JP2671218B2 - Transfer recording medium - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention is a transfer recording medium suitable for printing high-resolution characters or images, and particularly color transfer recording suitable for multi-color or full-color recording. Regarding the medium.

<Prior Art> In recent years, various terminals have been required due to the development of office automation. Among them, there is a great demand for a recording device for converting an electric signal into a visible image, a so-called printer, but the performance is satisfactory. There are few things. For example, as a commonly used recording method, there are an inkjet method, an electrophotographic method, a thermal transfer method, and the like. However, maintenance of the apparatus and complexity of operability by using liquid or powder such as toner, Alternatively, since a thermal head is used, there is a problem that the life of the head is short and the printing speed is slow.

Therefore, a recording method using a discharge transfer recording medium containing a photodecomposable compound is proposed as one of the means capable of forming characters or images at a high density on paper with high speed and relatively good resolution and low surface smoothness. In this regard, for example, Japanese Patent Application Sho
The discharge transfer recording media of 61-205608 and 62-261635 have been proposed. Hereinafter, a conventional electric discharge recording medium will be described with reference to the drawings.

FIG. 1 is a sectional view of the transfer recording medium, in which a light-reflecting layer 2 is provided on the upper surface of a light-transmissive support 1, and a photothermal conversion layer 3 containing a photodegradable compound and a photothermal conversion substance for improving transferability is provided on the lower surface.
The thermal transfer ink layer 4 is provided in order. To perform recording using this transfer recording medium, the light reflection layer 2 is removed according to the pattern of information by a known discharge breakdown recording means, and the thermal transfer ink layer 4 is formed as shown in FIG.
The surface coated with is brought into close contact with the image receiving sheet 5, and the light reflection layer 2
A flash light including ultraviolet rays, visible rays and infrared rays is emitted from above by a xenon flash lamp 6.

Thereby, the flash light applied to the portion where the light reflection layer 2 remains is reflected, and the flash light applied to the portion where the light reflection layer is removed passes through the support 1 and reaches the photothermal conversion layer. The photothermal conversion substance in the photothermal conversion layer absorbs this flash energy and effectively converts it into heat energy. At the same time, the photodecomposable compound also contained in the photothermal conversion layer generates a photodecomposition gas. As a result, the thermal transferable ink layer 4 starts thermal melting or thermal sublimation, and is further pressed and transferred along the roughness of the surface of the image receiving sheet 5 by the pressing force due to the volume expansion of the photolytic gas and transferred. Then, the transfer recording medium and the image receiving sheet 5 were peeled off to obtain a transferred image.

In the case of color superposition, a method is adopted in which the above steps are repeated for each single color thermal transfer ink layer consisting of yellow, magenta, cyan and, if necessary, black, and the above steps are repeated for subtractive color mixing. It was

<Problems to be Solved by the Invention> However, the above-mentioned conventional transfer recording medium has a subtractive color mixing property of each ink of yellow, magenta, and cyan, that is,
There are major problems in color superposition characteristics and density uniformity.

That is, when the ink of the first color is transferred, the ink is transferred very well due to the volume expansion of the gas generated as a result of the photodecomposition of the photodecomposable compound, but on the other hand, the ink has a strong pressing force due to the gas expansion. As a result, the air permeability of the transferred ink surface is significantly increased as a result of being penetrated into the surface of the image receiving paper, and the ink layer in the heat-melted or heat-sublimated state has a sharp gas generated as a result of photolysis. Since the jetting force and the gas thereof stay in the ink layer and solidify in a roughened state, a smooth surface cannot be maintained. As a result, when the second color ink is transferred onto the surface of the first color ink layer, it is transferred onto the surface of high air permeability and conversely low smoothness.

