JPH01103489A - Transfer recording medium - Google Patents

Abstract

PURPOSE:To obtain a uniform image free of ununiformity in density by sequentially providing an intermediate layer comprising a photolyzable compound and a photo-thermal converting substance, a barrier layer comprising a film-forming substance and a thermally transferable solid ink layer on one side of a transparent base. CONSTITUTION:An intermediate layer 9, a barrier layer 12 and a thermally transferable solid ink layer 4 are sequentially provided on one side of a transparent base 1. When the back side of this transfer recording medium is irradiated with optical energy, a photo-thermal converting substance contained in the intermediate layer 9 absorbs light, and converts the optical energy into thermal energy. The thermal energy is conducted through the barrier layer 12 in the thickness direction of the layer to bring a thermally transferable solid ink provided on the ink layer 4 into a heat-fused or heat-sublimed state. At the same time, a photolyzable compound is photolyzed to generate a gas, which is expanded in volume to strongly press the ink layer 4 through the barrier layer 12 against the surface of an image-receiving sheet 5, whereby the surface of the ink transferred is made to be highly smooth. Consequently, at the time of transferring the second and latter inks, the contact area of the ink is increased, and transferring with a uniform and high density can be achieved.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is a transfer recording method suitable for recording high-resolution characters or images, and particularly a color transfer recording method suitable for multi-color or full-color recording. Regarding the medium.

<Prior art> As shown in FIG. 1, a conventionally proposed transfer recording medium includes a light-reflecting layer 2 on the surface of a light-transmitting support 1, and a photodegradable compound on the bottom surface for improving transferability. The photothermal conversion layer 3 has a structure in which a thermally transferable solid ink layer 4 is provided on the lower surface of the photothermal conversion layer 3. In order to perform recording using the transfer recording medium, the light reflective layer 2 is removed according to the information pattern by a well-known discharge destruction recording method, and the thermally transferable solid ink layer 4 is removed as shown in FIG. The surface coated with the photoreceptor 5 is brought into close contact with the image receiving paper 5, and a xenon flash lamp 6 irradiates flash light containing ultraviolet rays, visible rays, and infrared rays from the light reflecting layer 2.

Then, the flashing light irradiated onto the portion where the light-reflecting layer 2 remains is reflected, and the flashing light irradiating the portion where the light-reflecting layer is removed passes through the support 1 and reaches the photothermal conversion layer 3. The photothermal conversion layer absorbs flash energy and effectively converts it into thermal energy. As a result, the thermally transferable solid ink layer 4 starts thermal melting or thermal sublimation and is transferred onto the surface of the image receiving sheet 5. Thereafter, a transferred image was obtained by peeling off the discharge recording medium and the image receiving sheet.

When layering colors, we adopt a method of subtractive color mixing by repeating each of the above steps for each monochromatic heat transferable solid ink layer consisting of yellow, magenta, cyan, and if necessary black. Ta. However, the above-mentioned conventional transfer recording medium has major defects in the subtractive color mixing properties of yellow, magenta, and cyan inks, that is, the color overlapping characteristics and density uniformity.

That is, when the first color ink is transferred, the ink is transferred very well due to the volumetric expansion of the gas generated as a result of photodecomposition of the photodegradable compound, but on the other hand, the ink is transferred under a strong pressing force due to the gas expansion. As a result, the air permeability of the transferred ink surface increases significantly, and the ink layer, which is in a thermally melted or thermally sublimated state, is exposed to the rapid ejection force of gas generated as a result of photolysis. Due to the retention of this gas in the ink layer, the ink layer solidifies in a roughened state, making it impossible to maintain a smooth surface. As a result, when the second color ink is transferred onto the surface of the first color ink layer, it is transferred onto a surface with high air permeability (on the contrary, it is transferred onto a surface with low smoothness).

Therefore, it becomes extremely difficult to dissipate the gas generated as a result of photolysis, and the transferred ink surface becomes even rougher than in the case of the first color. Furthermore, due to the rapid ejection force of gas,
A trapping problem occurs in which a portion of the first color ink is attached to the medium side and peeled off depending on the degree of surface roughening. Furthermore, since the transfer is to a surface with low smoothness, the situation is disadvantageous for the transfer of the second color ink. For the same reason, the transferability of the third color becomes even more difficult, and satisfactory color overlapping becomes impossible. Furthermore, if there is a distribution of light energy over the area to be irradiated, and the part that has been irradiated with light twice before the image-receiving sheet and transfer recording medium are separated is the part that has been irradiated with light once; Since there is a large difference in the air permeability and smoothness of the ink surface, this results in uneven density. Therefore, when a color transfer image is obtained by repeating light irradiation, it is difficult to obtain a uniform density without unevenness.

