JPH0356200B2 - - Google Patents

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, thermal transfer methods, and inkjet methods have been developed. Various hard copy methods have been proposed, some of which have also been put into practical use.

However, none of these methods can provide sufficient gradation expression, and the method using silver salt is superior to other methods in this respect. However, on the other hand, silver salt requires a complicated processing process, and is inferior to 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 silver salts, and among these, a method using a heat-developable photosensitive material is attracting attention.

Regarding heat-developable photosensitive materials, for example,
Nos. 4921 and 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, and a reducing agent. In these heat-developable photosensitive materials, a latent image is formed on silver halide by exposure, and this latent image is used as a catalytic nucleus to perform an oxidation-reduction reaction using an organic silver salt and a reducing agent during heating, thereby forming a silver image through a so-called dry physical development process. This is what you get.

Furthermore, many attempts have been made to obtain color images by heat development. For example, US Patent No.
As described in No. 3531286, No. 3761270, and No. 3764328, an aromatic amine developing agent and its oxidized product are coupled to form dyes such as Y (yellow), M (magenta), and C (cyan). For example, a method using a flexible coupler can be mentioned.

Furthermore, a similar color development type is Research Disclosure (hereinafter abbreviated as RD).
No. 12146, No. 1508, No. 15127, JP-A No. 1983-
No. 27132 is also mentioned. Also US Patent No. 3985565
No. 4022617, method using leuco dye as described in RD12533, etc., JP-A-52-105821,
A method using the SDB method described in No. 52-105822, etc.
Those in which the dye is bleached with a reducing agent in the unexposed area as described in RD15676, etc., and RD15126,
There are various methods, such as one that is itself a reducing agent and is bleached in the exposed area, as in No. 17706. However, when full-color heat-developable photosensitive materials are considered, the stability of the photosensitive materials is poor, and the color tones that can be obtained are 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. This consists of a dry silver layer on both sides of a transparent support (for example, a film base), three sheets coated with a sublimable dye having a color tone that is complementary to the spectral sensitivity of this dry silver layer, and a yellow layer on the back side of the regular dry silver layer. A regular sheet, a magenta sublimable dye on the back side of the ortho dry silver layer, and a cyan sublimable dye on the back side of the panchromatic dry silver layer, viewed from the exposed side. The sheet and the panchromatic sheet are stacked in this order and exposed through the color original from the regular layer side.

After exposure, heat development is performed, three sheets are separated, the image-receiving layer and the sublimable dye surface are overlapped, and the silver image area is irradiated with infrared rays to generate heat and transfer the sublimable dye to the image-receiving layer. . For each sheet of Y, M, and C, thermal transfer by infrared irradiation is applied to the image receiving layer.
A full color print can be obtained by overlapping the two layers several times. This method has a very simple structure because it is possible to use a normal monochrome photothermographic material as it is as a photothermographic material, and because it only uses a sublimable dye as it is as a coloring material. It has characteristics. However, since it involves the step of superimposing the Y, M, and C images on the image-receiving layer three times, it has the drawback that the process is complicated, such as difficulty in aligning the three colors.

In order to solve the above-mentioned drawbacks, the present inventor filed a patent application filed in 1983-
No. 186142, after exposing an imaging element consisting of a mosaic filter layer containing a thermally transferable dye or dye-donor 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 heat-developable photosensitive layer, heat-developing it at a temperature below the heat transfer temperature of the heat-transferable dye or dye-providing material, the mosaic filter surface containing the heat-transferable dye and the image-receiving layer. We have proposed an image forming element in which a heat transferable dye or a dye-donating substance is transferred to an image-receiving layer by uniform irradiation with infrared rays and high-intensity light, and heat generated in the image area.

The dye or dye-donating substance in this proposal is preferably one that can be sublimated, but as a specific means for making a mosaic filter layer containing the dye, etc., it is possible to prepare it in advance in a binder such as gelatin by some method such as ball milling, etc. After finely dispersing the dye etc. using a method such as sand mill ultrasonic dispersion and adding potassium dichromate, pattern exposure is carried out with ultraviolet rays, and then the parts other than the photocured parts are washed away with water. Further, a layer of dichromium gelatin in which another colorant or the like is dispersed is recoated, and the areas other than the areas photocured in the first exposure and development are exposed and developed again in a pattern. Furthermore, if necessary, a method for obtaining a mosaic or stripe pattern layer of thermally transferable dyes is mentioned by repeating the same operation for the third and subsequent colors.

