JPS59159398A - Thermal transfer image-forming method - Google Patents

Abstract

PURPOSE:To obtain an image-forming method simple in operation, favorable in image quality and excellent from the viewpoint of environmental problems, by a method wherein a sublimable coloring matter is produced in a hydrophilic binder on a base by a silver halide coupler-in-type color developing method, and the coloring matter is transferred by a thermal pattern. CONSTITUTION:A photosensitive material comprising an undercoat layer 2 and a silver halide emulsion layer 3 provided on a base 1 is exposed to light 5 imagewise in a mosaic pattern through a photo-mask 4 for the first color, e.g., cyan color, followed by a coupler-in-type color developing treatment to produce a cyan pattern 5a. Similarly, the second and third patterns 5b, 5c are produced by using photo-masks 4, and the film is deprived of silver by a bleach fixing step. An image-receiving sheet is brought into contact with the thus obtained coloring matter doner sheet, and is exposed imagewise to multicolor spectral light containing the absorption wavelength of the coloring matter doner layer 3 through an original by a number of times corresponding to the kinds of mosaic picture elements to produce a thermal pattern, thereby producing a multicolor image.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer image forming method, and particularly to a method of transferring and recording a sublimable dye by heating.

(Prior art) In recent years, in response to the desire to easily obtain color prints from CRTs or their electrical signals in various computer terminals such as medical equipment and industrial equipment, electrophotographic methods, thermal methods, and thermal transfer methods have been developed. Various hard copy methods have been proposed, such as the ink side method, and some have been put into practical use.

However, none of these methods can convert light into light, and the method using @salt is superior to other methods in this respect. However, on the other hand, silver salt requires a complicated processing process, and is one step ahead of other methods in this respect. Therefore, there is a need for an image forming method that can produce color hard copies through simple processing while making full use of the characteristics of quince salt, and among these, a method using a heat-developable photosensitive material is attracting attention.

Regarding heat-developable photosensitive materials, for example, Japanese Patent Publication No. 43-492
No. 1 and No. 443-4924, etc., disclose photosensitive materials comprising an organic silver background, silver halide, and a reducing agent. These heat-developable photosensitive materials are exposed to light to form a latent image on silver halide, and this latent image is used as a catalyst nucleus to perform a redox reaction using an organic silver base and a reducing agent during heating.
A silver image is obtained by a so-called dry physical development process.

Furthermore, many attempts have been made to erase a single color image by thermal development. For example, U.S. Patent No. 3.5
31. ．． No. 286, No. 3,761,270, No. 3,
764; As described in No. 32B, Y (yellow) is produced by cambling with the oxidized product of the Touka family amine thread developing agent and this oxidized product.
, M (magenta), C (cyan), etc., using couplers that can form dyes.

Furthermore, as a color development type similar to 1, Research Disclosure (hereinafter abbreviated as RD) 1214G+5
, No. 1508, No. 15127, JP-A-56-271
No. 32 etc. cannot be mentioned either. Also, U.S. Patent No. 3,985,56
No. 5'', July 4,022, 617, RD No. 12533 Chi-, method using leuco dye, JP-A-52
A method using the SDB method described in RD No. 105821 and No. 52-105822, etc., a method in which the dye is bleached with a reducing agent in the unexposed area as described in RD No. 15676, etc.
There are various methods, such as RDI5126 S and RDI No. 17706, which are themselves reducing agents and are decolored in the exposed area. In the case of full-color heat-transferred photolithography, the stability of photosensitive control is poor, and the color tA+ that can be obtained is limited. Furthermore, since there is no method for fixing color images, no method that is fully satisfactory has yet been found.

On the other hand, as another method, a system as described in US Pat. No. 3,767,394 has been proposed. The dough consists of three sheets coated with a sublimable dye having a color tone complementary to the sensitivity - one layer of dry silver on both sides (till) of a transparent support (for example, a film base). 1-, 3 sheets with yellow sublimable dye applied to the back side of one layer of regular dry silver, magenta sublimable dye applied to the front side of one layer of ortho dry silver, and cyan sublimable dye applied to the back side of one layer of panchromatic dry silver. The sheets are stacked in the order of regular sheet, ortho sheet, and panchromatic sheet when viewed from the exposure side, and exposed through the color original from the regular layer side.

After exposure, thermal development was performed and 7.3 sheets were separated into 1. The image-receiving layer and the sublimable dye surface are overlapped, and irradiated with infrared rays etc. 1
．． , the sublimable dye is transferred to the image-receiving layer by generating heat in the silver image area. By carrying out thermal transfer using infrared irradiation on each of the Y and MXC sheets by superimposing them on the image receiving layer three times, a full color print can be obtained. This method has the advantage that it is possible to use only a normal monochrome thermal image-sensitive material as a heat-developable photosensitive material, and that it is extremely academic and pure because it only uses sublimable dyes for hue. It has certain characteristics, such as having a certain composition.

However, the image-receiving layer is YX! Since the process of superimposing the ViX C images three times is involved, it has the disadvantage that it is difficult to align the three colors, and the images become sloppy.