<Problems to be Solved by the Invention> In view of the above-mentioned circumstances, the present invention provides a transfer recording medium with improved subtractive color mixing characteristics so that a uniform image without density unevenness can be obtained.

Means for Solving the Problems> In view of the above circumstances, the present invention has been made as a result of intensive studies to solve the problems. The outline is that a transfer recording medium is prepared by sequentially providing an intermediate layer containing a photodegradable compound and a light-to-heat conversion layer material, a barrier layer consisting of a film-forming material, and a thermally transferable solid ink layer on one side of a light-transmitting support. A second invention is a transfer recording medium, further comprising a light reflective layer removable by discharge destruction recording on the other surface of the light-transmitting support constituting the transfer recording medium. .

First, the structure of the transfer recording medium according to the present invention will be explained in the third section.
This will be explained with reference to FIG. FIG. 3 shows a type in which a light reflection layer 2 is provided, and FIG. 4 shows a type in which a light reflection layer 2 is not provided. That is, in FIG. 3(A), a light reflective layer 2 removable by discharge destruction recording is provided on one side of a light-transmitting support 1, and an intermediate layer 9, a barrier layer 12, and a thermally transferable solid are provided on the other side. Ink layers 4 are successively provided. Figure 3 (f) is
The barrier layer 12 at the third head is replaced by the first barrier layer 1
0 and a second barrier layer 11. In FIG. 3(C), a peeling layer 13 is provided between the light-transmitting support 1 and the intermediate layer 9 in FIG. 3(A). In FIG. 3), a peeling layer 13 is provided between the light-transmitting support 1 and the intermediate layer 9 in FIG. 3). FIGS. 4(a), (c), (c) and 2) show other configurations of the transfer recording medium of the present invention, and FIGS. 3(a), 2), (c) and This is a type of transfer recording medium in which the light reflection M2 is not provided.

Next, the materials of each layer structure will be explained in detail below.

[Light-transparent support]

Various heat-resistant resin films such as polyethylene terephthalate, polyimide, polycarbonate, cellophane, and aromatic polyamide are used as the light-transmissive support used in the present invention, and the thickness of the film is 1 to 100 μm, preferably 4 to 30 μm. The range is appropriate.

[Light reflective layer]

Vapor-deposited films of metals such as aluminum, zinc, and tin, which are easily destroyed by electrical discharge, are applied. At this time, in order to improve discharge recording characteristics, a highly transparent roughened layer containing fine particles of silica, alumina, tin dioxide, hydrated alumina, etc. is provided between the support and the light reflective layer. It is preferable.

[Middle layer]

The intermediate layer in the present invention is formed by dissolving or dispersing a photodegradable compound and a photothermal conversion substance in a binder. In this case, suitable binder materials for the intermediate layer include organic solvent-soluble resins such as acrylic resins, styrene resins, and vinyl resins, and water-soluble resins such as polyvinyl alcohol, polyvinyl butyral, and isobutylene/maleic anhydride copolymers. It can be appropriately selected from among resins, various waxes, and rubbers.

Next, it is essential that the photodegradable compound blended into the intermediate layer be rapidly photodecomposed by light including ultraviolet rays, visible light, infrared rays, and the like. Material systems suitable for this purpose include diazo compounds and azide compounds. Among these, the diazo compounds include those conventionally used in the field of diazo copying materials.

That is, specific examples thereof include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-benzoylamino-2,5-jethoxybenzene, 4-diazo-1- Morpholinobenzene, 4-diazo-1-morpholino-2,5-dimethoxybenzene, 4-diazo-1-morpholino-2,5-jethoxybenzene, 4-diazo-1-pyrrolidino-3-methylbenzene, 4-diazo -1-pyrrolidino-2-methylbenzene 0.4-diazo-1-dimethylamino-2-
(4°chlorophenoxy)-5-chlorobenzene and the like can be mentioned.

On the other hand, as the azide compound, aromatic azide compounds are particularly effective, but in addition, 4,4'-diazide-diphenylsulfone, 4,4°-diazidebenzosulfone, 4.
4'-Diazidostilbene, 4,4'-diazidobenzalacetone, 2,6-di(4-azidobenzal)-4
-Methylcyclohexanone and the like can be applied to the present invention.