However, this manufacturing method has drawbacks such as the long time it takes to disperse the sublimable dye and the dispersed particle size being large, making it difficult to obtain uniform dispersion. Furthermore, dichromic acid is harmful to the human body, and there is room for improvement in terms of treatment.

(Object of the invention) The object of the present invention is related to the above-mentioned problems, and
The objective is to provide an image forming method that is easy to operate, has improved image quality, and greatly reduces environmental problems. A second object is to provide a thermal transfer photosensitive material that meets the above objectives and has good image sharpness and, as a result, improved resolution, and also does not cause occupational health or pollution problems.

(Structure of the Invention) The object of the present invention is to form a sublimable dye in a hydrophilic binder provided on a support by a silver halide external color development method, and to form a sublimable dye by a thermal pattern. This can be achieved by a thermal transfer image forming method in which the image is transferred to an image-receiving layer.

That is, the drawing step of the thermal transfer image forming method of the present invention is as follows:
Hydrophilic dyes or dye-providing sublimable substances (hereinafter collectively referred to as sublimable dyes) are produced and contained in a hydrophilic binder layer provided on a support using a silver halide external color development method. A dye-donating layer surface (sublimation transfer surface) of a dye-donating sheet for thermal transfer (hereinafter simply referred to as a dye-donor sheet) having a binder layer, that is, a dye-donor layer for thermal transfer (hereinafter simply referred to as a dye-donor layer) and an image-receiving layer surface are brought into contact with each other. By applying imagewise exposure to the dye-donating layer according to the original image, the sublimable dye is heated by a thermal pattern having a temperature distribution corresponding to the imagewise exposure and transferred to the image-receiving layer to create an image. It is something to do.

A feature of the present invention is that the sublimable dye contained in the dye-donating layer is formed by an external color development method using silver halide, and therefore the formed sublimable dye grains are extremely fine. Because the particle size is uniform and distributed in the hydrophilic binder at a uniform density,
It has a good sublimation response to temperature, and therefore a fast development speed, and the image quality and sharpness of the generated image is high, and as a result, the resolution is also improved.

The image-receiving layer may be integrally provided on the dye-donating sheet via a light-blocking layer and a reflective layer, or an image-receiving sheet having the image-receiving layer provided on another support may be provided separately.
It may be brought into contact with the dye-donating layer during drawing.

In a preferred embodiment of the present invention, a pattern is formed in which two or more sublimable dyes formed by a silver halide external color development method are distributed to mosaic or stripe surface elements (hereinafter, both will be collectively referred to as Examples include an embodiment in which a dye-donating layer is formed in a hydrophilic binder layer to form a mosaic pattern (referred to as a mosaic pattern) and is present in a hydrophilic binder layer. Such embodiments are suitable for producing multicolor images.

Furthermore, the effects of the present invention can be improved by providing a structure in which the functions of the dye-donating layer are separated and reinforced. For example, in order to select colored light from an original image, a mosaic filter layer made of non-sublimable dye is provided using a silver halide photosensitive material, and the colors and positions are matched to the mosaic filter according to negative-positive or positive-positive drawing. By forming a two-layer structure with a mosaic sublimable dye layer in which surface elements containing a sublimable dye are allocated, or by taking the same consideration as above, a non-sublimable dye and the dye function as a filter. By mixing sublimable dyes with matching colors and positions in the same area, it is possible to improve the accuracy of color separation and the ease and reliability of operation.
The thermal pattern function for supplying heat of sublimation can be achieved by providing a thermal pattern generation layer that supports an image-like pattern of a heat storage medium such as black silver using a heat-developable photosensitive material. By separating and reinforcing the sublimable dye, the thermal transfer efficiency (development speed and development strength) of the sublimable dye can be increased. Furthermore, in the case where a thermal pattern generation layer is provided and a separate image-receiving sheet is used, simply by repeating the contact between the dye-donating sheet and the image-receiving sheet and heating, the sublimable dye can be applied to the area where the sublimable dye is present in the dye-donating layer. You can make multiple copies by

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, it is generated as a high-low temperature distribution in the dye-donating layer.