Therefore, it is extremely difficult to dissipate the gas generated as a result of photolysis, and the transferred ink surface is roughened more than in the case of one color. Furthermore, the rapid ejection of gas causes the inks of the first and second colors to mix remarkably 1
There is a problem of trapping in which a part of the color ink is attached to the medium side and peeled off depending on the degree of roughening. Further, since the transfer is to a surface with low smoothness, it is in a disadvantageous state for transferring the second color ink. For the same reason, the transferability of the third color becomes more difficult,
Satisfied color overlapping is impossible. Furthermore, when there is a distribution of light energy over the irradiated area, and when the light irradiation is performed twice before the image receiving sheet and the transfer recording medium are peeled off, the light irradiation is performed once.
As a result, there is a large difference between the air permeability and the smoothness of the ink surface, which results in uneven density. Therefore, when obtaining a color transfer image by repeating light irradiation,
It was difficult to obtain a uniform density without unevenness.

In view of the above circumstances, the present invention provides a transfer recording medium having improved subtractive color mixture characteristics so that a uniform image without density unevenness can be obtained.

<Means for Solving the Problems> The present invention has been made as a result of earnest studies in order to solve the problems in view of the above circumstances. The outline is, in one side of the light-transmissive support, an intermediate layer containing a photodegradable compound and a photothermal conversion substance, a barrier layer and a thermal transferable ink layer in which a thermal transferable ink layer is sequentially provided, in the barrier layer,
It contains at least one film-forming substance with a glass transition temperature (DSC method) of 50 ° C or higher and a melting point (DSC method) or softening point (JIS K 2531 ring and ball method) of 150 ° C or higher, and tensile rupture of the barrier layer. Strength (ASTM D 638-61T) and tensile breaking elongation (ASTM D 638-61T) are 500 to 2500 kg / cm ² , 30 to 150, respectively.
The transfer recording medium is characterized by being in the range of%.

First, the structure of the transfer recording medium according to the present invention will be described with reference to FIGS. FIG. 3 shows a type provided with a light reflection layer, and FIG. 4 shows a type not provided with a light reflection layer.
That is, FIG. 3A shows that the light-reflective layer 2 which can be removed by discharge breakdown recording is provided on one surface of the light-transmissive support 1, and the intermediate layer 9, the barrier layer 12, and the thermal transfer ink are provided on the other surface. Layers 4 are provided in sequence. FIG. 3 (B) shows the barrier layer 12 in FIG. 3 (A) converted into two layers of the first barrier layer 10 and the second barrier layer. Third
In FIG. 3C, a peeling layer 13 is provided between the light transmissive support 1 and the intermediate layer 9 in FIG. 3A. FIG. 3D shows the light-transmitting support 1 and the intermediate layer 9 shown in FIG.
The peeling layer 13 is provided between and. Figure 4 (a),
(B), (c), and (d) show another configuration of the transfer recording medium of the present invention, respectively, as shown in FIG.
In the transfer recording mediums (b), (c) and (d), the type is provided with no light reflection layer.

 Next, the material of each layer constitution will be described in detail below.

(Light transmitting support)

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

[Light reflection layer]

A vapor-deposited metal film of aluminum, zinc, tin, or the like, which is easily broken by discharge, is applied. Examples of the vapor deposition method include a resistance heating vapor deposition method, a direct current or high frequency sputtering method, an ion plating method, an ion beam vapor deposition method, and a cluster ion beam vapor deposition method. The thickness of the light reflection layer is 0.00
A range of 1 to 1 μm, preferably 0.01 to 0.1 μm is suitable.

Further, in order to stabilize the discharge breakdown recording, it is desirable to provide a roughening layer between the light transmissive support and the light reflecting layer to give the surface of the light reflecting layer a certain roughness.

The roughened layer here is a layer formed by dispersing at least an inorganic or organic pigment or fine particles in a binder. In this case, the binder material system suitable for the roughened layer is preferably a resin having high mechanical strength and stability, heat resistance strength and stability, and chemical resistance. Specific examples thereof include polyester resins, polyurethane resins, polystyrene resins, various fiber-based resins, polyimide resins,
Examples include various thermoplastic resins such as silicone resin, fluororesin, polyarylate resin, epoxy resin, and alkyd resin, and thermosetting resins. When the above-mentioned one can be cured, for example, when the curing means is heat, a curing agent, a chain extender, a catalyst and the like can be added to the main resin. When the curing means is light, especially ultraviolet rays, a resin monomer (or oligomer), a photopolymerization initiator, a thermal polymerization inhibitor, and various sensitizers can be added to the main resin. When the curing means is an electron beam, various sensitizers can be added to the base resin.