The above diazo compounds and azide compounds can be used alone or in combination of two or more. The appropriate amount of these photodegradable compounds to be used is 0.1 to 80 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total solid content in the intermediate layer.

Next, the photothermal conversion substance that is simultaneously incorporated into the intermediate layer is carbon black, which has the ability to absorb light energy including ultraviolet rays, visible light, infrared rays, etc. over a wider wavelength range and convert it into thermal energy more effectively. graphite,
Various organic pigments and dyes can be applied.

These photothermal conversion substances can be used alone or in combination of two or more. The amount of the photothermal conversion substance used is 1 to 50 parts by weight based on 100 parts by weight of the total solid content in the layer.
A suitable range of 3 to 30 parts by weight is preferred.

The intermediate layer paint contains the above-mentioned binder, photodegradable compound,
It is obtained by adding a photothermal conversion substance and various additives as necessary, and dissolving or dispersing it in a suitable solvent, and coats it on the support surface with a solvent coating method.
The coating is applied to a coating thickness of 1 to 20 μm, preferably 0.1 to 10 μm.

[Barrier layer - single layer structure]

The following items can be listed as the barrier layer composed of a single layer and the characteristics required when setting the layer.

(2) It must have sufficient heat resistance to prevent softening, melting, carbonization, thermal decomposition, etc., from the heat generated in the intermediate layer as a result of photothermal conversion.

2> It must have sufficient gas barrier properties so that the gas generated in the intermediate layer as a result of photolysis does not permeate into the thermally transferable solid ink layer.

3) Even if the layer is relatively thin, it should have sufficient mechanical strength so that the barrier layer will not be destroyed or ruptured by the force of the gas generated in the intermediate layer.

4) When laminated onto the intermediate layer, the intermediate layer is not significantly eroded and the properties of the intermediate layer are not impaired.

Materials for the resin forming the barrier layer made of a film-forming substance that satisfies the above characteristics include polyacrylic resin,
Polystyrene resin, polyvinyl resin, polyvinylidene resin, polyamide resin, polyimide resin,
Polyester resins, polyacetal resins, modified polyphenylene oxide resins, polyurethane resins, polycarbonate resins, polyarylate resins, polysulfone resins, fluorine resins, silicone resins, and copolymer resins between these resins, etc. Resin systems classified as thermosetting resins and other heat-resistant polymers (Tatsu Mita, Industrial Chemistry, Vol. 73, p. 1361, 197
(published in 2010), etc. These resins can be used alone or in combination of two or more, but the resins are not limited to these.

The solvent of the coating material for the barrier layer is required to have at least the properties of a solvent for dissolving these resins or a dispersion medium for dispersing them. In addition, during multilayer coating, coating streaks and coating unevenness can be generated at the interface between the intermediate layer and the barrier layer without significantly corroding the intermediate layer.
There must be no problems such as elution of photodegradable compounds or photothermal conversion substances in the intermediate layer. Specific examples of solvents for these barrier layer coatings include aliphatic hydrocarbons, aromatic hydrocarbons,
Examples include halogenated hydrocarbons, alcohols, ethers, ketones, esters, nitriles, carbon tetrachloride, carbon disulfide, and water. These solvents may be used alone or as a mixed solvent of two or more, but the solvents are not limited to these.

The barrier layer consisting of a single layer is prepared by adding the above-mentioned resin and additives such as a curing agent, a catalyst, a mold release agent and a surfactant as necessary, dissolving or dispersing it in an appropriate solvent, and then applying a solvent coating method. Laminated on the middle layer.

The thickness of the barrier layer composed of a single layer is 0.05~
A range of 10 μm, preferably 1 to 5 μm is suitable.

[Barrier layer - two-layer structure] Among the barrier layers composed of two layers, the first barrier layer provided in contact with the intermediate layer is the second barrier layer provided on top of this layer. The organic solvent in the barrier layer paint significantly erodes the intermediate layer, resulting in
This is provided to completely prevent problems such as coating streaks and uneven coating at the interface between the intermediate layer and the second barrier layer, and elution of photodegradable compounds and photothermal conversion substances in the intermediate layer. be. Therefore, the first barrier layer must have the organic solvent barrier properties of the second barrier layer coating. At the same time, the solvent of the first barrier layer coating should have little or no attack on the intermediate layer. It has been found that a resin that is water-soluble or soluble in a mixed solvent of water and an organic solvent is most suitable for the first barrier layer that satisfies these requirements. That is, specific examples include polyvinyl alcohol, polyvinyl butyral, polyethylene oxide, polyacrylic acid, polyamide, isobutylene/maleic anhydride copolymer resin, ethylene/vinyl alcohol copolymer resin, polyvinylidene chloride resin, vinylidene chloride, Examples include acrylonitrile copolymer resin, vinyl chloride/vinylidene chloride copolymer resin, propylene/vinyl chloride copolymer resin, and the like.