When creating a multicolor image, select one dye-donor sheet from among 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 dye-donor sheet. The sublimable dye contained in the dye-donating layer is thermally transferred to the image-receiving layer of an image-receiving sheet by exposing the dye-donor layer to multicolor separated light or white light that includes the absorption wavelength of the dye-donor layer, and then transfer the dye-donor sheet to another dye-donor sheet. A multicolor image can be obtained by replacing the sheets, aligning the image positions, superimposing them, and thermally transferring them in the same manner as described above, and repeating this operation as many times as there are dye-providing sheets.

When the thermal pattern generating layer is provided in the dye donating layer, imagewise exposure and development is performed with light having a wavelength in the photosensitive region of the thermal pattern generating layer to form an imagewise pattern of the thermal storage medium; If necessary, unnecessary photosensitive components in the thermal pattern generation layer are fixed and removed, and after drying, the image position is aligned with the image receiving layer, the layer is brought into contact with the layer and heated, and the sublimable dye is transferred. The above operations are repeated to create a multicolor image.

In the case of using a dye-donating layer configured with a mosaic pattern of two or more sublimable dyes mentioned as a preferred embodiment of the present invention, the dye-donating layer and the image-receiving layer provided separately on the image-receiving sheet or When the dye-donor sheet is brought into contact with the image-receiving layer provided integrally with the image-receiving layer, the mosaic surface is created by light split into wavelength ranges that are absorbed by the mosaic surface element containing two or more types of sublimable dyes. A multicolor image can be created by imagewise exposing the medium a number of times corresponding to the type of material to generate a thermal pattern, or by forming an imagewise pattern of a heat absorbing medium and heating it if it has a thermal pattern generating layer. can be created.

Furthermore, by adding a filter function in the dye-donor layer that is color and position matched to the mosaic pattern, a single imagewise exposure with white light is sufficient to generate the thermal pattern, and the operation is simple. This is extremely simple and reliable, and the accuracy of color separation is improved.

The exposure used for generating the thermal pattern or forming the heat absorbing medium pattern according to the present invention can be arbitrarily used, such as scanning exposure, contact exposure, or projection exposure light, and the exposure light source may be according to the above-mentioned exposure method.
Light sources commonly used in photography can be used, such as various laser light sources, strobes, tungsten incandescent lamps, halogen lamps, or LEDs. A filter is also used if necessary.

The heat storage medium formed in the thermal pattern generating layer provided in the dye-donating layer may be heated by a method using heat conduction such as light or infrared radiation from the light source described above, thermal panel pressure bonding, hot air blowing, etc. I can do it.

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

The present inventors focused on the fact that the crystals generated in the protective colloid are extremely fine, have a practically uniform particle size, and are uniformly dispersed. By borrowing a silver photosensitive material or an external color silver halide photosensitive 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.
Complicated processes related to mosaic pattern formation preferably used in the present invention, occupational hygiene using dichromic acid, etc.
We discovered that we can be freed from environmental problems all at once.

The dye-providing sheet according to the present invention has a desired color after the above-described silver halide photosensitive material, preferably a black and white silver halide photosensitive material, is subjected to a predetermined exposure,
Since it has a relatively small molecular weight and is nonpolar, it can be easily formed by selecting a combination of a coupler and a color developing agent that produce a sublimable dye and performing external color development.

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

The sheet is a photosensitive material having at least one silver halide emulsion layer provided on a support, and the emulsion layer is exposed to a first color mosaic pattern, and then external color development is performed to form the first color dye and silver. Next, the unexposed area containing silver halide is exposed to a second color mosaic pattern, and external color development is performed to form a mosaic pattern consisting of the second color dye and silver. By repeating the same process of forming a mosaic pattern consisting of the third color and subsequent colors and silver, a mosaic pattern of at least two colors is formed, and after the final color development process, a desilvering process is performed to form a dye-donating layer. can be formed and created. In the formation of the dye-donating layer, it is preferable to add a treatment such as black and white development or latent image bleaching treatment after at least one color development step other than the final one to prevent color development from proceeding any further.

The dye-providing sheet having a mosaic pattern according to the present invention will be explained in more detail with reference to the drawings. FIG. 1 shows an example of a light-sensitive material used in the present invention. is provided, and a silver halide emulsion layer 3 is provided thereon. This photosensitive material is subjected to image exposure 5 through a photomask 4 to form a mosaic pattern of, for example, cyan, which corresponds to the first color of the dye used in multiple colors, as shown in FIG. The light source used for this exposure may be any light source that emits light at a wavelength to which the silver halide emulsion layer is sensitive, for example, white light.