Next, pigments or fine particles to be mixed in the roughened layer are silica, alumina, tin dioxide, hydrated alumina, inorganic pigments such as glass beads, crosslinked polystyrene resin, phenol resin, polymethylmethacrylate resin, silicone resin, Examples thereof include fine particles of benzoguanamine resin, benzoguanamine / formaldehyde polycondensation resin, melamine / formaldehyde polycondensation polymer and the like. It is preferable that these pigments or fine particles have relatively high transparency. Further, they may be used alone or in combination of two or more. The amount of these used is appropriately in the range of 0.6 to 60 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total solid content in the roughened layer. Roughening layer paint is
It is obtained by adding the above-mentioned binder, pigment or fine particles and, if necessary, various additives such as a curing agent and a catalyst, and dissolving or dispersing them in an appropriate solvent. The coating material is applied onto the light-transmissive support by a solvent coating method so as to have a coating thickness of 0.01 to 20 μm, preferably 0.1 to 10 μm.

(Intermediate layer)

The intermediate layer in the present invention is formed by dissolving or dispersing a photodecomposable compound and a photothermal conversion substance in a binder. In this case, as a material system suitable for the intermediate layer, an acrylic resin, a styrene resin, an organic solvent-soluble resin such as a vinyl resin, polyvinyl alcohol, polyvinyl butyral, a water-soluble resin such as isobutylene / maleic anhydride copolymer, or the like, It can be used by appropriately selecting from various waxes and rubbers.

Next, the photo-decomposable compound to be mixed in the intermediate layer is an ultraviolet ray,
Prompt photolysis by light including visible light and infrared rays is an essential condition. Suitable material systems for this include diazo compounds and azido compounds. Among these, as the diazo compound, those conventionally used in the field of diazo copying materials can be mentioned as they are. That is, specific examples thereof include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-dipropylaminobenzene, 4-diazo-1-methylbenzylaminobenzene,
4-diazo-1-dibenzylaminobenzene, 4-diazo-1-ethylhydroxyaminobenzene, 4-diazo-1-diethylamino-3-methoxybenzene, 4-diazo-1-dimethylamino-2-methylbenzene, 4 −
Diazo-1-benzoylamino-2,5-diethoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-dimethoxybenzene,
4-diazo-1-morpholino-2,5-diethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-1-morpholino-2,5-isopropoxybenzene, 4- Diazo-1-anilinobenzene, 4-diazo-1-dimethylamino-3-carboxybenzene, 4-diazo-1-toluylmercapto-
2,5-diethoxybenzene, 4-diazo-1,4-methoxybenzoylamino-2,5-diethoxybenzene, 4-diazo-1-pyrrolidino-3-methylbenzene, 4-diazo-1-pyrrolidino-2 -Methylbenzene, 4-diazo-1-dimethylamino-2- (4'chlorophenoxy) -5-chlorobenzene and the like can be mentioned.

On the other hand, as the azide compound, an aromatic compound is particularly effective, but in addition to this, 4,4'-diazide-diphenyl sulfone, 4,4'-diazidobenzosulfone, 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 may be used alone or in admixture of two or more. The amount of these photodecomposable compounds used is appropriately in the range of 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 mixed in the intermediate layer at the same time is an inorganic or organic pigment having the ability to absorb light energy including ultraviolet rays, visible rays, and infrared rays over a wider wavelength range, and convert it into heat energy more effectively or dye,
UV absorbers, infrared absorbers, etc. are applied. Specific examples thereof include carbon black, graphite, iron powder, chromium powder, aluminum powder and other metal powders, metal oxides, sulfides, selenides, ferrocyanides, chrome hydrochloric acid, inorganic pigments such as silicates, Azo pigment, dye lake pigment, nitro pigment,
Organic pigments such as nitroso pigments, phthalocyanine pigments, metal complex pigments, perylene pigments, isoindolinone pigments, quinacridone pigments, nitrone dyes, nitro dyes, azo dyes, stilbene azo dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, Dyes such as thiazole dyes, azine dyes, oxazine dyes, sulfur dyes, anthraquinone dyes, indigoid dyes and phthalocyanine dyes,
Salicylic acid-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel-dibutyldithiocarbamate, benzoate-based quenchers, and ultraviolet absorbers such as hindered amines, commercially available infrared absorbers (Mitsui Toatsu's IR absorber-PA- 1001, PA-1005, PA
-1006, IRF-905, IRF-700 manufactured by Fuji Film Co., Ltd.) and the like. These photothermal conversion substances may be used alone or in combination of two or more. The amount of the photothermal conversion substance used is appropriately in the range of 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total solid content in the layer.

