JPH0679975A - Sheet to receive thermal transfer - Google Patents

Abstract

PURPOSE:To obtain a coloring image having the continuous gradation like a photograph directly from an electric signal by providing a part, which is hardened by ionizing radiation and an unhardened part on an accepting layer. CONSTITUTION:A substrate 2 is provided. An accepting layer is provided ion the substrate 2 and formed of a synthetic resin layer, wherein the dye which is transferred from a thermal transfer sheet when the sheet is heated with energy is accepted. Thus a sheet to be thermally transferred 1 is obtained. Here, the accepting layer 3 has a part, which is hardened by ionizing radiation, and unhardened part. The accepting layer 3 is formed by the following way. The compound, which can be crosslinked by electron beams, ultraviolet rays or the like, is applied on the entire surface of the substrate. The electron beams or the ultraviolet rays are applied to the compound, and crosslinking is performed in, e.g. a grid pattern. The part, which is or crosslinked, is made to be a first region 4, and the crosslinked part is made to be a second region. Thus, the coloring image having the high density and the high transparency is obtained, and the coloring image having the continuous gradation such as a photograph is directly obtained from an electric signal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat transfer sheet, and more particularly to a heat transfer sheet which is used in combination with a heat transfer sheet for performing heat printing according to image information by a thermal head or a laser.

[0002]

In order to obtain an image according to image information by a thermal head or a laser, a thermosensitive coloring paper has been mainly used. In this heat-sensitive color-developing paper, a colorless or light-colored leuco dye and a developer provided on the base paper are brought into contact with each other by heating to obtain a color-developed image. As such a color developer,
Phenolic compounds, zinc salicylate derivatives, rosins and the like are commonly used. However, the above-mentioned thermosensitive coloring paper has a fatal defect that the obtained colored image is erased when stored for a long period of time, and color printing is limited to two colors and has continuous gradation. It was not possible to obtain a color image.

On the other hand, in recent years, heat-sensitive transfer paper, in which a heat-melting wax layer having a pigment dispersed therein is provided on a base paper, has begun to be used. When the heat-sensitive transfer paper and the transfer-receiving paper are superposed and heat printing is performed from the back surface of the heat-sensitive transfer paper, the wax layer containing the pigment is transferred onto the transfer-receiving paper to obtain an image. According to such a printing method, a durable image can be obtained, and a multicolor image can be obtained by printing a plurality of times using a thermal transfer paper containing pigments of three primary colors. It is not possible to obtain a photographic image having continuous gradation.

By the way, in recent years, there has been an increasing demand for directly obtaining an image such as a photograph from an electric signal, and various attempts have been made. One of such attempts is a method of displaying an image on a CRT and photographing it with a silver salt film, but when the silver salt film is an instant film, there is a drawback that running costs increase, and If the silver salt film is a 35 mm film, there is a drawback that it is not immediate because it requires post-shooting phenomenon processing.
As another method, an impact ribbon method or an inkjet method has been proposed, but the former has a drawback that the image quality is poor, and the latter requires image processing, so it is difficult to easily obtain an image like a photograph. There is a drawback that.

In order to solve such a drawback, a thermal transfer sheet provided with a sublimable disperse dye layer having a property of transferring by heating is used in combination with a thermal transfer sheet, and the thermal transfer sheet is controlled while controlling the sublimable disperse dye. A method has been proposed in which the image is transferred onto a sheet to obtain a photographic image with gradation. According to this method, an image having continuous gradation can be obtained from a television signal by a simple process, and a device used at that time is not complicated, and therefore, it is attracting attention. As one of the conventional techniques close to such a method, the dry transfer printing method of polyester fiber is a paint in which a dye such as a sublimable disperse dye is dispersed or dissolved in a synthetic resin solution, and the paint is applied to thin paper. This is a method of applying a pattern and drying it to form a thermal transfer sheet. The thermal transfer sheet is superposed on the polyester fiber which is the thermal transfer sheet and heated in close contact, and a disperse dye is dyed on the polyester fiber to obtain an image.

However, the thermal transfer sheet as described above and the thermal transfer sheet made of polyester fiber are overlapped,
Even if this is heated and printed by a thermal head or the like, a high density color image cannot be obtained. The reason is
It can be mentioned that the surface smoothness of the polyester fiber cloth is not good, but it is considered to be mainly due to the following reasons. That is, in the usual dry transfer printing method or dry-wet transfer printing method, transfer of the sublimable dye onto the polyester fiber cloth is carried out for a sufficient heating time, whereas heating by a thermal head is usually performed. Extremely short,
For this reason, the dye does not sufficiently migrate onto the fiber cloth. Incidentally, in the dry transfer printing method, the transfer of the dye is achieved by heating at 200 ° C. for about 1 minute, whereas in the heating by the thermal head,
It is as short as several msec at 00 ° C.

The present inventors have found the following facts as a result of researches aimed at achieving the above drawbacks mainly by improving the heat transferable sheet.

When clay-coated paper or synthetic paper is used as a heat transfer sheet, there is a drawback that the dye transferred from the heat transfer sheet cannot be sufficiently received and therefore a high density color image cannot be obtained. is there.

On the other hand, when a heat transferable sheet having a low melting point synthetic resin as a receiving layer is used, the heat and pressure applied to the thermal transfer sheet causes the synthetic resin layer itself to have thermal adhesiveness, so that the thermal transfer sheet is thermally transferred. The layer may be transferred onto a heat-transferable sheet, and as a result of research on the clarity and resolution of the obtained image, the above-mentioned drawbacks can be solved at once by using a heat-transferable sheet having a specific constitution. It was found that the present invention was completed.