The exposed photosensitive material is then subjected to a first external color development process. For example, when such a photosensitive material is developed with an external color developing solution containing a cyan coupler, a pattern 5 consisting of cyan dye and silver particles is formed in the exposed area.
a, 5a', etc. are formed. After the first development is completed, the photosensitive material is washed with water and, if necessary, dried. Next, using the same photomask 4 and using a magenta color developer, magenta patterns 5b, 5b', etc. are similarly formed into cyan patterns 5a, 5b', etc. as second colors.
It is formed next to 5a' etc. (Fig. 3). Furthermore, by performing the same operation using the same photomask 4 and a yellow color developing solution, yellow patterns 5c, 5c', etc. are formed between the magenta and cyan patterns 5a', 5b, etc. (FIG. 4) Thereafter, the film having the mosaic pattern of these dyes is desilvered by passing through a bleach-fixing process.

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-methyl-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-
It is an alkaline aqueous solution of methoxyethylaniline, 3-methyl-4-amino-N,N-dimethylaniline, etc., and contains various color couplers described below in this alkaline aqueous solution. This aqueous solution usually contains salts such as sodium sulfate, PH regulators and buffers such as sodium hydroxide, sodium carbonate, and sodium phosphate, and anti-capri agents such as alkali halides such as potassium bromide. It is something.

Typical developing agents that can be advantageously used in the present invention include those described above, but those having a relatively small molecular weight of 250 or less and having no polar groups are preferred in order to obtain a sublimable coloring dye.

Also, as a coupler, for example, U.S. Patent No. 3510306
No. 3619189, Special Publication No. 40-33775, No. 44-
Yellow coupler described in No. 3664, etc., German Patent Publication (OLS) No. 2016587, U.S. Patent No.
Magenta coupler described in US Pat. No. 3152896, No. 3615502, Special Publication No. 44-13111, etc. US Patent No. 3002836,
There are cyan couplers described in British Patent No. 3542552, British Patent No. 1062190, etc., but among these, the molecular weight is relatively small (preferably 300 or less), and the polarity of the sulfone group, carboxy group, or quaternary amino group is Couplers without groups are preferred. However, it may contain a group that is eliminated during color development, such as a sulfo group substituted at the active site of the coupler.

Typical couplers used in the present invention include, but are not limited to, the following.

1 2-acetoacetanisidide 2 Acetoacetanilide 3 2-Benzoylacetanilide 4 Benzoylacetanilide 5 Pivaloylacetanilide 6 1-Phenyl-3-methylpyrazolone 7 α-cyanoacetophenone 8 1-( 4-chlorophenyl)-3-methylpyrazolone 9 1-phenyl-3-methoxypyrazolone 10 1-(2,4,6-trichlorophenyl)-3
-Methyl-pyrazolone 11 2-chlorophenol 12 2,6-dichlorophenol 13 Phenol 14 2,4-dichloronaphthol 15 2,4-dibromnaphthol 16 α-naphthol 17 4-sulfo-1-naphthol 18 2-methoxy Phenol 19 α-(o-methoxybenzoyl)acetanilide 20 α-(o-methoxybenzoyl)acetanilide 21 α-(p-chlorobenzoyl)acetanilide 22 α-(4-chlorobenzoyl)acetanilide 23 2,5-dichlorophenol 24 2-cyanoacetylbenzofuran 25 α-cyanoacetanilide 26 α-cyanoacetophenone 27 3-phenyl isoxazol-5-one 28 5-chlorocoumaran-3-one 29 2-aniline-4-phenylthiazole For the desilvering treatment used in this process, all bleaching solutions used in ordinary color photographic processing can be applied. That is, potassium ferricyanide or iron-ETA complex salt is used as the oxidizing agent, and for example, potassium bromide is added for rehalogenation.

The fixing agent for silver halide is generally a well-known arbitrary silver halide solvent (e.g., sodium thiosulfate, sodium thiocyanate), and the solution containing the fixing agent may optionally contain a preservative (e.g., sodium sulfite, PH). Contains buffering agents (eg, boric acid), PH regulators (eg, acetic acid), chelating agents, etc.