The intermediate layer coating is obtained by adding various additives such as the above-mentioned binder, photodecomposable compound, photothermal conversion substance and, if necessary, dispersant and curing agent, and dissolving or dispersing in an appropriate solvent. 0.01 to 20 μm, preferably 0.1 to 10 μm on the surface of the support by the coating method
The coating thickness is m.

[Barrier layer-single-layer structure]

The barrier layer composed of a single layer and the properties required when setting the layer include the following items.

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

(2) It has a sufficient gas barrier property so that the gas generated in the intermediate layer as a result of photolysis does not permeate into the heat transferable ink layer.

(3) Even if it is a relatively thin layer, it must have sufficient mechanical strength so that the barrier layer does not break or burst due to the jetting force of the gas generated in the intermediate layer.

(4) When laminated on the intermediate layer, the characteristics of the intermediate layer are not impaired without significantly eroding the intermediate layer.

In order to form a barrier layer that satisfies the above characteristics,
It is necessary to contain at least one kind of film-forming substance described below. The material system of the film-forming substance, polyacrylic resin, polystyrene resin, polyvinyl resin, polyvinylidene resin, polyamide resin, polyimide resin, polyester resin, polyacetal resin, modified polyphenylene oxide resin, Classified as polyurethane-based resin, polycarbonate-based resin, polyarylate-based resin, polysulfone-based resin, fluorine-based resin, silicone-based resin and copolymer resins between these resins, various thermosetting resins, and other heat-resistant polymers Resin system (Tatsumi Mita, Industrial Chemistry, Vol. 73, page 1361, 1970
Annual publications) and the like having a glass transition temperature of 50 ° C. or higher and a melting point or softening point of 150 ° C. or higher.

These resins may be used alone or in combination of two or more, but the resin is not limited to these.

The barrier layer may be formed by processing these resins into a film by an injection molding method, an extrusion molding method, or the like, and forming a barrier film by laminating, or by dissolving or dispersing these resins in an appropriate solvent. The paint may be set by the solvent coating method.

Here, first, a case where the barrier layer is set by laminating will be described.

For laminating, one having an intermediate layer set on the above-mentioned light-transmitting support and one for laminating the barrier film, and after setting the above-mentioned intermediate layer on one surface of the barrier film, light-transmitting In some cases, it is attached to the sexual support through an intermediate layer. A means for applying pressure and / or heating can be considered as a means for laminating these. The pressure at the time of laminating may be, for example, only passing between pressure rollers, but by exposing the barrier film with an infrared lamp or the like, the binder of the intermediate layer, and the light transmissive support and the intermediate layer. When there is a peeling layer between and, the peeling layer may be laminated while being softened by heat. Or,
Immediately before passing between the pressure rollers, the barrier film is exposed with an infrared lamp or the like, so that a binder for the intermediate layer and a release layer when a release layer is present between the light-transmitting support and the intermediate layer. It may be heat-softened and then passed through a pressure roller. In this case, the linear pressure between the pressure rollers is 0.1 to 10 kg / cm, preferably 1 to 5 kg / cm. Also, the heating temperature in this case is 40 ~
It is 150 ° C., preferably in the range of 50 to 100 ° C.

Next, the case where the barrier layer is set by the solvent coating method will be described.