The present invention is intended to solve the drawbacks associated with the prior art, and comprises a thermal transfer sheet having a thermal transfer layer containing a heat transferable disperse dye and a thermal transfer sheet having a specific structure. By using them in combination, it is intended to achieve the following objects. a) Obtaining a color image having continuous gradation like a photograph directly from an electric signal. b) In addition to obtaining a high density and highly transparent colored image,
To obtain a clear, high-resolution image that does not lose its color even when stored for a long period of time. c) To provide a combination of a thermal transfer sheet and a thermal transfer sheet, in which there is no peeling transfer of the thermal transfer layer to the thermal transfer layer during thermal transfer, and the thermal transfer sheet does not fuse.

In order to achieve the above objects, the present invention provides a heat transferable sheet provided with a receiving layer having the following properties, and this heat transferable sheet is used in combination with the heat transfer sheet. .

That is, the heat transfer sheet according to the present invention is
A heat transferable sheet used in combination with a heat transfer sheet having a heat transfer layer containing a heat transferable dye, wherein the heat energy according to an image signal is applied from a thermal head or a laser to the heat transfer sheet. In a thermal transfer sheet to form an image with a heat transferable dye, a base material, provided on the base material,
And a receptive layer comprising a synthetic resin layer that receives a dye that migrates from the thermal transfer sheet when heated by the energy, the receptive layer having a portion cured by ionizing radiation and an uncured portion. It is characterized by having.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention shown in the drawings will be described below. The thermal transfer sheet 1 according to the present invention is configured by providing a receiving layer 3 on a base material 2 as shown in FIG. 1. However, as shown in FIG. May be configured. When the receiving layer 3 is provided on the base material 2, the heat of the receiving layer 3 is about 3 to 50 μm, preferably about 5 to 15 μm. On the other hand, when the thermal transfer sheet is composed of the receiving layer 3 alone, the heat of the receiving layer 3 is 6
It is from 0 to 200 μm, preferably from 90 μm to 150 μm.

The receiving layer 3 comprises a first region 4 and a second region 5, as shown in FIG. The first area 4 is −
A synthetic resin having a transition temperature of 100 to 20 ° C., preferably −50 to 10 ° C. and a polar group such as an ester bond, a urethane bond, an amide bond, a urea bond, a C—CN bond and a C—Cl bond. Has been formed.

On the other hand, the second region 5 is formed of a synthetic resin having a glass transition temperature of 40 ° C. or higher, preferably 50 to 150 ° C., and preferably the synthetic resin forming the second region also has a polar group. is doing.

As the synthetic resin that can form the first region,
The following may be used having a Lath transition temperature of -100 to 20 ° C, preferably -50 to 10 ° C. (A) Those having an ester bond Polyester resin, polyacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin, etc. (B) Polyurethane resin etc. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resin as described above, a mixture or copolymer of these may be used.

If the glass transition temperature of the synthetic resin forming the first region is too high even when the above-mentioned half-entry is included or if it does not have a polar group, the dye transferred from the thermal transfer layer during heating cannot be sufficiently received, resulting in a clear image. Colored image cannot be obtained.

As the synthetic resin which can form the second region,
The following substances having a glass transition temperature of 40 ° C. or higher, preferably 50 to 150 ° C. are used. (A) The above-mentioned resins having a polar group used when forming the first region. (B) Resins having no polar group, but having a glass transition temperature of 40 ° C. or higher.

Styrene resin, styrene copolymer resin, polyvinyl alcohol resin, cellulose resin, rubber resin, polyvinyl butyral resin, ionomer resin,
Olefin resin etc.

When the glass transition temperature of the synthetic resin forming the second region is lower than 40 ° C., the color image once obtained is discolored with time, which is not preferable.

Both the first region and the second region formed of the above resin are exposed on the surface of the receiving layer,
The first region is 15% or more of the surface of the receiving layer, preferably 15 to 9
It accounts for 5%. The first regions exist in an island shape independently of each other, and the length of each island portion in the longitudinal direction is 0.5 to 200 μm, preferably 10 to 100 μm.
m. Further, it is desirable that the first region is substantially substantially surrounded by the second region. This is because the first region mainly receives the dye transferred from the thermal transfer sheet upon heating, while the second region functions to prevent the dye received in the first region from diffusing to other parts. It is thought to be because of this.

The following method can be considered for forming the receiving layer having the first region and the second region as described above. (I) A synthetic resin for forming the first region and a synthetic tree for forming the second region are selected from synthetic resins having poor compatibility with each other,
These synthetic resins are dissolved in a solvent, and the obtained solution is applied on a substrate or the like and then dried to separate the above synthetic resins into phases. (Ii) The synthetic resin for forming the first region and the synthetic resin for forming the second region are sufficiently kneaded, and this kneaded product is applied onto a substrate or the like. (Iii) A synthetic resin for forming the second region is prepared as a sheet, and a synthetic resin coating material for forming the first region is printed thereon by a printing method such as an offset method or a gravure method. (Iv) A synthetic resin for forming the second region is prepared as a sheet, and silicone is provided on the pattern by the printing method as described above, and then a synthetic resin paint for forming the first region is formed thereon. It is applied over the entire surface, and the part where the silicone is provided in a pattern is repelled. (V) A compound that can be crosslinked by electron beams or ultraviolet rays is applied over the entire surface of the substrate, and the compound is irradiated with electron beams or ultraviolet rays to crosslink in a lattice pattern, for example, and the uncrosslinked portion is first Let the area | region and a bridge | crosslinking part be a 2nd area | region.

When a coating composition in which a synthetic resin for forming the first region and the second region is dissolved or dispersed is used in forming the receiving layer, various additives may be added to the coating. These components should be selected from those that do not interfere with the fastening of the dye that migrates from the thermal transfer sheet when heated. Examples of such an additive include a cured product of a silicone compound, such as a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil, which enhances releasability from the thermal transfer sheet.
Further, an ultraviolet absorber can be used as an additive to prevent fading of a color image due to light.

The heat transfer sheet as described above is used in combination with the heat transfer sheet. As shown in FIG. 4, a typical thermal transfer sheet 6 is configured by providing a thermal transfer layer 8 on one surface of a support 7, and this thermal transfer layer 8
When heated, the dye or pigment contained therein migrates onto the heat-transferred sheet.