” - In order to solve the drawbacks mentioned above, the present inventor filed a patent application in 1983-1.
No. 86142, after exposing an imaging element consisting of a mosaic filter layer containing a thermally transferable dye or dye-providing substance and a light-absorbing image-forming photosensitive layer, if said photosensitive layer is a silver halide photosensitive layer, After developing and fixing the layer, or in the case of a thermal or stretchable photosensitive layer, after thermally developing the layer at a temperature below the thermal transfer/transfer temperature of the thermally transferable dye or dye-providing substance, a layer containing a thermally transferable dye 5- Infrared light on the mosaic filter surface and image-receiving layer?
1) An image forming element was proposed in which a heat transferable dye or a dye-providing substance is transferred to an image-receiving layer by uniform irradiation with high-intensity light or the like and heat generated in an image area.

The dye or dye-donor substance in this proposal is preferably a sublimable substance, but as a specific number for making a layer of a mosaic filter that holds the dye, etc., it is necessary to prepare it in advance in a binder such as gelatin. An example of this method is to finely disperse pigments, etc. using ball mills, sand mills, ultrasonic dispersion, etc.
After adding potassium chromate, apply pattern fog light using ultraviolet rays, wash off with water except for the photo-cured areas, and apply a dichromate gelatin layer with another pigment dispersed with a ladle. 7.1st time The areas other than the areas photocured by exposure and development are exposed to pattern light again and developed. Furthermore, if necessary, repeating the same operation for the third color and subsequent colors provides a method of obtaining a mosaic 77, a perfectly uniform pattern layer of thermally transferable dyes.

However, this manufacturing method has drawbacks such as it takes a long time to disperse the sublimable dye, and the dispersed particle size is also very large, making it difficult to obtain uniform dispersion. Also, dichromic acid
It is harmful to the human body and there is room for improvement in the punishment.

(Objective of the Invention) The object of the present invention is to solve the above-mentioned problems, and the first object is to improve image quality with ease of operation and greatly reduce environmental problems.
An object of the present invention is to provide a method for forming an image. The second object is to provide a thermal transfer photosensitive material which has good image sharpness in terms of image quality that satisfies the above-mentioned purpose, and therefore has improved resolution as well, and which does not cause any labor health or pollution problems.

(Structure of the Invention) The object of the present invention is to form a sublimable dye by an imaging method using a color-developing method outside silver halide in a hydrophilic binder provided on a support, and to receive an image of the sublimable dye by a thermal pattern. This can be accomplished by a thermal transfer imaging method that transfers the image to a layer.

That is, in the image forming process of the thermal transfer image forming method of the present invention, a sublimable dye or a dye-donating sublimable substance (hereinafter referred to as both at once) is added to a hydrophilic binder layer provided on a support by silver halide external coloring or 91 imaging method. A single layer of a hydrophilic binder that forms and contains a sublimable dye (referred to as a sublimable dye), that is, a dye-providing layer for thermal transfer (
The dye-donating layer surface (sublimation transfer surface) of a thermal transfer dye-donating sheet (hereinafter simply referred to as dye-donating sheet) having a dye-donating layer (hereinafter simply referred to as dye-donating layer) and the image-receiving layer surface are brought into contact with each other, and the dye-donating layer is imagewise exposed according to the original image. The sublimable dye is heated by a thermal pattern having a temperature distribution corresponding to the nuclear image-like exposure when the dye is applied, and is transferred to the image-receiving layer to create an image.

The feature of the present invention is that the sublimable dye contained in the MfJ dye-donating layer is formed by an external color development method using silver halide, and therefore the formed sublimable dye grains are extremely fine and have a particle size. Because they are distributed in a hydrophilic binder with a uniform density of 1 to 1, they have good sublimation response to temperature, so the development method IW is fast, and the image quality produced is high, with high sharpness and resolution. Improved.

The image-receiving layer may be integrally provided on the dye-donating sheet via a light-blocking layer and a reflective layer. Two or more types of sublimable dyes are individually photographed in the form of a mosaic or stripe to form a pattern (hereinafter collectively referred to as a mosaic pattern), and the dye-donating layer present in a single layer of a hydrophilic binder is formed. Examples of uses include: Such embodiments are suitable for producing multicolor images.

Furthermore, the effects of the present invention can be improved by providing a structure that separates and reinforces the function of the dye-donating layer. For example, in order to select colored light from an original image, a mosaic filter made of non-sublimable dye is provided using a silver halide photosensitive material, and colors and positions are matched to the mosaic filter according to negative-positive or positive-positive drawing. 9 By forming a two-layer structure with a mosaic sublimable dye layer containing a sublimable dye, or by taking the same consideration as above.
By mixing a non-sublimable dye that functions as a filter and a sublimable dye that matches the color and position of the dye in the same area, color separation accuracy, ease of operation, and reliability are achieved. In addition, a thermal pattern generating layer that supports an image-like pattern of a heat absorbing medium such as black silver can be created using a heat-developable photosensitive material, etc. Separating the thermal pattern function by providing
The reinforcement can increase the thermal transfer efficiency (development speed and development strength) of the sublimable dye. Furthermore, in the case where a thermal pattern generation layer is provided and a separate image-receiving sheet is used, simply by repeatedly bringing the dye-donating sheet and the image-receiving sheet into contact with each other and heating, the sublimable dye can be applied to the range where it exists in the dye-donating layer. You can make multiple copies.