These resins can be used alone or in combination of two or more, but the resins are not limited to these.

The first barrier layer is prepared by dissolving the resin described above in water or a mixed solvent system of water and an organic solvent, and adding a curing agent, catalyst, etc. as necessary.
Various additives such as surfactants are added and laminated onto the intermediate layer using a solvent coating method. The thickness of the first barrier layer is 0.01-10uI111 preferably 0.5-5
A range of μm is suitable.

The second barrier layer is made by dissolving the resin listed above as the barrier layer material in a single layer in various organic solvents, and then
If necessary, various additives such as a curing agent, a catalyst, and a mold release agent are added, and the layer is laminated on the first barrier layer. The thickness of the second barrier layer is suitably in the range of 0.05 to 10 um, preferably 1 to 5 um.

[Thermal transferable solid ink layer]

The thermally transferable solid ink layer is mainly composed of a binder, a colorant, and, if necessary, a softener. In this case, binders include waxes, higher fatty acids, higher fatty acid esters, higher alcohols, amides, ester gums, rosin derivatives such as rosin phenol resins, polymeric compounds such as terpene resins and cyclopentadiene resins, stearylamine, and palmitinamine. Examples include higher amines such as polyethylene glycol, polyethylene oxide, etc.

The colorant can be selected from conventionally known dyes or pigments. As specific examples, cyan color pigments include magenta color pigments such as Diaceriton Fast Brilliant Blue R (manufactured by Mitsubishi Kasei Co., Ltd., trade name), Kayalon Polyester Blue B-8F Conc (manufactured by Nippon Kayaku Co., Ltd., trade name), etc. Examples include Diaceriton Fast Red R (manufactured by Mitsubishi Kasei Co., Ltd., trade name), Kayalon Polyester Pink RCL-E (manufactured by Nippon Kayaku Co., Ltd., trade name), etc., and yellow pigments include Kayalon Polyester Light Yellow 5G-3. (manufactured by Nippon Kayaku Co., Ltd., trade name), Eisensviron Yellow-GRH (manufactured by Hodogaya Chemical Co., Ltd., trade name), and the like. In addition, cyan pigments include cerulean blue and phthalocyanine blue, magenta pigments include brilliant carmine and alizarin lake, yellow pigments include Hansa yellow and bisazo yellow, and black pigments include carbon black, graphite, and oil. Black etc. can be given.

Heat-sublimable or heat-vaporizable colorants include disperse dyes, oil-soluble dyes, acid dyes, mordant dyes, vat dyes, basic dyes, etc., which are generally used in transfer printing of textiles and heat transfer inks. You can choose.

Specific examples include azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone,
Examples include azomethine dyes, coumarin dyes, and condensed polycyclic dyes. The sublimation starting temperature of these dyes is 150℃
The following are desirable.

A thermoplastic resin such as an ethylene/vinyl acetate copolymer, a butyral resin, or a polyamide resin, a plasticizer, or an oil agent such as mineral oil or vegetable oil may be added to the above thermally transferable solid ink layer. Further, if necessary, antiblocking agents, inorganic and organic pigments, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, etc. may be added. The ink layer may have a single-layer structure or a multi-layer structure in which the functions of each layer are separated. A thermally transferable solid ink layer is formed on the barrier layer by hot melt coating or solvent coating.

The thickness of the ink layer is 0.1 to 10 ums, preferably 1 to 5 um.
A range of μm is suitable.

In the layer structure of the transfer recording medium of the present invention, it is preferable to provide a release layer made of a silicone compound, a fluorine compound, or the like between the light-transmitting support and the intermediate layer. This is because by reducing the interfacial adhesive force between the light-transmitting support and the intermediate layer, the pressing effect of the residue generated as a result of photodecomposition of the photodegradable compound in the intermediate layer can be more effectively suppressed. The ink can be transferred to one layer and good thermal transferability can be ensured.

On the other hand, the image receiving sheet transferred from the transfer recording medium of the present invention having the above configuration generally has a high surface smoothness (and has a high air permeability in the cross-sectional direction of the sheet) in order to improve ink adhesion. Paper with low density (low density) is required.