The support 7 has a role of holding the thermal transfer layer 8, and since heat is applied to the thermal transfer layer, it is desirable that the support 7 has a mechanical strength that does not hinder handling even in a heated state. Moreover, in many cases, the thermal energy for thermal transfer is applied from the side of the support 7 on which the thermal transfer layer 8 is not provided, and therefore it is desirable that the support 7 also has the property of easily transmitting the thermal energy.

Specific examples of such a support 7 include condenser paper, glassine paper, sulfuric acid paper, highly sized paper, or a flexible thin layer sheet such as a plastic film. Of these, capacitor paper and polyethylene terephthalate film are often used, when heat resistance is important, capacitor paper is mainly used, and when rupture prevention during handling by a mechanical device is important, polyethylene terephthalate film is used. Mainly used. The thickness of the support 7 is usually 3 to 50 μm, preferably 5 to 15 μm.

The thermal transfer layer 8 contains a coloring material which, when heated, escapes from the thermal transfer layer and escapes from the thermal transfer layer to the receiving layer of the thermal transfer layer.

As such a coloring material, about 150-40
Examples thereof include disperse dyes having a relatively small molecular weight of about 0, oil dyes, certain basic dyes, and intermediates that can be converted into these dyes. Among these, thermal transfer temperature, thermal transfer efficiency, hue, It is selected and used in consideration of color rendering and weather resistance.

The coloring material is dispersed in an appropriate synthetic resin binder for forming the thermal transfer layer, and is provided on the support 7. As such a synthetic resin binder, usually,
It is preferable to select a material that has high heat resistance and does not hinder the transfer of the coloring material that occurs when heated. For example, the following materials are used. (I) Cellulose-based resin Ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxycellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, etc. (Ii) Vinyl resin Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, polyester, polyacrylamide and the like.

Among the above synthetic resin binders, polyvinyl butyral resin or cellulose resin is preferable from the viewpoint of heat resistance and the like.

To provide the thermal transfer layer 8 on the support 7, a coloring material and a synthetic resin binder are kneaded together with a solvent or a diluent to prepare a coating composition for the thermal transfer layer, which is supported by an appropriate printing method or coating method. It may be provided on the body 7. In addition, you may add an arbitrary additive in the coating composition for thermal transfer layers as needed.

The basic structure of the thermal transfer sheet is as described above. However, when the surface of the support is directly heated by a contact type heating means such as a thermal head, as shown in FIG. A lubricant layer 9 containing a lubricant such as wax or a release agent on the side of the support 7 where the thermal transfer layer is not provided.
By providing the heating element, it is possible to prevent fusion between the heating means such as a thermal head and the support and improve the slip.

The thermal transfer sheet may be in the form of a single sheet cut into the required size, may be in the form of a continuous sheet or in the form of a roll, and may be in the form of a tape having a narrow width.

When the thermal transfer layer 8 is provided on the support 7, the surface of the support 7 may be entirely coated with the coating composition for the thermal transfer layer containing the same coloring material, but in some cases, A plurality of coating compositions for thermal transfer layers each containing different coloring material may be formed on different areas of the surface of the support 7. For example, as shown in FIG. 6, a thermal transfer sheet in which a black thermal transfer layer 10 and a red thermal transfer layer 11 are laminated in parallel on a support 7, or a yellow thermal transfer layer 12, a red thermal transfer layer as shown in FIG. The thermal transfer sheet in which the thermal transfer layer 13, the blue thermal transfer layer 14, and the black thermal transfer layer 15 are repeatedly provided on the support can be used. By using such a thermal transfer sheet provided with a plurality of thermal transfer layers having different hues, there is an advantage that a multicolor image can be obtained by one thermal transfer sheet.

The thermal transfer sheet may be provided with a perforation, or may be provided with a registration mark for detecting the position of an area having a different hue, thereby facilitating use.

The thermal transfer sheet and the thermal transfer sheet prepared as described above are superposed facing each other so that the thermal transfer layer of the thermal transfer sheet and the receiving layer of the thermal transfer sheet are in contact with each other as shown in FIG. The coloring material in the thermal transfer layer is transferred to the receiving layer by applying thermal energy according to image information to the interface between the receiving layer and the receiving layer.

As the heat source for giving the heat energy, in addition to the thermal head, arable land such as laser light, infrared flash and hot pen can be used. The type of applying thermal energy may be performed from the side of the thermal transfer sheet, may be performed from the side of the thermal transfer sheet, or may be from both sides. From the viewpoint of effective utilization of thermal energy, the thermal transfer sheet side is preferred. However, when the heat energy is applied from the heat transfer sheet side, the applied heat energy is controlled to express the gradation of the light and shade of the image, or the color material is promoted to diffuse on the heat transfer sheet. This is preferable in the sense of further ensuring the expression of the continuous gradation, and in the method of applying heat energy from both sides, the advantages of both methods can be simultaneously enjoyed.

When a thermal head is used as a heat source for applying heat energy, the applied heat energy can be changed continuously or in multiple steps by modulating the voltage or pulse width applied to the thermal head.

When a laser is used as a heat source for giving heat energy, the heat energy to be given can be changed by changing the light quantity of the laser beam or the irradiation area. If a dot generator with a built-in acousto-optic element is used, it is possible to give heat energy according to the size of the halftone dot. When using a laser beam, it is advisable to bring the thermal transfer sheet and the thermal transfer sheet into close contact with each other.
Further, the surface irradiated with the laser light may be colored black, for example, in order to improve absorption of the laser light.

When an infrared flash lamp is used as a heat source for providing heat energy, it is preferable to perform it through a colored layer such as black as in the case of using laser light.
Alternatively, a pattern or a halftone dot pattern that continuously expresses shades of an image such as black may be used and may be performed through these patterns, or a coloring layer such as black on one surface and a negative of the above pattern may be used. Corresponding negative patterns may be combined.