In the present invention, the thermal pattern for thermally transferring the sublimable dye contained in the dye-donating layer to the image-receiving layer is a process in which the light energy of imagewise exposure from the original image is transferred with the dye-donating layer and the image-receiving layer in contact with each other. By absorbing it into the dye-donating layer, a high-low temperature distribution in the dye-donating layer is generated.

When creating a multicolor image, select one of the number of dye-donor sheets corresponding to the number of colors, bring the dye-donor layer of the dye-donor sheet into contact with the image-receiving layer of the image-receiver sheet, and pass the original image through. The sublimable dye contained in the dye-donating layer is thermally transferred to the image-receiving layer of an image-receiving sheet by fully exposing the dye-donor layer to multicolor separated light or white light that includes the absorption wavelength, and then the dye-donor sheet is transferred to another dye-donor sheet. The multicolor image can be changed by replacing the two sheets with each other, aligning the image positions, and performing thermal transfer by overlapping them in the same manner as above, and repeating this operation by the number of dye-providing sheets.

When the thermal pattern generation layer is provided in the dye donor layer, imagewise exposure is performed with light having a wavelength in the photosensitive region of the thermal pattern generation layer 1 to form the imagewise pattern of the thermal storage medium. After forming the layer, fixing and removing unnecessary photosensitive components of the thermal pattern generating layer if necessary, and drying, aligning the image position with the image receiving layer and contacting it, heating 1 to transfer the sublimable dye. The above operations are repeated to create a multicolor image.

In the case of using a dye-donating JWI in which a mosaic pattern is formed of two or more p-sublimable dyes mentioned as a preferred embodiment of the present invention, the dye-donating layer and the above-mentioned separately provided on the receiver 1 bed sheet are used. Ukei'8! A wave surface area that is absorbed by a mosaic surface element containing two or more types of chromatic color systems in a state in which it is in contact with an image-receiving layer provided integrally with a color donor sheet or a dye-donor sheet. A thermal pattern is generated by exposing an image to people a number of times corresponding to the type of mosaic surface element by the light decomposed into the mosaic, or if it has a thermal pattern generation layer, an image-like pattern of a thermal storage medium is formed. Multicolor images can be created by heating.

Furthermore, by adding a filter function in the dye-donor layer that matches the color and position of the mosaic pattern, the imagewise exposure to generate the thermal pattern only needs to be done once with white light, making it extremely easy to operate. It is simple and reliable, and the tA In- of color separation can be improved by 1 or more.

Exposure used for generating a thermal pattern or forming a heat absorbing medium pattern according to the present invention - 1 scanning exposure, contact exposure, projection exposure, etc. can be used arbitrarily, and each glaze is Laser light source, strobe,
Light sources commonly used in photography, such as a tungsten incandescent lamp, a halogen lamp, or an LED, can be used. A filter is also used if necessary.

The heat storage medium formed in the thermal pattern generation layer provided in the dye donor layer can be heated by a method using heat conduction such as light or infrared radiation from the light source described above, thermal panel compression bonding, hot air blowing, etc. .

Next, the present invention will be explained in detail and specifically.

The present inventors discovered that the crystals formed in the protective colloid are extremely fine, have a practically uniform particle size, and are uniformly dispersed. By borrowing a black-and-white silver halide light-sensitive material or an external color halide light-sensitive material and subjecting it to an external color development method according to a known method, the number of man-hours required for finely pulverizing the dye, etc., can be reduced. I would like to be freed from the laborious process involved in mosaic pattern formation, industrial health and environmental problems caused by chromic acid, etc. all at once.

The dye-providing sheet according to the present invention is prepared by applying a predetermined exposure to a black and white halogen-based photosensitive material described in 7 above, and then applying a desired color using a molecular plate. (a) Since it is relatively small and non-polar, it can be easily formed by external color development using a combination of a coupler that produces a sequential dye, a color-forming type, and an image-based type.

Next, a dye-donor sheet comprising a mosaic pattern of two or more sublimable dyes, which is preferably used in the present invention, will be described.

The sheet is prepared by exposing at least one silver halide emulsion layer on a support, and exposing the emulsion layer for each photosensitive state to a mosaic pattern of a first color, and then exposing it to a second color using a second color-developing image.
A mosaic pattern consisting of a colored pigment and silver is formed, and then a mosaic pattern of a second color is exposed on the unexposed area containing silver halide, and external color development is performed. Form a mosaic pattern, and then repeat the same process to form a mosaic pattern consisting of a third or subsequent color dye and silver if necessary. L7: Final color development process. A dye-donating layer can be formed and created by performing a desilvering treatment later. In the formation of the dye-donating layer, after at least one color development step other than the final color development step, color development is performed by adding a black and white treatment, a white color bleaching treatment, etc. It's so bright.