However, the image-receiving sheet applied to the present invention is not subject to any restrictions on smoothness or air permeability, and a fairly wide range of papers and sheet-like materials can be used. For example, Bekk smoothness is 20
In addition to standard thermal transfer paper with a smoothness of 0 to 1000 seconds,
PPC copy paper with a smoothness of 0 to 100 seconds and a smoothness of 1 to 1.
A fairly wide range of sheets can be used, such as bond paper with a rough surface, which is often used for office purposes in Europe and the United States, and polyethylene terephthalate film with a smoothness of 10,000 seconds or more. The thickness of the image receiving sheet in this case is 50 to 150μ
m position is preferable in terms of handling properties.

Furthermore, when obtaining a full-color recorded image of higher image quality, an ink-receiving layer is provided on the surface of paper as a base material to form an image-receiving sheet, and the ink receptivity of the transfer ink (ink r
Preferably, this seven is the one that subtly controls eceptivity. In this case, the ink-receiving layer can be formed by dispersing an inorganic pigment such as calcium carbonate or silica or an organic pigment such as polystyrene or polyacrylate in a binder and then using a solvent coating method. In this case, especially when the colorant in the ink layer is dye-based, using polyesters, polyamides, or various curing resins will improve the dye adhesion (and therefore, the storage stability of the transferred image). can significantly improve performance.

Next, the process of the transfer recording method using the transfer recording medium having the above structure is shown in FIG. 5(a).
, (2) and (3) will be explained below in order.

In this case, the top of Figure 5 indicates the transfer recording medium (in Figure 3),
The beginning of Figure 5 is an example using the transfer recording medium shown in Figure 4), and Figure 5 (C) is an example using the transfer recording medium shown at the beginning of Figure 4.

(1) First, as shown in FIGS. 5(a), 5(a) and 5(c), the surface of the image-receiving sheet 5 is brought into close contact with the surface of the thermally transferable solid ink layer 4 constituting the transfer recording medium.

(2) Irradiate the back surface of the transfer recording medium (the surface opposite to the thermally transferable solid ink layer via the support) with light energy based on image information. In this case, as a means of irradiating light energy based on image information, for example, as shown in Figure 5), the surface opposite to the thermally transferable solid ink layer of the transfer recording medium can be removed by electric discharge destruction recording. If a light reflective layer is provided, the light reflective layer is removed in accordance with the information pattern, and then a flash 7 is irradiated from above the light reflective layer, just as in the discharge transfer method described above.

■As shown in Figure 5, the metal vapor deposited film 2 is placed on the transparent substrate 14.
A so-called negative mask sheet 15 is created by removing the deposited film image-wise by discharge destruction or a peeling development method using a photopolymer (Beer-Apart method), which is then placed on the back side of the transfer recording medium. Flash light 7 is irradiated by superimposed xenon, iodine lamps, etc. 6.

■As shown in FIG.
Irradiation is performed while scanning with AG laser, helium/cadmium laser, argon ion laser, krypton laser, excimer laser, nitrogen laser, metal vapor deposition laser, carbon dioxide laser, dye laser, semiconductor laser, etc. .

As a result, the photothermal conversion substance contained in the intermediate layer 9 absorbs light, converting light energy into thermal energy. The converted thermal energy is thermally conducted in the layer thickness direction of the barrier layer 12, and as a result, the thermally transferable solid ink layer 4 provided on this layer becomes a thermally melted area or a thermally sublimated area 17, and is transferred to the image receiving sheet 5. To make osmotic transfer possible. At the same time, as a result of the photodecomposition of the photodegradable compound contained in the intermediate layer 9, the generated gas significantly performs volume engraving and transfers the ink layer in a thermally molten state or thermally sublimated state to the image receiving sheet surface through the microlayer 12. Press firmly upwards.

(3) As shown in FIG. 6, by peeling and separating the transfer recording medium and the image-receiving sheet, a transfer image 8 made of thermally transferable solid ink is obtained on the image-receiving sheet.

Effect> When the back surface of the transfer recording medium (the surface opposite to the thermally transferable solid ink layer via the support) is irradiated with light energy based on image information, the photothermal conversion substance contained in the intermediate layer is exposed to light. As a result of absorption, this is effectively converted into thermal energy. The converted thermal energy is thermally conducted in the layer thickness direction of the barrier layer, thereby causing the thermally transferable solid ink provided on this layer to be in a thermally molten state or a thermally sublimated state.