When thermal energy is applied to the interface between the thermal transfer layer and the receiving layer as described above, the coloring material in the thermal transfer layer vaporizes or melts in an amount corresponding to the applied thermal energy, and the coloring material in the receiving layer. Heat transfer and acceptance.

By the above-mentioned thermal transfer recording, a color material corresponding to thermal energy is thermally transferred to the receiving layer to record an image of one color. It is also possible to obtain a color photographic tone color image formed by combining the respective colors by sequentially replacing the red, indigo, and if necessary black black thermal transfer sheets and performing thermal transfer according to each color. Incidentally, instead of using the thermal transfer sheet of each color in this way, a thermal transfer sheet having an area formed by separately coating each color as shown in FIG. 7 is used, and a yellow color separation image is first formed by using the yellow area. Thermal transfer, then using the red area of the thermal transfer sheet, yellow by repeating the following in sequence,
If a method of thermally transferring a color-separated image of red, indigo, and optionally black is adopted, there is an advantage that the replacement of the thermal transfer sheet becomes unnecessary.

The quality of the image obtained can be improved by appropriately adjusting the size of the heat source used for applying the heat energy, the adhesion between the heat transfer sheet and the heat transfer target sheet, and the heat energy.

The heat-transferable sheet according to the present invention is combined with a heat-transfer sheet to print using various printers of the thermal printing system, print production of photographs by facsimile or magnetic recording system, print production from television screen. It can be used for

For example, one screen of the received television is displayed on a storage medium such as a magnetic tape or a magnetic disk.
The signals of the color separation patterns of yellow, red, indigo, and black are stored as necessary, and the signals of the stored color separation patterns are output, and the thermal energy corresponding to the signals is output to the thermal head or the like. When the heat source is applied to the superposed body of the heat transfer sheet and the heat transfer sheet and the heat transfer is sequentially performed for each color, the screen of the television can be reproduced as a sheet-like print. When such a combination of a transfer sheet and a heat transfer sheet according to the present invention is used for a screen printout of such a television, a white transfer sheet is usually used as the heat transfer sheet. A receptive layer alone, or a colorless and transparent receptive layer lined with a substrate such as paper,
Alternatively, it is convenient to obtain a reflection image by using a white receiving layer lined with a substrate such as paper.

The same as the above can be carried out when a combination of characters, figures, symbols and colors formed on the CRT screen by using a computer or a graphic pattern is used as an original image. Is a fixed image such as a painting, photograph, or printed matter, or a person, still life,
When it is an actual object such as a landscape, it can be performed in the same manner as above by using an appropriate means such as a video camera as an intermediary. Further, when generating signals of each color separation pattern from the original image, an electronic plate making machine (color scanner) used for photolithography of printing may be used.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 A PET film having a thickness of 9 μm (Toyobo Co., Ltd. SPET) having one surface corona-treated was used as a support, and a coating composition for a thermal transfer layer having the following composition was wire-bar coated on the corona-treated film surface. To form a dry thickness of 1 μm, apply 1 or 2 drops of silicone oil (X-41.4003A, made by Shin-Etsu Silicone) on the back surface with a dropper, then spread on the entire surface and apply a back surface treatment coating for thermal transfer. It was a sheet. Paint composition for thermal transfer layer Disperse dye (Kayaset Blue 14 manufactured by Nippon Kayaku Co., Ltd. 14 parts by weight 36) Ethyl hydroxyethyl cellulose (Her 5 parts by weight manufactured by Cyures) Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight Dioxane 10 parts by weight 150 μm synthetic as a base material Paper (Oji Yuka YUPO-
FPG-150) was used to apply a coating composition for a receiving layer having the following composition onto the surface by wire bar coating so that the dry thickness was 10 μm to form a heat transferable sheet. Drying was performed with a dryer for temporary drying and then in an oven at 100 ° C. for 1 hour (the solvent was sufficiently removed). Receptor layer coating composition Byron 103 (Toyobo polyester resin 8 parts by weight resin, Tg = 47 ° C.) Elvalloy 741 (Mitsui Polychemical, 2 parts by weight EVA polymer plasticizer, Tg = −32 ° C.) KF-393 (Shin-Etsu Silicol, Amino 0.125 parts by weight modified silicone oil) X-225-343 (Shin-Etsu Silicone, 0.125 parts by weight epoxy modified silicone oil) Toluene 70 parts by weight Methyl ethyl ketone 10 parts by weight Cyclohexanone 20 parts by weight Byron 103 is The second region forming synthetic resin, the Elvalloy 741 is the first region forming synthetic resin,
Since these have poor compatibility with each other, when they are dissolved in a solvent and then applied on a substrate and dried, phase separation occurs and the first region and the second region are formed.

The surface of the receiving layer obtained as described above is
The Elvalloy 741 resin, which is the first region, is almost surrounded by the Byron 103 resin, which is the second region, and the size of the first region formed by being surrounded by the second region is in the range of 5 μm to 100 μm. The ratio of the integrated area on the surface was 30% of the entire first region.

The thermal transfer sheet and the thermal transfer sheet obtained as described above are superposed so that the thermal transfer layer and the receiving layer are in contact with each other, and the output of the thermal head is 1 W / dot, pulse from the support side of the thermal transfer sheet. Width 0.3-4.5 msec, dot density 3 dots / mm,
As a result of recording under the above condition, the optical reflection density of the high color density recording portion was measured with a Macbeth RD918 reflection densitometer, and a value of 2.0 was obtained. In addition, the color tone obtained at this time had the same transparency as that in which each dye monomolecularly dispersed to develop a color.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion acceleration test, no image disturbance due to dye diffusion was observed, and the density of the recording portion did not decrease.