Hereinafter, with reference to the drawings, the dye-bearing sheet B for producing a mosaic pattern according to the present invention will be explained in detail. If desired, an undercoat layer 2 is provided on the second layer of 1, and a silver halide emulsion layer 3 is provided on top of the undercoat layer 2. This photosensitive material is passed through a photomask 4 as shown in FIG. 2, and image exposure 5 is performed at L7 to form a mosaic pattern of, for example, cyan, which corresponds to the first color of the dye to be used in multiple colors. The light source used in this process is white light, as long as it emits light at a wavelength to which the silver oxide emulsion layer is sensitive. For example, when such a photosensitive dye 3 is developed with an external photochromic developer containing a cyan coupler, a pattern 5a consisting primarily of cyan dye and iron particles is formed.

5 a, etc. are formed. After the first development is completed, 'Ir'
Shunshu photosensitive materials are washed with water and dried in the event of a pitched battle. Next, using the same photomask 4, a magenta color pattern 5b is applied as a second color.
, 5b', etc. are formed next to the cyan patterns 5a, 5a', etc. (FIG. 3). Furthermore, by performing the same operation using a similar photomask 4 and using a yellow color developing solution, yellow patterns 5c, 5e', etc. are formed between the magenta and cyan patterns 5a', 5b, etc.

(FIG. 4) Further, the film having the mosaic pattern of these dyes is then subjected to a bleaching and aging process to be desilvered.

The external color developing solution used in the present invention is a compound whose oxidation product reacts with a coupler to form a coloring dye, that is, a color developing agent such as N,N-diethyl-p-phenylene-
Diamine, 3-Mef-4-amino-N, N-diethylaniline, N', N-dimethyl-p-phenylenediamine, 3-methoxy-4-amino-N, N-diethylaniline, 3-methoxy-4- Amino-N, N-dimethylaniline, 3-methyl-4-amino-N-ethyl-N
=methoxyethylaniline, 3-methyl-4-amino-
An alkaline aqueous solution such as N,N-dimethylaniline,
The aqueous alkali solution containing gold couplers of various colors, which will be described later, is used. In addition, salts such as sodium sulfate, pH regulators and buffers such as sodium hydroxide, sodium carbonate, and sodium phosphate, and ordinary antifoggants such as alkali halides such as potassium bromide are usually added to this aqueous channel. This is what is being done.

The developing agents that are advantageously used in the present invention are typically those mentioned above, but they have a relatively small molecular weight of 25
0 or less] and does not have a polar group, a sublimable coloring dye is obtained.

17- Also, as a coupler, U.S. Patent No. 3,510
, 306-Gin, No. 3.619, 189, Tokuko Sho 4
Yellow coupler described in No. 0-33775, No. 44-3664 ij, etc., German Patent Publication (OLS) No. 2
,016,587, U.S. Bamboo It No. 3.152.896
No., 1 unit 1 No. 3,615,502-1 Special Public [11j 4
Mabinta coupler U.S. version W described in No. 4-13111 etc.
t No. 3,002,836, t No. 3,542,552, UK IX! There is a cyan coupler described in Il Ship/Kitsuki No. 1,062,190, etc., or even these have a small specific molecular weight (preferably 300 or less, 1 [-2 is small, matasulfo group, carboxy group, etc.) 1J of polar groups such as quaternary tsumino groups
”, the coupler without is M00. (iii l.

Groups such as those used in the color development process, for example, t at the active site of the coupler.
i+-substituted sulfo groups, etc. may be omitted.C
- Typical kabukus that can be used once a month in the present invention include the following, but are not limited to kabuku.

12-Acetoacetoanidicito2 A7toacetoarbright 32-ben'Soylacedoanidicito4 Benzoylacedoanilide 5, Pivaloylacedoanilide 6.1-Phenyl-3-methylpyrazolone 7 α- Cyanoacetophenone 8, 1-(4-chlorophenyl)-3-methylpyrazolone 9 1-phenyl-3-methoxypyrazolone 10
, 1-(2,4,6-4licro'Jphenyl)-3
-Methyl-Hirazolone 112-Chlorphenol 122.6-Dichlorophenol 13 Phenol 14. 2.4--Dichloronaphthol 15, 2.4-dibromnaphthol 16, α-Nandol 17.4--Sulfo-1 -Naphthol 18.2-Methoxyphenol 19, α~(0-,methoxybenzoyl)acetanilide 20 α-(0-methoxybenzoyl)acetanilide 21, α-(p-chlorobenzoyl)acetanilide 22, α-(4-chlor -benzoyl)
Acetanilide 23, 2,5-dichlorophenol 24, 2-cyanoacetylbenzofuran 25, α-
cyanoacedoanilide 26, α-cyanoacetophenone 27.3-phenylisoxazol-5-one fat,
5-Chlorocoumaran-3-one 29,2-7 Nilino-4-phenylthiazole Also, all the bleaching solutions used in ordinary color photographic processing can be applied to the silver processing used in this process. That is, potassium ferricyanide and iron-EDTA are used as oxidizing agents.
For example, potassium bromide is added for halogenation.