At this time, as a result of photodecomposition of the photodegradable compound contained in the intermediate layer, the volume of the generated gas expands significantly.
The ink layer, which is in a thermally molten state or a thermally sublimated state, is strongly pressed onto the surface of the image-receiving sheet through the barrier layer. In this case, since a barrier layer made of a film-forming substance is provided in the present invention, the gas generated by photolysis is present either between the intermediate layer and the barrier layer or between the support and the intermediate layer. It is not emitted directly onto the ink layer surface. Therefore, the heat-transferable solid ink is pressed onto the image-receiving sheet surface through a barrier layer with excellent heat resistance and mechanical strength, so the transferred ink surface forms a highly smooth surface, and the second color During the subsequent transfer of ink, since the non-transfer surface is a smooth surface, the contact area is significantly increased, and uniform, high-density and reliable transfer is possible. The barrier layer constituting the transfer recording medium of the present invention can fundamentally improve the basic requirements in color transfer recording, namely subtractive color mixing, trapping of non-transfer ink, and density unevenness, due to the above-mentioned effects. can.

<Examples> Hereinafter, the present invention will be specifically explained with reference to Examples, but these Examples do not limit the present invention. Note that all blended parts are by weight.

Example 1 [Formation of light-reflecting layer] A roughened layer with a thickness of 6 μm containing silica (Sin) with an average particle size of 5 μm was formed on a light-transmitting support made of a polyethylene terephthalate film with a thickness of 12 μm. was provided, and a M vapor-deposited layer of about 50 OA was further provided on the roughened layer to provide a light reflecting layer that could be removed by discharge breakdown recording.

[Formation of intermediate layer]

Glass peas were added to the above liquid mixture, and after dissolving and dispersing the mixture in a paint shaker for 100 minutes, this was used as an intermediate layer paint. Next, the paint was applied onto the polyethylene terephthalate surface opposite to the light reflecting layer described above using a wire bar so that the coating thickness after drying was 2.0 μm to form an intermediate layer.

[Formation of barrier layer]

After stirring the above liquid mixture for 100 minutes to dissolve it, this was used as a barrier layer coating. Next, the paint was applied onto the intermediate layer using a wire bar so that the coating thickness after drying was 3.0 Jjm to form a barrier layer. The drying conditions were 100° C. for 2 minutes.

[Formation of thermal transferable solid ink layer] (a) Yellow ink (Y) ■Magenta ink (M) 0 cyan ink (C) ■Black ink (BK) Each mixture consisting of the above surface, ■, 0, and ■ was heated at 95°C. After melting and mixing with a homomixer, the mixture was stirred for 60 minutes to obtain a hot-melt ink. The melting points of the Y, M, C and BK inks were 75, 74.72 and 69°C, and the melt viscosities at 100°C were 126°34.22 and 120 cp. Each of the above inks is coated onto the barrier layer by a hot melt coating method so that each layer has a thickness of 3.5 um, and then the light reflective layer surface of the transfer recording medium is connected to the print head surface of a conventional discharge recording device and a platen. Applied pressure cuff 0
Image information was recorded in the form of a character pattern, a solid pattern, and a gradation pattern by a dither method, with a close contact of 0 g/cWl and a head applied voltage of 45 Vj. Thereafter, the surface of the heat-transferable solid ink layer of the yellow transfer recording medium was brought into close contact with the image-receiving sheet.

Next, a xenon flash device (manufactured by Riso Kagaku, F
X-150), the entire surface was irradiated with flash light from the light reflective layer side. At this time, the contact pressure between the thermally transferable solid ink layer surface and the image receiving sheet surface was adjusted to a constant value of 100 g/c+J, and the flash energy was adjusted to a constant value of 13 mJ/-. The image receiving sheet is a bond paper whose surface has a Bekk smoothness of 4 to 6 seconds, 50 to 60.
Four types of paper were used: copy paper for 2 seconds, thermal transfer paper for 300 to 320 seconds, and OHP sheet for 10,000 seconds or more.

Thereafter, the yellow transfer recording medium and the image-receiving sheet were peeled and separated by a 180° peeling method, thereby obtaining a yellow transfer image on the image-receiving sheet.

Thereafter, the yellow ink surface was brought into close contact with the thermally transferable solid ink surface of a magenta transfer recording medium recorded with a corresponding pattern. Subsequently, subtractive color mixing was performed by peeling and separating after irradiating light in the same manner as in the case of yellow.

Subsequently, the transfer ink surface was brought into close contact with the heat transferable solid ink surface of a cyan transfer recording medium recorded with a corresponding pattern. Subsequently, after irradiation with light, subtractive color mixing was performed by peeling and separating to obtain a color transfer image.