By combining the thermal transfer sheet and the thermal transfer sheet as described above, the relationship between the voltage application time to the thermal head and the obtained optical reflection density of the high color density recording section was investigated and obtained. The obtained results are shown in the curve 1 of FIG.
Shown in. Comparative Example 1 On the same substrate as in Example 1, a receptive layer-forming coating composition having the following composition was applied by wire bar coating so as to have a dry thickness of 10 μm to form a heat transferable sheet. Receptor layer forming coating composition Elvalloy 741 (manufactured by Mitsui Polychemicals) 10 parts by weight KF-393 (manufactured by Shin-Etsu Silicone) 0.125 parts by weight X-22-343 (manufactured by Shin-Etsu Silicone) 0.125 parts by weight Toluene 50 parts by weight Methyl ethyl ketone 50 parts by weight Recording was carried out in the same manner as in Example 1 using the thermal transfer sheet obtained as described above and the thermal transfer sheet similar to that obtained in Example 1 to obtain the recorded image. The optical reflection density of the high color density recording portion of the sheet was 2.1, which was higher than the density obtained in Example 1.

However, when the above-described recorded sheet was left in an oven at 60 ° C. for 7 hours and subjected to a thermal diffusion acceleration test, the image was remarkably disturbed by dye diffusion and a decrease in the overall recording area density was observed. The optical reflection density of the high color density recording portion decreased to 1.8. Comparative Example 2 On the same substrate as in Example 1, a receptive layer-forming coating composition having the following composition was applied by wire bar coating so as to have a dry thickness of 10 μm to form a heat transferable sheet. Receptor layer forming coating composition Byron 103 (Toyobo polyester resin 10 parts by weight fat) KF-393 (Shin-Etsu Silicone) 0.125 parts by weight X-22-343 (Shin-Etsu Silicone) 0.125 parts by weight Toluene 50 parts by weight Parts Methyl ethyl ketone 50 parts by weight Recording was carried out in the same manner as in Example 1 using the heat transferable sheet obtained as described above and the heat transfer sheet of Example 1, and a high color density recording portion of the obtained recorded sheet was obtained. The optical reflection density of was 1.4.

This value was lower than the color density of Example 1, and the obtained color tone was poor in transparency and lacked in color development as compared with Example 1.

When the above recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion loss test, no image disturbance due to dye diffusion was observed, but the color density was as high as 1.7. The color tone also changed to a transparent one similar to that when each molecule of each dye dispersed and developed a color.

On the same substrate as in Example 1, a receptive layer-forming coating composition having the following composition was applied by wire bar coating to a dry thickness of 10 μm to form a thermal transfer sheet. Receptor layer forming coating composition Byron 103 (manufactured by Toyobo, Tg; 47 ° C) 7 parts by weight Versalon 1138 (Henkel Japan poly 3 parts by weight amide resin Tg; -4 ° C) KF393 (Shin-Etsu Silicone) 0.125 parts by weight Parts X-22-343 (manufactured by Shin-Etsu Silicone) 0.125 parts by weight toluene 57 parts by weight xylene 13 parts by weight methyl ethyl ketone 6.3 parts by weight 2-butanol 14 parts by weight cyclohexanone 30 parts by weight Byron 103 is a synthesis for forming the second region. And a bar salon 1138 is a synthetic resin for forming the first region,
Since they have poor compatibility with each other, when they are dissolved in a solvent and then coated on a substrate and dried, phase separation occurs and
A region and a second region are formed.

As described above, the surface of the receptive layer thus obtained is almost completely surrounded by the Barsalon 1138 resin which is the first region and the Byron 103 resin which is the second region, and is surrounded by the second region. The size of the first region thus formed was in the range of 1 μm to 100 μm, and the ratio of the integrated area on the surface was 30% of the entire first region.

Recording was performed in the same manner as in Example 1 using the thermal transfer sheet obtained as described above and the same thermal transfer sheet as in Example 1, and the high color density recording portion of the obtained recorded sheet was obtained. Had an optical reflection density of 1.79.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion acceleration test, no disturbance of the image due to dye diffusion was observed, and the density of the recording portion did not decrease.

On the same base material as in Example 1, a receptive layer-forming coating composition having the following composition was applied by wire bar coating to a dry thickness of 10 μm to form a thermal transfer sheet. Receptor layer coating composition Pandex T5670 (Dainippon Ink Chemicals 3 parts by weight Polyurethane elastomer Tg; -35 ° C) S-REC BX-1 (Sekisui Chemical Polyvinyl 7 parts by weight rubutyral resin, Tg; + 83 ° C) KF -393 (manufactured by Shin-Etsu Silicone) 0.125 parts by weight X-22-343 (manufactured by Shin-Etsu Silicone) 0.125 parts by weight Toluene 70 parts by weight Methyl ethyl ketone 70 parts by weight Methyl isobutyl ketone 12 parts by weight Ethyl Cellosolve 5 parts by weight Pandex T5670 is S-REC BX-1 is a synthetic resin for forming the first region, and S-REC BX-1 is a synthetic resin for forming a second cool air. Since they have poor compatibility with each other, they are dissolved in a solvent and then coated on a substrate and dried. Then, phase separation occurs and the first region and the second region are formed.

The surface of the receptor layer obtained as described above is
The Pandex T5670 resin, which is the first region, is almost surrounded by the S-REC BX-1 resin, which is the second region, and the size of the first region formed by being surrounded by the second region is 20 μm or less. The ratio of the area to be back-coated on the surface was 15% of the whole in the first region.

Using the thermal transfer sheet thus obtained and the same thermal transfer sheet as in Example 1, Example 1 was used.
When recording was carried out in the same manner as above, the optical reflection density of the high color density recording portion of the obtained recorded sheet showed a value of 1.3.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion accelerating test, the image was not disturbed due to dye diffusion, and the density of the recording area did not decrease. Example 4 On the same substrate as in Example 1, a receptive layer-forming coating composition having the following composition was applied by wire bar coating to a dry thickness of 10 μm to form a heat transferable sheet. Receptor layer forming coating composition Byron 630 (Toyobo polyester resin 2 parts by weight fat Tg; 7 ° C) S-REC BX-1 (Sekisui Chemical Polyvinyl 4 parts by weight rubutyral resin Tg; 83 ° C) KF-393 (Shin-Etsu Silicone) 0.075 parts by weight X-22-343 (manufactured by Shin-Etsu Silicone) 0.075 parts by weight Toluene 46 parts by weight Methyl ethyl ketone 42 parts by weight Cyclohexanone 4 parts by weight Byron 630 is a synthetic resin for forming the first region, and S-REC BX-1. Is a synthetic resin for forming the second region, and since these are poorly compatible with each other, when they are dissolved in a solvent and then applied on a substrate and dried, phase separation occurs and the first region and the second region are formed. And are formed.