Also, as one of the above desilvering treatments, a one-bath bleach-fix solution, such as a mixed solution of red blood salt and sodium thiosulfate or a mixed solution of EDTA-Fe() and sodium thiosulfate, can also be used.

In the above description, the mosaic surface elements of each color are arranged so as to be in close contact with each other, but it is of course possible to form a mosaic dye-donating layer in which the mosaic surface elements are not in close contact with each other. Further, when a stripe pattern of the same width is used as a mosaic pattern, for example, the same photomask 4 shown in FIG. 2 can be used, and patterns of each color can be sequentially exposed while shifting the position.

As is clear from the above description, the mosaic dye-donating layer according to the present invention is formed by repeating multiple mosaic exposures and external color development on a fine-grain black-and-white silver halide photosensitive material to form a mosaic dye-donating layer in the same emulsion layer. Therefore, the width of the mosaic surface element is 1μm.
It is also possible to easily obtain a mosaic pattern with very high precision.

In the external color development, the development speed is generally slow, the progress of development slows down as the development time increases, and the development does not reach saturation. Although it is possible to saturate the development by performing the development for about 30 to 40 minutes for each color, the overall processing time becomes significantly longer in order to process multiple colors. Therefore, in order to shorten the development time of the color development step, if the development time for the first color, for example, cyan, is stopped at 15 minutes and the next step is started, then the development time for the second color, for example, magenta, is shortened. In this case, the first exposed area (reference numeral 5 in Figures 2 to 4), which should originally contain only cyan dye,
Magenta dye is also generated in the region a), and the cyan pattern becomes a mixed color of magenta. Although such color mixing is rather effective in special cases as described below, 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, in a short period of time (for example, about 5 minutes maximum), the latent image remaining in the color development process of the first color is easily saturated because it is developed by the rapid black-and-white developer, and the exposed area is no longer covered with silver. is not generated. In other words, color development will substantially no longer proceed in this area. Therefore, the magenta and yellow dyes of the second and third colors in the subsequent steps 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 of four or more colors, after performing color development for the second and subsequent colors (as there is no risk of color mixing in the final pattern formed, such processing is unnecessary). The pattern obtained by repeating the same process is completely free from color mixing.

The light-sensitive material subjected to external color development in this manner is then desilvered as described above to form a mosaic dye-donating layer regularly arranged as a mosaic of each color.

It is important that the black and white developer used in such an 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-aminophenol, and ascorbic acid. Add developer as needed.
alkaline agents (e.g. sodium hydroxide, sodium carbonate), pH adjusting or buffering agents (e.g. acetic acid,
Known compounds and compositions such as boric acid), anti-capri agents (e.g. potassium bromide), and preservatives (e.g. sodium sulfite) can be added. Furthermore, rapid developers or high contrast developers known in the field of photography are most preferred for such purposes. The quick developing solution or the high contrast developing solution is described, for example, in "Science Photography Handbook (Medium)" new edition, December 20, 1950, published by Maruzen Co., Ltd., pages 126 and 127.

Alternatively, if the latent image bleaching method is used, the first color pattern is developed (for example, red) to destroy the latent image, and then the second color pattern is image-exposed to partially overlap the first color pattern. By color-developing the second color pattern (for example, to green), the overlapping area of the first color pattern and the second color pattern becomes opaque to red, green, and blue light. Therefore, a so-called lux stripe can be formed between the first color pattern and the second color pattern. Also, by performing the same process between the second color pattern and the third color pattern (for example, blue), a mosaic dye with a preferable black stripe in which each color pattern is partitioned with black can be obtained. You can get layers. It goes without saying that such a black stripe can also be achieved by providing a black pattern between these patterns in the same way as forming patterns of each color.

In the above explanation, a cyan or red developer was used as the first developer, a magenta or green developer was used as the second developer, and a yellow or blue developer was used as the third developer. is optional, and it goes without saying that the process may include not three color development steps but two, four or more color development steps in any order.

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

Also, one of these dyes, for example, a yellow dye, is a sublimable dye and the other magenta dye is a non-sublimable dye, and a cyan dye and a sublimable magenta dye are formed in the same manner on the other surface elements, and A yellow dye and a sublimable cyan dye are formed on the remaining surface elements to form a mosaic dye-donating layer each having the functions of both a mosaic filter and a dye-donating layer.

At this time, since the external color developing bath used to form a non-sublimable dye does not need to form a sublimable dye, both the color developing agent and the coupler may have polar groups.

