dyes in Example-6 were replaced with dyes-2, 3 and a mixture of dyes-1, 2, and 3. Forming materials-13 to 15 were created.

Example 8 (Image Formation) Image forming materials 1 to 15 were exposed to a resolution pattern using an 815 nm infrared laser scanning exposure device. For these exposed image-forming materials, materials 1 to 9 were thermally developed at 120°C for 10 seconds, materials 10 to 15 were thermally developed at 140°C for 15 seconds, and then the image-forming materials were thermally developed. The dye-containing layer and the image-receiving layer surface of the image-receiving material were superimposed and exposed to infrared light from the support side of the image-forming material. On the image-receiving material, depending on the dye used, yellow,
Sharp, high-density magenta, cyan, or black images (
The maximum density of each image (shown in Table 1) was obtained.

The image-receiving material used was a resin-coated paper (RC paper) coated with a polyvinyl chloride layer (thickness: 10 μm). Further, when image forming materials-1 to 4, 8, and 10 to 15 are used, MS-1 (addition amount: 5 g/m
An image receiving material to which 2) was added was used.

Further, when image forming materials 1 to 9 were used, some staining due to the dye was observed in the thermal developing device, but no staining was observed with image forming materials 10 to 15.

Comparative Example 1 An image was formed by heating the image forming material from the support surface with a thermal head using the image forming material of the present invention (only the support was made of a polyethylene terephthalate base with a thickness of 5 μm) and an image receiving material. is formed, but the resolution is inferior to the image obtained by the image forming method of the present invention, and furthermore, in particular, only images of low density can be obtained with image forming materials 10 to 15.

Comparative Example-2 The material prepared in Example-1 was coated with the silver salt oxidizing agent-containing layer on the opposite side to the side on which the silver salt-containing layer was coated. Comparative image forming material coated with a dye-containing layer -
1 was created. Similarly, on the material coated with the silver salt oxidizing agent-containing layer used in Example-5, the dye-containing layer used in Example-5 is coated on the opposite side to the side coated with the silver salt-containing layer. Comparative image forming material-2 was prepared using the following methods.

When an image was formed on the obtained comparative material in the same manner as in Example 8, the image density and resolution were both inferior to the image obtained using the image forming material of the present invention. Note that the maximum density of the image is listed in Table-1.

[0057]
Table-1 Image forming material maximum density Image forming material maximum density
Material-1 1.78
Material-10 1.61
〃 2 1.98
〃 11
1.63 〃 3
1.91 〃 12
1.85 4
1.87 〃
13 1.80 〃
5 1.79
〃 14 1.81
〃 6 1.83
〃 15 1.67
〃 7 1.86
Comparison-1 1.5
7 〃 8 1.
72 〃 2
1.51 9
1.65 That is, according to the present invention, an image with high sharpness and high density can be obtained by a simple method.

Example-9 (Preparation of field-sequential full-color image forming material) Image forming materials-2 and 3 were prepared on the support used in Example-1.
The coating liquid used to create 4.
Image forming material 16 was prepared by repeatedly applying magenta and cyan in the order of surface. Similarly, image forming material-12,
Image forming material-17 was prepared by sequentially applying the coating solution using the coating liquid used in preparing materials Nos. 13 and 14.

Example 10 Image forming materials 16 and 17 were exposed to laser light in accordance with digitized full-color image signals, thermally developed, and overlaid with image-receiving material to heat the entire surface in yellow, magenta, and cyan. A high-resolution, high-density, full-color image was formed. By using an image forming material on which yellow, magenta, and cyan dye-containing layers are applied sequentially, sequential recording is possible using a simple device that has only one imagewise exposure section, one thermal development section, and one entire surface heating section. By doing this, a full color image can be obtained.

[0060]

According to the present invention, it has been possible to provide a light- and heat-sensitive transfer type image-forming material capable of producing high-resolution and clear color images through simple dry processing, and an image-forming method using the same.

Claims (7)

[Claims] 1. A light- and heat-sensitive transfer type image-forming material comprising at least a silver salt oxidizing agent, a reducing agent, a binder, and a heat-diffusible dye on the same surface of a support. 2. A layer containing at least a silver salt oxidizing agent, a reducing agent, a binder, and a yellow heat-diffusible dye on the same surface of the support;
2. The light-sensitive and heat-sensitive transfer image according to claim 1, further comprising a layer having a magenta heat-diffusible dye, and a layer having at least a silver salt oxidizing agent, a reducing agent, a binder, and a cyan heat-diffusible dye in plane order. Forming material. 3. The light- and heat-sensitive transfer type image forming material according to claim 1, wherein the heat-diffusible dye is a black image-forming dye. 4. The light- and heat-sensitive transfer image forming material according to claim 2, wherein the heat-diffusible dye is added in a dispersed state and the binder is a water-soluble polymer. 5. The light- and heat-sensitive transfer type image forming material according to claim 1, wherein the photosensitive region is from red light to near-infrared light. 6. A light-sensitive and heat-sensitive transfer image forming material having a layer consisting of at least a silver salt oxidizing agent, a reducing agent, a binder and a heat-diffusible dye on the same side of a support is subjected to imagewise exposure and then thermal development. An image forming method in which a silver image is formed in an image-wise manner by applying a silver image, and then the dye is image-wise transferred to the image-receiving material by overlapping it with an image-receiving material and exposing it uniformly to light. 7. The image forming method according to claim 6, wherein the light source for imagewise exposing the light- and heat-sensitive transfer type image-forming material is a laser beam.