The surface of the receptive layer obtained as described above is
The Byron 630 resin, which is the first region, is almost surrounded by the S-REC BX-1 resin, which is the second region, and the size of the first region formed by being surrounded by the second region is 1 μm to 100 μm. The ratio of the integrated area on the surface was 30% in the first region.

Recording was performed in the same manner as in Example 1 using the thermal transfer sheet obtained as described above and the thermal transfer sheet similar to that in Example 1. High color density recording of the obtained recorded sheet was performed. The optical reflection density of the part showed a value of 1.2.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion acceleration test, no image disturbance due to dye diffusion was observed and no decrease in the recording portion density occurred. Example 5 A receptive layer-forming coating composition having the following composition was applied and formed on the same substrate as in Example 1 by wire bar coating so that the thickness when dried was 15 μm to obtain a heat transferable sheet. Receptor layer forming coating composition Byron 103 (Toyobo polyester 8 parts by weight Tg; 47 ° C) Elvalloy 741 (Mitsui Polychemical T2 parts by weight; -32 ° C) KF-393 (Shin-Etsu Silicone) 0.125 Weight part X-22-343 (Shin-Etsu Silicone) 0.125 weight part Tinuvin 328 (Ciba-Geigy UV absorption 0.5 weight part sorbent) Toluene 70 weight part Methyl ethyl ketone 10 weight part Cyclohexanone 20 weight part Byron 103 is body 2 area Elvalloy 741 is a synthetic resin for forming the first region,
Since these have poor compatibility with each other, when they are dissolved in a solvent and then applied on a substrate and dried, phase separation occurs and the first region and the second region are formed.

Recording was carried out in the same manner as in Example 1 using the thermal transfer sheet thus obtained and the same thermal transfer sheet as in Example 1, and the hue and recording portion optical density were the same as in Example 1. Got the result.

The recorded sheet was left in an oven at 60 ° C. for 7 days to conduct a thermal diffusion acceleration test, and the same result as in Example 1 was obtained.

The recorded sheet was subjected to light irradiation with a Ducycle Super Long Life Sunshine Weather Meter (manufactured by Suga Test Instruments), and a light resistance test was conducted. As a result, the recorded sheet obtained in Example 1 was irradiated with light of 2 times.
Although the color changed to a reddish hue after a long time, the recorded sheet according to the recorded sheet of this example changed its color even after 2 hours of light irradiation because the ultraviolet absorber was contained in the receiving layer. Was not recognized. Example 6 The components below were dispersed in water and continuously stirred at 50 ° C. for 60 minutes, and then ultrasonically dispersed for 5 minutes to prepare a coating composition for forming a receiving layer. Receptor Layer Coating Composition Gohsenal T330 (Nippon Gosei Poly Poly 4 parts by weight Nyl Alcohol Tg; 68 ° C.) Polyzol EVA AD-5 (Showa High Polymer 10 parts by weight Ethylene Acetate Vinyl Emulsion Tg; 0 ° C.) Water 76 parts by weight Gossenal T330 is a synthetic resin for forming the second region, and Polyzol EVAAD-5 is a synthetic resin for forming the one region.

The coating composition for forming a receiving layer was applied by wire bar coating on the same substrate as in Example 1 so that the thickness when dried was 10 μm, to obtain a heat transferable sheet.

The surface of the receptive layer obtained above is formed such that the ethylene vinyl acetate resin which is the first region is almost surrounded by the polyvinyl alcohol resin which is the second region, and is surrounded by the first region. The size of the second region was in the range of 5 μm or less, and the ratio of the integrated area on the surface was 50% of the entire first region.

Recording was performed in the same manner as in Example 1 using the thermal transfer sheet obtained as described above and the thermal transfer sheet similar to that in Example 1, and thermal transfer was performed on the surface of the obtained recorded sheet. The transfer layer of the sheet has transferred. After removing the transferred portion with an adhesive tape, the optical reflection density of the high color density recording portion of the obtained recorded sheet was measured.
We got a value of 0.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and a thermal diffusion acceleration test was conducted, no disturbance of the image due to dye diffusion was observed, and the density of the recording area did not decrease. Example 7 A synthetic paper having a thickness of 150 μm (Yupo FPG-150 manufactured by Oji Yuka Co., Ltd.) was used as a base material, and a coating composition for forming a receiving layer having the following composition was wire-bar coated thereon to give a dry thickness of 5 μm. The coating was formed so that Receptor layer forming coating composition Elvalloy 742 (manufactured by Mitsui Polychemicals) 10 parts by weight KF-393 (amino-modified silicone oil 0.125 parts by weight Le Shin-Etsu Silicone Tg; -32 ° C.) X-22-343 (epoxy-modified silicone) 0.125 parts by weight Noil Oil Shin-Etsu Silicone) Toluene 50 parts by weight Methyl ethyl ketone 50 parts by weight On the other hand, a mask for patterning the receptor layer formed as described above was manufactured as follows.

A 0.1 mm thick iron thin plate was first washed, and then a photosensitive resin (FPR manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied thereon by spin coating so that the film thickness when dried was 5 μm. Next, a line width of 20 μm and a pitch of 200 μm
The above-mentioned line-shaped originals were overlaid, exposed for 1 minute with a printer (manufactured by Dojunkoki Co., Ltd.) equipped with an ultra-high pressure mercury lamp, and developed by a predetermined method. Then, the patterning image and the surface to be judged are covered with a resin and then etched with an iron chloride solution to obtain a line width of 20 μm and a pitch of 20 μm.
An iron mask having a 0 μm stripe pattern was obtained.