Further, in the method of the present invention, mosaic filters can be generated in advance in accordance with the above-described method, and sublimable dyes can be formed thereon at portions corresponding to each filter. This will be explained below with reference to the drawings.

FIG. 5 shows a mosaic filter layer 6 on a support 1.
FIG. FIG. 6 shows that a panchromatically sensitized silver halide emulsion layer 7 is provided thereon. FIG. 7 shows this image exposed to blue light from the support side. Next, this was color-developed with a color developer to form a mosaic surface element 7a containing a sublimable magenta dye, as shown in FIG. (To prevent further development, the exposed area was developed with a black and white developer to saturate the development.) Next, after exposing the entire surface to green light, 7b was formed on the cyan sublimable dye, and then red light was applied. After the entire surface was exposed to light, 7c was similarly formed on the yellow sublimable dye, and then bleach-fixed. As a result, a sublimable dye pattern corresponding to the mosaic filter is obtained as shown in FIG.

The dye-donating layer thus obtained is sublimated by a thermal transfer method using a heat-sensitive head, a heat mode dye transfer method using a laser, or a photothermography method as described in Japanese Patent Application No. 186142/1984. It can be advantageously used as an image forming method using a dye-donating layer having a mosaic of color dyes.

Examples of silver halide in the photosensitive silver halide emulsion used as a matrix for the dye-donating layer or mosaic filter layer related to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, Examples include silver iodobromide, silver chloroiodobromide, and mixtures thereof. The photosensitive silver halide can be prepared by any method known in the photographic field, 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. Light-sensitive silver halide emulsions prepared according to techniques including the following give 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 various methods such as 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 a random diameter of 1.5μ to about 0.001μ, more preferably about 0.5μ to about 0.001μ. It is 0.01μ.

Typical spectral sensitizing dyes for the silver halide include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like.

The amount of these dyes added is from 10 ^-4 mol to 1 mol per mol of silver halide or silver halide forming component. More preferably, it is 10 ⁻⁴ mol to 10 ⁻¹ mol.

A heat-developable photosensitive material preferably used for the thermal pattern generation layer can be obtained by mixing the above-mentioned photosensitive silver halide and photosensitive organic silver salt.

These photosensitive silver halides and photosensitive organic silver salt-forming components can be used in combination in various methods, and the amount used is 0.001 to 1 mole of the organic silver salt.
The amount is 5.0 mol, preferably 0.01 to 0.3 mol.
The amount of the organic silver salt applied is 0.05 to 10.0 g, preferably 0.2 g.
~2.0g.

Examples of the photosensitive organic silver salts used in the heat-developable photosensitive material of the present invention include aliphatic or aromatic carboxylic acid silver, imino group-containing silver salts, merkaft group- or thione group-containing silver salts, and the like. be able to.

Spectral sensitizing dyes for the above-mentioned heat-developable light-sensitive materials include merocyanine dyes having rhodanine nuclei, thiohydantoin or 2-thio-2,4-oxazolidinedione nuclei, thiobarbituric acid nuclei, or long-chain alkyl groups. A merocyanine dye having a polynuclear merocyanine dye 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, 3- Pyrazolidones, pyrazolones,
Examples include hydrazones and paraphenylene diamines.

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

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, thermal fog inhibitors, antihalation agents, plasticizers, spreading agents, and hardening agents.

Various binders can be used as the binder for the above-mentioned photosensitive silver halide photosensitive materials and heat-developable photosensitive materials, but suitable binders include hydrophilic binders, and hydrophobic binders for heat-developable photosensitive materials. Any desired binder can be used depending on the purpose. For example, white matter such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharite such as dextran, natural substances such as gum arabic, synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyvinyl acetal, and the size of photographic materials. Latex-like vinyl compounds and other synthetic polymers may also be included to increase thermal stability.

Various papers and film bases can be used as the image-receiving sheet according to the present invention, including baryta paper, art paper, ivory paper, etc., paper supports having various overcoat polymer layers, and even various mordants. A mordant layer containing a chelate-forming metal salt, a layer containing a complex, etc. may be overcoated. Alternatively, it may be an integral structure in which this image-receiving layer and the dye-donating layer are coated on the same support. If desired, the dye-donor layer can then include an opacifying layer that transmits 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 for reflection. The opacifying layer can contain various reagents to provide the necessary reflection, such as titanium dioxide.