The fixing agent for silver halide is any well-known silver halide solvent (e.g., sodium thiomimetic acid, sodium thiocyanate), and the solution containing the fixing agent may be optionally mixed with a preservative (e.g., sodium sulfite). , a pFI buffer (eg, boric acid), a pH adjuster (eg, acetic acid), and a chelating agent layer.

As one of the desilvering treatments mentioned above, a one-bath bleach-fix solution, such as a mixture of red blood salt and butyric sodium thiosulfate or P,'
It is also possible to use a mixed bath solution of DTA-Fe(III) and Naosulfuric acid (IJ).

In the explanation of the previous i-th item, the mosaic surface elements of each color were written so as to be in close contact with each other, but it goes without saying that a mosaic dye-donating layer may be formed in which the mosaic surface elements are not in close contact with each other. Further, when using, for example, a stripe pattern of the same width as a mosaic pattern, the same photomask 4 shown in FIG. 2 can be used, and the color-containing patterns can be sequentially exposed while shifting the positions.

As is clear from the above description, the mosaic dye-donating layer 1l-j according to the present invention is a fine-grain black-and-white silver halide photosensitive material, so the width of the mosaic surface element can be easily reduced to 1 μm, and the precision is extremely high. The high mosaic pattern can be changed.

In the external color development, the development speed is generally slow, and the progress of development slows down as the development time increases, and the development soon reaches saturation. It is flexible to saturate the development by performing 30 to 40 minutes of development at 21-49 degrees in the development process for each color, but the overall processing time is significantly longer in order to process multiple colors. Become. Therefore, in order to shorten the development time of the first color development step, the development time for the first color, for example, cyan, is stopped after 15 minutes and the development time for the second color, for example, magenta, is stopped at 15 minutes. During development, magenta dye is also generated in the first exposed area (region 5a in FIGS. 2 to 4), which should originally contain only cyan dye, resulting in the cyan pattern becoming a mixture of magenta. Although such color mixing is rather effective in special cases as will be described later, it is generally undesirable, so it is preferable to stop the development of the first color after 15 minutes, for example, and then perform rapid black-and-white development. As a result, the latent image remaining in the color development process of the first color is developed by the quick black and white developer within a short time (for example, about 5 minutes at most), so it is easily saturated and the exposed area is no longer covered with scissors. Not generated. That is, color development will substantially no longer proceed in this area. Therefore, the 22-magenta dye and yellow dye of the second and third colors in the subsequent process are not generated in the first color pattern, so that no color mixture occurs in the first color pattern. When forming a second color or a pattern with more than the surrounding area, color development of the second color [1 and above (such processing is unsatisfactory as there is no risk of color mixing in the final pattern formed) is performed. After that, by repeating the same process, the pattern obtained will have no color mixture.

A mosaic dye-donor layer arranged in a uniform manner is formed.

It is important that the black and white developer used in this embodiment has a characteristic that its development speed is at least faster than that of the color developer, and the developer used is generally one well known in the art. Examples include hydroquinone, pyrogallol, 1-phenyl-3-pyrazolidone, p-aminephenol, and ascorbic acid. The developing solution may contain alkali scrapers (e.g., hydroxide, sodium carbonate), pH adjusting or buffering agents (e.g., acetic acid, boric acid), anti-capri agents (e.g., potassium bromide), preservatives (e.g., sulfite). Known compounds and compositions such as sodium) can be added. Furthermore, rapid developing image or high contrast developing solutions known in the field of photography are most preferred for such purposes. A quick developer or a high-contrast developer is described, for example, in "Science Photography Handbook (Medium)" new edition, published by Himaruzen Co., Ltd. on December 20, 1950, pages 126 and 127.

Using the shady latent image cool white method, the first color pattern is developed (for example, red) to destroy the latent image, and then the second color pattern is partially overlapped with the first color pattern and 7 7. Then, the second color pattern is developed to develop (for example, green), and the parts of the first color pattern and the second color pattern are exposed to red, green, and blue light. Since the color is also opaque, a so-called black stripe can be formed between the pattern of the first color and the pattern of the second color. Also, by performing the same process between the second color pattern and the second color pattern (for example, blue), a mosaic dye-donating layer with a preferable plaque stripe in which the inside of each color pattern is partitioned with black can be obtained. can be obtained. However, it is not impossible to say that such black stripes can also be achieved by providing black patterns between these patterns in the same way as forming patterns of each color.

In the above explanation, the first developer is cyan or red developer, the second developer is magenta or green paddy, 1 home fluid is used, and the second developer is ±114 body fluid (yellow) or blue di).
-4 developing solutions were used, but the order of these developments is arbitrary; Of course, that's a good thing.

In addition, two or more couplers may be present in one developer to obtain a desired color tone.For example, a portion where a yellow dye has been formed may be bleached again with silver and exposed again to form a magenta dye. It is also conceivable to use a red dye-donor layer as a surface element.