Then, this mask was superposed on the receiving layer, and an electron beam was irradiated with an electron beam irradiation device at an accelerating voltage of 175 kV for 30 megarads to cure the receiving layer in a pattern. Further, after rotating the mask on the receptive layer at 90 ° C., it was similarly irradiated with an electron beam at 30 megarads to partially crosslink the receptive layer in a lattice form to obtain a heat transferable sheet. In addition,
The lattice-partially cross-linked portion corresponds to the second region.

Recording was performed in the same manner as in Example 1 using the thermal transfer sheet obtained as described above and the thermal transfer sheet similar to that in Example 1. High color density recording of the obtained recorded sheet was performed. The optical reflection density of the part showed a value of 1.8.

When the above-mentioned recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion acceleration test, no disturbance of the image due to dye diffusion was observed, and the density of the recording portion did not decrease. Example 8 Instead of Kayaset Blue 136 manufactured by Nippon Kayaku as a dye, Kayaset Red B manufactured by Nippon Kayaku, which is a magenta dye, is used.
A thermal transfer sheet and a thermal transfer sheet were obtained in the same manner as in Example 1 except that 2.5 parts by weight of was used. By combining these in the same manner as in Example 1, the relationship between the voltage application time to the thermal head and the obtained optical reflection density of the high color density recording portion was investigated, and the obtained result is shown by the curve 2 in FIG. Example 9 Instead of Kayaset Blue 136 manufactured by Nippon Kayaku Co., Ltd., a yellow dye PTY-52 manufactured by Mitsubishi Kasei Co., Ltd. was used as a dye.
A thermal transfer sheet and a thermal transfer sheet were obtained in the same manner as in Example 1 except that 6 parts by weight was used. By combining these in the same manner as in Example 1, the relationship with the optical reflection density of the high color density recording section where the voltage application time to the thermal head can be obtained was investigated, and the obtained result is shown by the curve 3 in FIG. Example 10 In Example 1, as a support for the thermal transfer sheet, the thickness was 9 μm.
m PET film was replaced by 10 μm thick condenser paper, and the backside treatment with silicone oil was omitted, and printing was carried out in the same manner as in Example 1. As a result, the optical reflection density of the high color density recording portion of the recorded sheet was 1.4
A value of 0 was shown. Example 11 The result of printing in the same manner as in Example 10 except that 2.5 parts by weight of Nippon Kayaku Kayaset Red B was added instead of Nippon Kayaku Kayaset Blue 136 as the dye in Example 10. The optical reflection density of the high color density recording portion of the recorded sheet was 1.38. Example 12 In Example 10, Mitsubishi Kasei PTY-52 was used as a dye in place of Kayaset Blue 136 manufactured by Nippon Kayaku Co., Ltd.
As a result of printing in the same manner as in Example 11 except that the weight part was added, the optical reflection density of the high color density recording part of the recorded sheet was 1.38. Comparative Example 3 A synthetic paper (YUPO-FPG-15 manufactured by Oji Yuka Co., Ltd.) whose surface was covered with calcium carbonate powder as a heat transferable sheet.
As a result of printing in the same manner as in Example 1 except that (0) was used, the optical reflection density of the high color density recording portion of the recorded sheet was a low value of 0.44. Example 13 A 100-μm-thick polyethylene terephthalate film (T-PET manufactured by Toray) was coated with a primer layer-forming coating composition having the following composition by a spin coater so that the layer thickness when dried was 1 μm. Drying was carried out by placing the PET film coated with the coating material in an oven at 90 ° C. for 1 minute.

Receptor layer forming coating composition AD502 (Toyo Morton Co., Ltd., Polyes 0.95 parts by weight terpolyol) Coronate L (Nippon Polyurethane Co., Ltd., 0.15 parts by weight isocyanate) Toluene 6 parts by weight Methyl ethyl ketone 6 parts by weight 7 parts by weight of ethyl acetate Next, a negative photoresist (Asahi Kasei Co., Ltd., A
PRG-22) has a thickness of 5 when dried by a spin coater.
It was applied to 0 μm and then dried in an oven at 100 ° C. for 10 minutes.

Next, the surface of the silver salt transparent original film on which the dot pattern in which the image system pattern having one side of 170 μm is arranged at intervals of 30 μm is formed and the negative resist layer surface are brought into close contact, and a point light source of a high pressure mercury lamp is used. It was exposed to a UV printer for 10 seconds and then heated to 50 ° C.
% Aqueous solution of sodium bicarbonate to dissolve and remove the uncured portions of the grid-like resist, and then wash with water to obtain a line width of 30 μm.
A grid-like pattern consisting of m and an interval of 170 μm was formed on the film. This lattice pattern is the second region (Tg of this region is 80 ° C.).

Next, a coating composition (I) for forming a receiving layer having the following composition was applied by a spin coater and then dried by a dryer. This process was repeated 3 times to form the first region in the portion surrounded by the grid pattern on the film. Receptor layer forming composition (I) Elvalloy 741 (Mitsui Polychemical Co., Ltd., 10 parts by weight EVA polymer plasticizer) Toluene 45 parts by weight Methyl ethyl ketone 45 parts by weight Further, the following receiving layer forming coating composition (II) is spin coated. A thermal transfer sheet was formed by coating with a machine so that the portion surrounded by the grid-like pattern of the film during drying is completely filled. Dry temporarily with a dryer and then 1
It was carried out at 00 ° C. for 1 hour. Receptor Layer Forming Composition (II) Elvalloy 741 (Mitsui Polychemical Co., Ltd., 10 parts by weight EVA polymer plasticizer) KF-393 (Shin-Etsu Silicone Co., Ltd., Ami 0.125 parts by weight unmodified silicone oil) X- 22-343 (manufactured by Shin-Etsu Silicone Co., Ltd., 0.125 parts by weight epoxy modified silicone oil) Toluene 45 parts by weight Methyl ethyl ketone 45 parts by weight In the surface of the receiving layer obtained above, the first region, Elvalloy 741 is the second region. It is almost surrounded by the negative photoresist, and the size of the first region formed by being surrounded by the photoresist is 100 μm to 200 μm.
The ratio of the integrated area on the surface in the range of m is
The first area was 70% of the whole.