The solvent for the coating material for the barrier layer is required to have at least the characteristics of a solvent for dissolving these resins or a dispersion medium for dispersing them. In addition, problems such as the occurrence of coating streaks and coating unevenness at the interface between the intermediate layer and the barrier layer, and elution of photodegradable compounds and photothermal conversion substances in the intermediate layer without significantly eroding the intermediate layer during multilayer coating There should not be. Specific examples of the solvent for these barrier layer paints include aliphatic hydrocarbons, alcohols, ethers, ketones, esters, nitriles,
Examples thereof include carbon tetrachloride, carbon disulfide, water and the like.
These solvents may be used alone or as a mixed solvent of two or more kinds, but the solvent is not limited to these.

The barrier layer composed of a single layer is formed on the intermediate layer by the above-mentioned method by adding the above-mentioned resin and, if necessary, additives such as a curing agent, a catalyst, a release agent and a surfactant.
The thickness of the barrier layer composed of a single layer is 0.5-10μ
m, preferably 1-5 μm.

[Barrier layer-two-layer structure] Of the two barrier layers, the first barrier layer provided so as to be in contact with the intermediate layer has the second barrier layer provided thereon, which significantly corrodes the intermediate layer. When laminated by a solvent coating method using an organic solvent, the organic solvent of the second barrier layer significantly corrodes the intermediate layer, which causes coating streaks and coating unevenness at the interface between the intermediate layer and the second barrier layer. It is provided in order to completely prevent problems such as generation or elution of the photodegradable compound or the photothermal conversion substance in the intermediate layer. Therefore, the first barrier layer needs to have the organic solvent barrier property of the second barrier layer coating material. At the same time, the solvent of the first barrier layer coating should be less corrosive or totally inert to the intermediate layer. It has been found that a water-soluble resin or a mixed solvent-soluble resin of water and an organic solvent is most suitable for the first barrier layer satisfying these requirements. That is, specific examples thereof include polyvinyl alcohol, polyvinyl butyral, polyethylene oxide, polyacrylic acid, polyamide, isobutylene / maleic anhydride copolymer resin, ethylene / vinyl alcohol copolymer, polyvinylidene chloride resin, vinylidene chloride / acrylonitrile. Examples thereof include copolymer resins, vinyl chloride / vinylidene chloride copolymer resins, propylene / vinylidene chloride copolymer resins, and the like. These resins may be used alone or in combination of two or more, but the resin is not limited to these.

The first barrier layer is formed by dissolving the above-mentioned resin in water or a mixed solvent system of water and an organic solvent, adding various additives such as a curing agent, a catalyst, and a surfactant, if necessary, and forming an intermediate layer by a solvent coating method. Stacked. The thickness of the first barrier layer is 0.1 to 10 μm, preferably 1 to 5 μm.

The second barrier layer is prepared by dissolving the resin mentioned as the barrier layer material composed of a single layer in various organic solvents, and then adding various additives such as a curing agent, a catalyst and a release agent, if necessary. Laminated on one barrier layer. The thickness of the second barrier layer is 0.5 to 10 μm, preferably 1 to 5 μm.

[Thermal transfer ink layer]

The heat transferable ink layer is mainly composed of a binder (or vehicle), a colorant, and, if necessary, a softening agent. In this case, it is an essential condition that the binder is a heat-melting or heat-softening resin composed of a substance having a low melting point or a substance having a low glass transition temperature, and as a suitable material system for this, its melting point is 40 to 120. Mention may be made of solid or semi-solid substances in the range of ° C. Specific examples thereof include carnauba wax, paraffin wax, microcrystalline wax, ester wax, oxidized wax, waxes such as montan wax, higher fatty acids such as stearic acid and behenic acid, higher alcohols such as palmityl alcohol and stearyl alcohol, Higher fatty acid esters such as cetyl palmitate and cetyl stearate, amides such as acetamide and stearic acid amide,
Examples thereof include ester gum, rosin derivatives such as rosin phenol resin, polymer compounds such as terpene resin and cyclopentadiene resin, higher amines such as stearylamine and palmitinamine, polyethylene glycol, polyethylene oxide and the like. These low melting point substances may be used alone or in admixture of two or more.