(Example) Next, the present invention will be explained in more detail using Examples.

Example 1 A silver halide emulsion containing 50 g of gelatin and 64 g of silver iodobromide (grain size 0.06 μm, iodine content 2%) was
It was coated and dried to a dry film thickness of 3 μm on a polyethylene terephthalate base that had been undercoated to a thickness of 30 μm. The width of the transparent part of this photosensitive material
A stripe filter mask made using a printing plate film with a 42 μm pitch and 125 μm was closely attached, exposed to white light (tungsten lamp), and developed with a cyan color developing solution having the following composition. (24℃ 10
) Cyan color developer N,N-diethyl-p-phenylenediamine hydrochloride 3g Sodium sulfite 5g Sodium carbonate 60g Potassium bromide 2g Add water to make 1. Dissolve 1g of 2-chlorophenol in this and 50ml of methanol. Add.

After washing with water for 5 minutes, develop with a developer of the following composition (24
℃ for 5 minutes) to saturate the development of the exposed area and prevent further development.

Developer 1-phenyl-3-pyrazolidone 0.5g Sodium sulfite (anhydrous) 50g Hydroquinone 12g Sodium carbonate (monohydrate) 60g Potassium bromide 2g Benztriazole 0.2g 1-Phenyl-5-mercaptotetrazole
5mg phenazine-2-carboxylic acid 1g Add water to make 1.

Next, soak it in a stop solution with the following composition for 2 minutes, and then
After washing with water for a minute, it was dried. A mixed pattern of cyan dye and silver was thus obtained.

Stop liquid 10ml glacial acetic acid Sodium sulfate 45g Add water to make 1.

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

Magenta color developer Sodium sulfite 5g Diethyl-p-phenylenediamine hydrochloride 3g Sodium carbonate 60g Potassium bromide 2g Add water to make 1, and then add 1-phenyl-3
- 1 g of methyl-5-pyrazolone is dissolved in 50 ml of methanol and added.

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

After cyan development was stopped, it 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 stripe filter mask, the magenta pattern was aligned so that the transparent part of the mask was next to it, and then exposed, and then developed with a yellow color developing solution having the following composition (24°C 10°C).
minutes).

Yellow color developer Sodium sulfite 5g Diethyl-p-phenylenediamine hydrochloride 3g Sodium carbonate 60g Potassium bromide 2g Add water to make 1. To this was added 1 g of o-acetoacetanisidite dissolved in 50 ml of methanol.

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

Bleaching solution Potassium ferricyanide 100g Potassium bromide 30g Water 1000ml Fixing solution Sodium thiosulfate 240g Sodium sulfite 3g Glacial acetic acid 5ml Potassium alum 6g Water 1000ml Cyan, magenta, and yellow sublimable dyes with no visible color mixture when washed with water for 5 minutes and dried. A striped pattern was obtained.

Next, this stripe pattern was adhered to art paper as an image receiving sheet, and a 50 mW helium neon laser (NEC 5800) was focused on a beam spot of 20 μm and scanned at a speed of 25 cm/sec from the base side. When the paper was pulled apart, a cyan line was transferred along the scan line.

Then, when the paper was similarly scanned using a 4W argon ion laser (GLG3302 manufactured by NEC Corporation) at a scanning speed of 5 m/sec, a magenta line was observed on the art paper. Then similarly 100mW
25 with He-Cd laser (manufactured by Kinmon Electric; CD4002R)
When scanned at a speed of cm/sec, it was confirmed that a yellow line was transferred.

Example 2 A striped filter with a pitch of 100 μm and a blue, green, and red filter line width of 33 μm was formed on polyethylene terephthalate by the method described in US Pat. No. 3,284,208 (FIG. 5). Next, a 3 μm dry film of a panchromatically sensitized silver iodobromide gelatin emulsion (grain size: 0.06 μm, silver iodide content: 2 mol%, containing 64 g of silver iodobromide and 50 g of gelatin) was deposited on this filter as shown in Figure 6. I applied it so that it was thick. The entire surface of this photosensitive material was exposed to blue light from the base side, and developed for 10 minutes at 24°C with the same magenta developer as in the example. After washing with water for 5 minutes, the film was developed with the above-mentioned black and white developer, and the exposed area was further developed at 24° C. for 5 minutes to prevent further development. Next, the same stopping water washing and drying as in Example 1 was performed. Next, the entire surface was exposed to green light from the back side, and developed with the same cyan developer as in Example 1 at 24° C. for 10 minutes. After washing with water for 5 minutes, development was performed at 24°C for 5 minutes using the same black and white developer to saturate the development of the exposed areas.