Heat Transfer Transfer Sheet Obtained Above and Example 1
Recording was performed in the same manner as in Example 1 using the same thermal transfer sheet as in Example 1, and the optical reflection density of the high color recording portion of the recorded sheet obtained was 1.9.

When the recorded sheet was left in an oven at 60 ° C. for 7 days and subjected to a thermal diffusion accelerating test, no image disturbance due to dye diffusion was observed and no decrease in the recording area density occurred. Example 14 The following respective component liquids were sufficiently kneaded with a three-roll mill to prepare a coating composition for forming a receiving layer having a viscosity of 2500 ps. Receptor layer forming coating composition Polyethylene glycol (Molecular weight 2000) 5 parts by weight Terpene phenolic resin (Yasuhara Yushi Kogyo Co., Ltd., 12 parts by weight YS Polystar S145) Dioctyl phthalate 2 parts by weight Triethylene glycol-mono-n-butyl 6 parts by weight Ruether Kaolin (Kaolin ASP 14 parts by weight made by Kaolin Tsuchiya-170 parts by weight) A silicone resin layer is formed on the surface of a photographic manuscript in which square patterns (black portions) having a side of 150 μm are regularly arranged at intervals of 30 μm in both length and width. A waterless planographic printing plate was prepared and printed on a mirror-coated paper with the above-mentioned coating composition for forming a receiving layer to obtain a heat transferable sheet having repeating 150 μm square island patterns. Printing was performed in the same manner as in Example 1 using the thus-transferred thermal transfer sheet and the same thermal transfer sheet as in Example 1 to obtain a colored image with a maximum density of 1.4. 50 sheets of this recorded sheet
After heating at ℃ for 7 days, the image was not blurred because the color-developed areas were completely separated from each other.

The waterless planographic printing plate used above was prepared as follows. Preparation of Silicone Resin 266 parts of acryloxypropyltrichlorosilane was dropped into a mixture of 500 parts of water, 100 parts of toluene and 50 parts of isopropanol at 5 to 10 ° C. for 1 hour, and then the hydrochloric acid layer was separated to pH 6.8. Washed with water. Next, 612 parts of α, ω-dihydroxydimethylorganopolysiloxane of the following formula, 0.5 part of potassium acetate and 0.5 part of hydroquinone were added to this siloxane and toluene layer,
The reaction was carried out at ˜115 ° C. for 8 hours, and then toluene was distilled under reduced pressure to obtain a solid organopolysiloxane having a pale yellow and transparent pour point of 45 ° C., and the yield was 754 parts.

[0084]

[Chemical 1] Preparation of sensitizer A Grignard reagent was prepared in tetrahydrofuran from 0.2 mol of 4-trimethylsilylchlorobenzene and 0.2 mol of magnesium, reacted with 0.2 mol of 4-dimethylaminobenzaldehyde, and then reacted with benzaldehyde.
4-Dimethylamino-4'-trimethylsilylbenzophenone was synthesized by adding 2 mol and conducting the Oppenauer oxidation reaction. Photopolymerization organopolysiloxane obtained in the preparation of lithographic printing plate 1000 parts 4-dimethylamino-4'-tri 5 parts obtained with 5 parts methylsilylbenzophenone toluene 1000 parts A waterless planographic printing plate was obtained by spin-coating the coated film so that the coating thickness was about 5 μm and drying. A photographic original was adhered to the non-aluminum surface of the waterless lithographic printing plate obtained in the preparation of the lithographic printing plate in a reduced thickness, irradiated with light from a 3 kW high pressure mercury lamp 40 cm away for 30 seconds, and then developed with xylene. A lithographic printing plate that did not require fountain solution was obtained. The printing plate obtained by printing was printed using an offset 1-color machine (KOR type printing machine, manufactured by Heidelberg), except that the water bar was removed.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a thermal transfer sheet according to the present invention.

FIG. 2 is a cross-sectional view of a thermal transfer sheet according to the present invention.

FIG. 3 is a schematic enlarged view of the surface of the receiving layer.

FIG. 4 is a cross-sectional view of a thermal transfer sheet used in combination with a thermal transfer sheet.

FIG. 5 is a cross-sectional view of a thermal transfer sheet used in combination with a thermal transfer sheet.

FIG. 6 is a cross-sectional view of a thermal transfer sheet used in combination with a thermal transfer sheet.

FIG. 7 is a sectional view of a thermal transfer sheet used in combination with a thermal transfer sheet.

FIG. 8 is a schematic view when a heat transfer target sheet and a heat transfer sheet are used in combination.

FIG. 9 shows the relationship between the voltage application time to the thermal head and the obtained optical reflection density of the high color density recording section when the thermal transfer sheet and the thermal transfer sheet according to the present invention are combined and heated. FIG.

[Explanation of symbols]

 1 Thermal Transfer Sheet 2 Base Material 3 Receptive Layer 4 First Area 5 Second Area 6 Thermal Transfer Sheet 7 Support 8 Thermal Transfer Layer 9 Sliding Layer

Claims (1)

[Claims] 1. A thermal transfer sheet used in combination with a thermal transfer sheet having a thermal transfer layer containing a heat transferable dye, wherein thermal energy according to an image signal is applied from a thermal head or a laser. In a thermal transfer sheet, which is configured to form an image with the heat transferable dye on a thermal transfer sheet, a base material and a base material provided on the base material, and transferred from the thermal transfer sheet when heated by the energy. And a receiving layer made of a synthetic resin layer that receives the dye.
The thermal transfer sheet, wherein the receiving layer has a portion cured by ionizing radiation and an uncured portion.