Example 2 A transfer recording medium of the present invention was obtained in the same manner as in Example 1, except that the barrier layer was changed to the following.

[Creation of film-forming substance]

The above mixture was put into a flask equipped with a stirrer and a beaded cooler capable of nitrogen gas injection and vacuum suction, and esterification was carried out at a temperature of 190 to 220°C in a nitrogen gas atmosphere for 240 minutes. The reaction was carried out. After this, 23
After raising the temperature to 0 to 250°C and carrying out a condensation reaction in a vacuum state of 1 to 10 Torr, a film-forming material made of a heat-resistant polyester resin containing a sulfonic acid group was obtained.

[Formation of barrier layer]

After thoroughly stirring the above liquid mixture, this was used as a barrier layer paint. Next, the paint was applied onto the intermediate layer using a wire bar in the same manner as in Example 1 so that the coating thickness after drying was 3.5 μm to form a heat-resistant barrier layer. The drying conditions were 100°C for 3 minutes, and then 5 minutes.
Cure treatment was performed at 0°C for 2 days.

Note that the transfer recording method was also performed in the same manner as in Example 1.

Example 3 A transfer recording medium of the present invention was obtained in the same manner as in Example 1, except that the barrier layer was changed to the following two-layer structure of a first barrier layer and a second barrier layer.

[Formation of the first barrier layer] The above mixed solution was put into a flask equipped with a stirrer and a cooler with beads, and after dissolution treatment was performed by stirring at a temperature of 60°C for 200 minutes, this was dissolved in the first barrier layer. It was a one-barrier layer paint. Next, the paint was applied onto the intermediate layer using a wire bar so that the coating thickness after drying was 1.5 μm to form a first barrier layer. Drying conditions are 1
The temperature was 00°C for 3 minutes.

[Formation of second barrier layer] The above-mentioned mixed solution was put into a flask equipped with a stirrer and a cooler with beads, and after dissolution treatment was performed by stirring for 100 minutes at a temperature of 60°C, this was dissolved in the second barrier layer. It was a two-barrier layer paint. Next, the paint was applied onto the first barrier layer using a wire bar so that the coating thickness after drying was 2.0 IJII to form a second barrier layer. The drying conditions were 100° C. for 3 minutes.

Note that the transfer recording method was also performed in the same manner as in Example 1.

Example 4 [Formation of release layer] Glass peas were added to the above mixed solution, and after performing a dispersion treatment for 100 minutes in a paint shaker, this was used as a release layer paint. Next, apply the paint onto the polyethylene terephthalate surface using a wire bar until the coating thickness after drying is 0.5.
A release layer was formed by coating to a thickness of μm. The drying conditions were 100° C. for 3 minutes. - [Formation of Intermediate Layer] Glass peas were added to the above liquid mixture, and after dissolving and dispersing the mixture in a paint shaker for 100 minutes, this was used as an intermediate layer paint. Next, the paint was applied onto the release layer described above using a wire bar so that the coating thickness after drying was 2.0 μm to form an intermediate layer. The drying conditions were 120° C. for 2 minutes. Thereafter, curing was performed at 50°C for 2 days.

[Formation of barrier layer]

The mixture was stirred for 30 minutes to dissolve it, and then used as a barrier layer coating. Next, a wire bar was used on the intermediate layer that had been cured with the paint so that the coating thickness after drying was 2. A barrier layer was formed by coating to obtain Oua+. The drying conditions were 140°C for 3 minutes.

Thereafter, a thermally transferable solid ink layer was formed on the barrier layer in the same manner as in Example 1 to obtain a transfer recording medium of the present invention.

Note that the transfer recording method was also performed in the same manner as in Example 1.

Example 5 A transfer recording medium of the present invention was obtained in the same manner as in Example 1, except that the support was changed to a polyethylene terephthalate support with a thickness of 6u+e, which was not provided with a roughened layer and an aluminum vapor deposition layer. .

On the other hand, image information was recorded only on the sheet provided with the light-reflecting layer, which was used as a support in Example 1, in the same manner as in Example 1, thereby producing a negative mask sheet. The polyethylene terephthalate surface of the mask sheet and the back surface of the transfer recording medium prepared above, that is, the polyethylene terephthalate surface, were overlapped, and at the same time, the image-receiving sheet was brought into close contact with the thermally transferable solid ink surface. In the same manner as in Example 1, a color transfer image was obtained by repeating the process of transferring and peeling each of yellow, magenta and cyan onto the surface of an image receiving sheet.