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

Next, the entire surface was exposed to red light from the back side, and the same yellow external color developing solution as in Example 1 was used.
The film was developed at 24°C for 10 minutes, washed with water for 3 minutes, and then bleached and fixed in the same manner as in Example 1. After washing with water for 5 minutes and drying, a pattern was obtained in which magenta, cyan, and yellow sublimable dyes corresponding to the blue, green, and red striped filters shown in FIG. 9 were very finely and uniformly dispersed.

Next, a heat-developable photosensitive layer was coated on the stripe filter using the following formulation.

First, add alcohol to 11.4g of benztriazole silver.
200 ml and 250 ml of an 8% polyvinyl butyral aqueous solution (Electric W-201 manufactured by Sekisui Chemical Co., Ltd.) were added and dispersed in a ball mill for 24 hours to prepare a dispersion. Next, this dispersion was stirred to form a pavan chromatic silver iodobromide emulsion (60 gelatin in 1 kg of silver iodide 5 mol% emulsion).
13 ml of cubic emulsion grains with an average grain size of 0.06 μm containing 0.353 mol of silver and 0.353 mol of silver were added. (This silver iodobromide emulsion contains 5-(3-methylbenzthiazolin-2-ylidene)-3-carboxymethyl rhodanine as a regular sensitizing dye.
600 mg per 0.353 mole, 5-(2-{3-ethyl-thiazolidin-2-ylidene}ethylidene-3-carboxymethylrhodanine 650 mg as ortho-sensitizing dye, 3-ethyl- as panchromatic sensitizing dye)
5-[(3-ethyl-2-benzthiazolinylidene-ethylidene]-2-(3-ethyl-4-oxo-
800 mg of 2-thio-5-thiazolidinylidene-4-thiazolidone was added). Additionally, 38ml of 20% ascorbic acid aqueous solution, phthalic acid (10% methanol solution)
40ml, Phthalazine (20% methanol solution) 15ml,
Add 8 ml of a 2% methanol solution of 4-ethyl-3-amino-5-mercapto-1,2,4-triazole as a color toning agent, and place on the striped filter mentioned above so that the amount of silver per 1 m ² is 0.5 g. A heat-developable layer 8 was applied (FIG. 10).

After drying, the sample was divided into three parts: one was wedge exposed to blue light for 1 minute (A), the other was wedge exposed to green light for 1 minute (B), and the other was wedge exposed to red light for 1 minute ( C).

Next, samples A, B, and C were thermally developed by pressing the base surfaces against a heat block at 120° C. for 20 seconds.

Next, using ivory paper as an image-receiving sheet for samples A, B, and C, the heat-developed surface was brought into close contact with the ivory paper, and then the RISO TORAPEN- manufactured by Riso Kagaku Co., Ltd.
Strobe flash light was applied through the base surface using UPTU-275 (approximately 4 Joule/cm ² ) Sample A produced a magenta wedge image with Dmin=0.02Dmax=0.54, and sample B produced a cyan image with Dmin=0.03Dmax=0.88. , Sample C gave a yellow wedge image with Dmin=0.01Dmax=0.46.

[Brief explanation of drawings]

FIG. 1 shows a silver halide light-sensitive material as a base material for forming a dye-donating layer, and FIGS. 2 to 4 show the procedure for forming a mosaic dye-donating layer. Further, FIG. 5 shows a mosaic filter layer, and FIGS. 6 to 9 show the procedure for creating a mosaic dye-donor layer whose color and position are matched to the mosaic filter layer. Additionally, FIG. 10 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.

Claims (1)

[Scope of Claims] 1. A sublimable dye is formed in a hydrophilic binder layer provided on a support by a silver halide external color development method, and the sublimable dye is applied to an image-receiving layer by a thermal pattern. A thermal transfer image forming method characterized by transferring. 2. The thermal transfer image forming method according to claim 1, characterized in that at least two kinds of the sublimable dyes are formed in the hydrophilic binder layer in a mosaic shape or a stripe shape.