As shown in FIG. 5, the transfer recording medium used in the present invention is surface-sequentially coated with three colors (yellow, magenta, cyan) or four colors (addition of black). Therefore, the colorant needs three colors (yellow, magenta, cyan) or four colors (addition of black), and these can be selected from various conventionally known dyes or pigments. As a specific example thereof, as a cyan dye, diaceriton fast brilliant blue R (manufactured by Mitsubishi Kasei Co., Ltd.), Kayaron polyester blue B-SF Conc (manufactured by Nippon Kayaku Co., Ltd.,
(Product name) etc., as magenta color dyes, Diaceriton Fast Red R (product name, manufactured by Mitsubishi Kasei), Kayaron Polyester Pink RCL-E (product name, manufactured by Nippon Kayaku Co., Ltd.)
Examples of the yellow dye include Kayaron Polyester Light Yellow 5G-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and Aizen Spiro Yellow GRH (trade name, manufactured by Hodogaya Chemical Co., Ltd.). Further, as cyan pigments, cerulean blue, phthalocyanine blue, etc., as magenta pigments, brilliant carmine, arzaline lake, etc., as yellow pigments, Hansa yellow, bisazo yellow, etc., as black pigments, carbon black, graphite, oil black. Etc. can be mentioned.

The heat sublimable or heat vaporizable colorant is generally used in transfer printing or thermal transfer ink of fibers, from disperse dyes, oil-soluble dyes, acid dyes, mordant dyes, vat dyes, basic dyes, etc. You can choose. Specific examples thereof include azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone, azomethine, coumarin, and condensed polycyclic dyes. The sublimation initiation temperature of these dyes is preferably 150 ° C or lower.

Into the above heat transferable ink layer, a thermoplastic resin such as ethylene vinyl acetate copolymer, butyral resin or polyamide resin, or a plasticizer, or an oil agent such as mineral oil or vegetable oil may be added. If necessary, antiblocking agents, inorganic and organic pigments, antioxidants, ultraviolet absorbers, antistatic agents, surfactants and the like may be added. The ink layer may have a single structure or a multi-layer structure.

The heat transferable ink layer is formed on the barrier layer by the hot melt coating method or the solvent coating method. The thickness of the ink layer is 0.1 to 10 μm,
The range of 1 to 5 μm is preferable.

The thermal transferable ink layer has a structure in which monochromatic color thermal transferable ink layers each having a hue of yellow, magenta, cyan and, if necessary, black are sequentially arranged in a plane (hereinafter,
"It is called" field sequential "). For example, Figure 5 (a)
As shown in FIG. 4, the monochromatic color heat transferable ink layers 4-1, 4-2, 4-3 and 4 are sequentially arranged along the flow direction of the support.
-4 may be provided, and as shown in FIG. 5B, the above-mentioned monochromatic color thermal transfer ink layers 4-1, 4-2, 4-3 and 4 are formed along the width direction of the support. The hue 4-4 corresponds to, for example, yellow, magenta, cyan, and black.

[Peeling layer]

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

On the other hand, the image receiving sheet transferred from the transfer recording medium according to the present invention having the above-mentioned constitution generally has a high surface smoothness and an air permeability in the cross-sectional direction of the sheet in order to improve its ink adhesion. Low-density (low-density) paper is required. However, the image receiving sheet applied to the present invention is not restricted by the smoothness and air permeability, and a wide range of papers and sheet-like materials can be applied. For example, in addition to standard thermal transfer paper with a Bekk smoothness of 200 to 1000 seconds, PPC copy paper with a smoothness of 10 to 100 seconds is commonly used for office work in Europe and the United States with a smoothness of 1 to 10 seconds. A wide range of sheets such as a bond paper having a rough surface and a polyethylene terephthalate film having a smoothness of 10,000 seconds or more can be used. The thickness of the image receiving sheet in this case is
About 50 to 150 μm is suitable in terms of handling property.

Furthermore, when a full-color recorded image of higher image quality is obtained, an ink receiving layer is provided on the surface of the paper as a substrate to form an image receiving sheet, and the ink receptivity of transfer (ink receptivit
It is preferable to control y) delicately. In this case, the ink receiving layer can be formed by a solvent coating method after dispersing an inorganic pigment such as calcium carbonate or silica or an organic pigment such as polystyrene or polyacrylate in a binder. At this time, the binder, especially when the colorant of the ink layer is a dye-based material, has good dyeing property of the dye when polyesters, polyamides or various cured resins are used.
The storage stability of the transferred image can be significantly improved.