Also, among these dyes, for example, yellow dye, 25-
Take one sublimable dye, use the other magenta dye as a non-sublimable color chip, and use L2 to form a cyan dye and a sublimable magenta dye on the other surface element in the same way, and then use the remaining →- surface element as A dye-donor layer containing a yellow dye and a sublimable cyan dye is formed.

In addition, the method of the present invention involves generating mosaic filters in advance according to the method described in Section 111, and placing 7 sections corresponding to each filter on the mosaic filters. It is possible to form sublimable dyes.

The details will be explained below with reference to the drawings.

FIG. 5 is a schematic diagram showing a single layer 6 of a polysaccharide filter formed on the support 1. As shown in FIG. FIG. 6 shows a portion where a panchromatically sensitized silver halide emulsion layer 7 is provided. Figure 7 shows the support (from lull) to this.
1- Exposure to 1-light is the shield. Then, P''i1 was color-developed using a color developer to form a mosaic surface element 7a containing a sublimable magenta dye. (Developed with a developer to saturate the development.) Next, the whole blood was exposed to clean light, and then the cyan sublimable dye was formed to form pairs j to 7b, and then the entire surface was exposed to red light, and then the yellow sublimable dye was formed. On the other hand, 7C was formed in the same manner and then subjected to bleach-fixing treatment.As a result, a sublimable dye pattern corresponding to the mosaic filter 17 was obtained as shown in FIG.

The dye-donating layer thus obtained can be prepared by a heat-sensitive transfer method using a heat-sensitive head, by a heat-mode dye transfer method using a laser, or by a photo-zer mogshifi method as described in Japanese Patent Application No. 186-142-1982. [7] Advantageously, an image forming method using a dye donor layer having a mosaic of sublimable dyes can be used.

The silver halides of the photosensitive f1 halogenated emulsion used as analogues of the dye-donating layer or mosaic filter layer related to the present invention include chloride tablets, silver bromide, iodide salts, chlorobromide salts,
It contains silver chloroiodide, silver iodobromide, silver chloroiodobromide, or a mixture thereof. The photosensitive silver halide can be prepared by any method known in the photographic art, such as a single jet method or a double jet method, but in particular in the present invention, a silver halide gelatin emulsion is prepared. Photosensitive norogenated emulsions prepared according to the comprehensive procedure yield favorable results.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Examples of such sensitization methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned light-sensitive emulsion may have coarse or fine grains, but the preferred grain size is from about 1.5 μ to about 00 μ, more preferably from i to about 00 μ. It is about 0.5μ to about 0.01μ.

Typical spectral sensitizing dyes for silver halide include cyanine, merocyanine, complex (3
Examples include 4-nucleated) cyanine, holopolar cyanine, styryl, hemicyanine, and oginnol.

The amount of these dyes to be added is 1 (1' mol - 1 mol) per 1 mol of silver saponide or halide-forming component, preferably from 10 -4 mol to 10 -1 mol.

The heat-developable photosensitive material preferably used for the thermally patterned X-enhanced layer can be obtained by mixing the above-mentioned photosensitive material, a halogenated compound, and a photosensitive organic silver salt.

These photosensitive +! 1 Silver halide and a photosensitive organic silver background-forming component can be used in combination in the divine method, and the amount used is 0.001 to 5.0 mol per 1 mol of the organic silver salt. 001 to 0.3 mol. The coating range of the organic silver salt is 0.05 to 10. (1, good luck 0.2
~2. It is Ov.

Further, as the photosensitive organic silver salt used in the heat-developable photosensitive material related to the present invention, aliphatic or aromatic carboxylic acid, a silver base having an imino group, a silver salt having a merkaft group or a thione group, etc. The spectral sensitizing dye for the above l-thermally developable photosensitive material and 1
-7 is a merocyanine dye having a rhodanine nucleus, a thiohydantoin 129- or 2-thio-2,4-oxazolidinedione nucleus, a thibarbyl acid nucleus or a long chain-
A merocyanine dye having an alkyl group of 1 or a polynuclear merocyanine dye can be used.

The reducing agents used in the heat-developable photosensitive material include phenols, sulfonamide phenols, polyhydroxybenzenes, naphthols, hydroxybinaphthyls, methylene bisnaphthols, methylene bisphenols, ascorbic acids, Included are 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

Two or more of these reducing agents may be used in combination. The amount used is usually 1 to 0.05 to 10 mol, preferably 0.1 to 3 mol, per 1 mol of the organic silver salt.

Furthermore, various additives may be added to the heat-developable photosensitive material as required. Examples include development accelerators, color toning agents, antifoggants, stabilizers, printout inhibitors, heat antifoggants, antihalation agents, tsJ plasticizers, spreading agents, and film agents.

Although it is possible to use the above-mentioned pl (& light 4'l-halogenated scissors, photosensitive old needles and heat development 3), the binder of the photosensitive month and the binder of the gods of I7, it is possible to use the binder of the QJ, but what is a suitable binder? - For hydrophilic, heat-developable photosensitive systems, more hydrophobic binders can be used depending on the purpose.For example, gelatin, gelatin derivatives, white members, cellulose derivatives, dextran, etc. natural materials such as polysancharide, gum arahia, etc., synthetic polymers such as polyvinyl alcohol, polybyrrolidone, water-bathable polyvinyl acetal, etc., and to increase the dimensional stability of photographic materials. Radical vinyl compounds and other synthetic polymers may also be included.