Example 6 An image receiving sheet was brought into close contact with the thermally transferable solid ink surface of the transfer recording medium obtained in Example 4. Next, using a 25 watt argon ion laser as a light source, laser light with a beam diameter of 10 μI was irradiated from the polyethylene terephthalate support side at a speed of 10 + e/sec while scanning in a line pattern based on electrical signals. did. A color transfer image was obtained by repeating transfer and peeling of each of yellow, magenta and cyan colors by irradiation with a laser beam corresponding to each color.

Comparative Example 1 A comparative transfer recording medium was prepared and transfer recording was performed in the same manner as in Example 1, except that no rear layer was provided.

Comparative Example 2 A comparative transfer recording medium was produced in the same manner as in Example 1, except that the barrier layer coating material was replaced with a methyl ethyl ketone solution of ethyl cellulose, which has a small gas barrier effect. However, when the barrier layer was laminated, the intermediate layer was significantly attacked by methyl ethyl ketone, and as a result, a part of the photodegradable compound in the intermediate layer was eluted into the barrier layer. Note that the transfer recording method was also performed in the same manner as in Example 1.

When the image quality obtained from each of the above Examples and Comparative Examples was evaluated, as shown in Table 1, excellent transferred images were obtained on a wide variety of image receiving papers. The image quality evaluation shown in Table 1 is based on visual inspection and visual judgment using enlarged photographs (25x and 50x). The characteristics of the film were evaluated, including chipping, discontinuity, blurring, white spots in the solid transfer area, solid unevenness, and gradation.

The evaluation criteria are as follows.

◎... All of the above characteristics are met (no problems and the solid Macbeth reflection density is 1.5 or more) O... There is a problem with one of the above characteristics, but the severity is not significant △... Above Problems in 3 or less of the above characteristics and the extent of the problem is relatively noticeable x: Problems in 3 or more of the above characteristics and the extent of the problem is extremely noticeable.

[Margin below]

<Effects of the Invention> Since the present invention has the above configuration, excellent subtractive color mixing is possible during color transfer, and it is possible to transfer from highly smooth image receiving sheets (including OHP sheets) to bond paper with extremely low smoothness. It has now become possible to transfer colors faithfully and reliably to image information to a wide variety of image-receiving sheets. In addition, the problem of trapping of non-transferred ink when the transfer recording medium and image-receiving sheet are separated is solved, and at the same time, the distribution of light energy or the density is uniform even if irradiation occurs twice (and uniform color is achieved). Transfer density is obtained.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a conventional transfer recording medium, and FIG. 2 is a sectional view of a conventional transfer recording medium.
Figures 3 (a) to 3) showing the conventional transfer recording method are as follows:
Figure 4 (A) shows an example of the structure of the transfer recording medium of the present invention.
-) are diagrams showing another configuration example of the transfer recording medium of the present invention, and Figs. 5 and 6 are diagrams showing the transfer step in the transfer recording method used in the present invention. 1... Light-transmitting support 2... Light-reflecting layer 3...
・Light-heat conversion layer 4...Thermal transferable solid ink layer 5...
・Image receiving sheet 6...Xenon flash lamp 7
...Flash 8...Transfer image 9...
Intermediate layer lO...first barrier layer 11.
...Second barrier layer 12...Barrier layer 13.
...Peeling layer 14...Transparent substrate 15...
・Mask sheet 16...Focusing lens 17...
・Heat melting part or heat sublimation part 18...laser light

Claims (1)

[Claims] 1) An intermediate layer containing a photodegradable compound and a photothermal conversion substance, a barrier layer made of a film-forming substance, and a thermally transferable solid ink layer are sequentially provided on one side of a light-transmitting support. Transfer recording medium. 2) A light-reflecting layer removable by discharge destruction recording is provided on one side of a light-transmitting support, and an intermediate layer containing a photodegradable compound and a photothermal conversion substance and a film-forming substance are provided on the other side of the support. 1. A transfer recording medium comprising a barrier layer and a thermally transferable solid ink layer sequentially provided. 3) The transfer recording medium according to claims 1 and 2, wherein the barrier layer made of the film-forming substance is composed of a single layer. 4) The barrier layer made of the film-forming substance is composed of two layers: a first barrier layer made of a resin that is water-soluble or soluble in a mixed solvent of water and an organic solvent, and a second barrier layer made of a resin that is soluble in an organic solvent. 3. The transfer recording medium according to claim 1, wherein the first barrier layer is provided in contact with the intermediate layer.