Various papers and film bases can be used as the image-receiving sheet according to the present invention, including baryta paper, art paper, Aibo IJ paper, and paper supports with various overcoat grainers, and may be overcoated with a mordant layer containing various mordants, a layer containing a chelate-forming substance, a complex, etc.

Alternatively, the image-receiving layer and the dye-providing layer may be coated on the same support, forming an integral structure. If there is a battle, the color-donor layer may then include an opacifying layer, which provides the desired amount of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. It is used to reflect. The opacifying layer can contain various reagents to provide the necessary reflection, such as titanium dioxide.

(Example) Next, the present invention relates to mFl more specifically using Examples.

Example-1 Gelatin 50f and silver iodobromide 642 (particle size 0.06 μm
A silver halide emulsion containing iodine (2%) was deposited to a thickness of 30 μm.
It was coated and dried on a polyethylene terephthalate base that had been undercoated to a dry film thickness of 37° C.m. This photosensitive material has a width of 42 μm and a pitch of 1
A striped filter mask made using a 25 μm printing plate film was closely attached and exposed to white (tungsten lamp) light, followed by development with a cyan color developing solution having the following composition. (24°C 1o min) Cyan color developer N, N-diethyl-p-phenylenediamine mR salt
3r Sodium sulfite 5
? Sodium carbonate 60
f Potassium bromide 21 Add water to make 1 t. To this, add 50 d of methanol in which 2-chlorophenol from 14 was dissolved.

After washing with water for 5 minutes, it was developed with a developer having the following composition (24° C., 5 minutes) to saturate the development of the exposed area and prevent further development.

Developer 1-phenyl-3-pyrazolidone 0.52
Sodium sulfite (anhydrous) 5o1 Hydroquinone 12 Sodium carbonate (monohydrate) 6o2 Potassium bromide 22
Benztriazole 0.2
S'1-phenyl-5-mercaptotetrazole 5
〃3-Phenazine-2-carboxylic acid 1y Add water to make 1t.

Next, it was soaked in a stop solution having the composition shown below for 2 minutes, washed with water for 5 minutes, and then dried. In this way, patterns 1 to 1 of mixing cyan dye and silver were obtained.

Stop solution glacial acetic acid 1(-) m
1 Sodium sulfate 452 Add water to make 1 t.

Next, using the stripe filter mask, the transparent part of the mask was aligned so that it was right next to the cyan pattern, exposed as before, and then developed with a magenta color developer with the following composition (24°C 10fi).

Magenta color developer Sodium sulfite 5v Diethyl-p-phenylenediamine hydrochloride 3y Sodium carbonate 6() Potassium dibromide
22 Add water to make 1 t, and then add 1-phenyl-3-methyl-5-pyrazolone 1'/ dissolved in 50 ml of methanol.

After washing with water for 5 minutes, the film was developed with a ml black and white developer to saturate the development of the exposed area (24° C., 5 minutes).

After cyan development was stopped, the film was washed with water for 5 minutes and dried. Thus a magenta stripe was obtained next to a cyan stripe.

Next, in the same manner, using the above Strise filter mask, the transparent part of the mask was positioned next to the magenta pattern, and it was exposed to light at 1~ and developed with a yellow color developing solution having a composition below (24°C for 10 minutes). ).

Yellow color developer sodium sulfite 5? Diethyl-p-phenylenediamine hydrochloride 3y Sodium carbonate 60F Potassium bromide
22 Add water to make ]t.

Is this 0-acetoacedoanidicyto1'? 50fnl
Dissolve in methanol and add.

After washing with water for 3 minutes, it was immersed in a bleaching solution of the following composition for 2 minutes, washed with water for 1 minute, and treated with a fixing solution of the following composition (20° C. for 2 minutes).

Bleach solution Potassium ferricyanide 100 Potassium bromide 30 r Water
1o
oo y fixer sodium thiosulfate 240v*mm
Storium 3v Glacial acetic acid 5-potassium alum 6v Water
1000. ,,
f.

After washing with water for 5 minutes and drying, a striped pattern of cyan, magenta, and yellow sublimable dyes with no visible color mixing was obtained.

Next, the stripe pattern and the image receiving sheet were tied together with art paper, and from the base side, a 50 mW helium neon laser (NEC 5800) was focused to a beam spot of 20 μm and scanned at a speed of 25 tyn/sec. When the paper was pulled apart, a cyan line was transferred along the top of the scan line.

Then, in the same manner, 5 tn
A magenta line was visible on the art paper when I scanned it with /BeQ's scanning speed box. Then 100. ,
mW He-Cd laser (manufactured by Shauchi Denki; CD 4
(102R) at a speed of 25 cm/sec, it was confirmed that a yellow line was transferred.

Example-2 The pitch was 1001 by the method described in U.S. Patent Publication No. 3,284,208! Stripe filters each having a filter line width of 33 μm for blue, green, and red colors were formed on polyethylene V terephthalate (FIG. 5). Next, a panchromatically sensitized silver iodobromide gelatin emulsion (grain size: 006 μm, 2 molt of chloride, containing 649 silver iodobromide and 502 gelatin) was deposited on this filter to a dry film thickness of 3 μm as shown in FIG. I applied it to make it look like this. This photosensitive material was exposed to blue light over the entire surface from the base side [Developed for 10 minutes at 24°C with the same magenta developer as in Example 7. After washing with water for 5 minutes, the exposed area was developed with the above black and white developer and further incubated at 24°C for 5 minutes.
After that, I made sure that the second development did not proceed. Next, the same stopping water washing and drying as in Example 37-1 was performed. Next, the whole image was exposed with green light from the back side of the palm. 1. Developed at 24°C for 10 minutes with a developing solution of Example-1 and Cyan. After washing with water for 5 minutes,
Developed for 5 minutes at 24°C with the same black and white developer.
I was able to play 9 o 11.

Then, it was stopped, washed with water, and then dried.

Next, the entire surface was exposed to red light, and developed with the same yellow outer color developer 1y as in Example 1 for 10 minutes at 24°C. After washing with water for 3 minutes, After washing with water for 5 minutes and drying, the magenta, cyan, and yellow pigments corresponding to the blue, green, and red stripe filters shown in Figure 9 were uniformly dispersed in very small amounts. A pattern was obtained.

Next, a heat-developable photosensitive layer was applied to the above stripe filter using the following recipe =+~/ζ-0, first, Penztriaseal silver 1], 4? Alcohol 200m/
! , 8 polyvinyl butyral aqueous solution (Niletsuku W2O1, manufactured by Block Chemical Co., Ltd.) 250 III/! was added and dispersed in a ball mill for 24 hours to prepare a dispersion liquid. Next 3
8- Panchromatic iodobromation while stirring this dispersion☆
1. ! Emulsion (Iodide Frog 5M Emulsion I K9A containing 60? of gelatin and JTLO, 353M), average grain size 0.
13 mJ of cubic emulsion 0.06 pm was added. (This silver iodobromide emulsion contains 5-(
3-Methylbenzthiazolin-2-ylidene)-3-calphokydimethylrhodanine in silver iodobromide emulsion 0353
600 μ per mole, 5-(,
2-(nee-3-ethyl-thiazolidin-2-ylidene)
Ethylidene-3-carboxine methylrhodanine 650
my Hankro sensitizing dye as 3-ethyl-5-1 (3
2-thio-5
-thiazolidinylidene-4-thiazolidone 800i1i
7). Furthermore, 20% ascorbic acid aqueous solution 38
me, phthalic acid (10% methanol solution) 40
ml, phthalazine (20% methanol solution) 15m/
, color toning agent and 1 to 4-ethyl-3-amino-5-mercapl---1,2,4-triazole in 2-thimethanol solution 8Tn1. was added, and a heat-developable layer (
8) was applied (Figure 10).

After drying, the sample was divided into three parts: one was wedge exposed to blue light for 1 minute (A), and the other was wedge exposed to green light for 1 minute (B).
, the other was also wedge-exposed with red light for 1 minute (C
)0 In step A, the base surface of the AXBXC sample was pressed against a heat block for 20 seconds at 120° C. for thermal development.

Next, using Ipoly paper as an image-receiving sheet for each AXBXC sample, the heat-developed surface was brought into close contact with the Ipoly paper.
RISOTORAPEN-UPTU-275 manufactured by Riso Kagaku
to give a strobe crash light through the base surface (approximately 4
Joule layer) Sample A has Dmtn = 0.02 Dmax = 05
4, the magenta wedge image of sample B is I) min =
Sample C gave a cyan image of 0.03 Dmax = 0J38, and sample C gave a yellow wedge image of Dmin = 0.01 Dmax = O12.

[Brief explanation of the drawing]

FIG. 1 shows the silver halide photosensitive material used as the basis for preparing the dye-donating layer, and FIGS. 2 to 4 show the procedure for preparing the mosaic dye-donating layer. Also, Figure 5 shows a single layer of mosaic filter,
FIGS. 6 to 9 show the procedure for creating a mosaic dye-donor layer in which color and orientation are matched to one layer of a mosaic filter. Figure 70 shows a mosaic dye-donor layer with a thermal pattern generating layer. 1... Support, 3 and 7... Photosensitive material, 4... Photomask, 6... Mosaic filter 8... Heat developable photosensitive material. Agent Yoshimi Kuwahara 41-

Claims (2)

[Claims] (1) A sublimable dye is formed on a hydrophilic binder grown on a support by a silver halide external color development method,
A thermal transfer image forming method characterized in that the sublimable dye is transferred to an image receiving medium using a thermal pattern. (2) The thermal transfer ijf+i image forming method according to claim 1, characterized in that at least two or more types of the dyes are formed in a mosaic or stripe shape in one layer of the hydrophilic binder.