Next, the process of the transfer recording method performed by using the transfer recording medium having the above-described structure will be described below in order with reference to FIGS. 6 (a), 6 (b) and 6 (c).

In this case, FIG. 6 (a) shows the transfer recording medium of FIG. 3 (b), FIG. 6 (b) shows the transfer recording medium of FIG. 4 (b), and FIG. 6 (c) shows 4 is an example in which the transfer recording medium of FIG. 4 (a) is used.

(1) First, as shown in FIGS. 6A, 6B and 6C, the surface of the image receiving sheet 5 is brought into close contact with the surface of the thermal transferable ink layer 4 constituting the transfer recording medium.

(2) The back surface of the transfer recording medium (the surface opposite to the heat transferable ink through the support) is irradiated with light energy based on image information. As means for irradiating the light energy based on the image information in this case, for example, as shown in FIG. 6 (a), a light reflection layer removable by discharge breakdown on the opposite side of the thermal transferable ink layer of the transfer recording medium. Is provided, after removing the light reflection layer according to the pattern of information, just as in the discharge transfer method described above,
A flash 7 is emitted from above the light reflection layer.

As shown in FIG. 6B, a metal vapor deposition film 2 is provided on the transparent substrate 14, and the vapor deposition film is image-wise removed by discharge breakdown or peeling development method using a photopolymer (peeling apart method). Then, a so-called negative mask sheet 15 is prepared, and this is superposed on the back surface of the transfer recording medium, and a flash 7 is emitted by a xenon, iodine lamp 6 or the like.

As shown in FIG. 6 (c), the laser light 18 condensed by the condenser lens 16 controlled imagewise, that is, YAG laser, helium / cadmium laser, argon ion laser, krypton laser, excimer laser, nitrogen is used. Laser, metal deposition laser, carbon dioxide laser,
Irradiation is performed while scanning with a dye laser, a semiconductor laser, or the like.

As a result, the photothermal conversion substance contained in the intermediate layer 9 absorbs light, and as a result, the light energy is converted into heat energy. The converted heat energy is thermally conducted in the layer thickness direction of the barrier layer 12, so that the heat transferable ink layer 4 provided on this layer becomes a heat melting portion or a heat sublimation portion 17 and penetrates into the image receiving sheet 5. Set it so that it can be transferred.
At the same time, as a result of the photodecomposable compound contained in the intermediate layer 9 being photodecomposed, the generated gas is significantly expanded in volume, and the ink layer in the heat-melted state or the heat-sublimated state is transferred through the barrier layer 12 to the surface of the image receiving sheet. Press firmly upward.

(3) As shown in FIG. 7, the transfer recording medium and the image receiving sheet are separated and separated to obtain a transfer image 8 made of thermal transfer ink on the image receiving sheet.

<Operation> When the back surface of the transfer recording medium (the surface opposite to the heat transferable ink layer through the support) is irradiated with light energy based on image information, the photothermal conversion substance contained in the intermediate layer absorbs light. As a result, is effectively converted into heat energy. The converted heat energy conducts heat in the layer thickness direction of the barrier layer, and as a result, the heat transferable ink provided on this layer is brought into a heat melting state or a heat sublimation state. At this time, at the same time, as a result of photolysis of the photodegradable compound contained in the intermediate layer, the generated gas is significantly expanded in volume, and the ink layer in the heat-melted state or the heat-sublimated state is transferred to the image-receiving sheet via the barrier layer. Press strongly on the surface. At this time, the quality of the transferred image depends on various characteristics of the film-forming substance forming the barrier layer, that is, the glass transition temperature (DSC method) and melting point (DSC method).
Alternatively, it is affected by the softening point (JIS K 2531 ring and ball method), the physical strength of the barrier layer, that is, the tensile breaking strength (ASTM D 638-61T) and the tensile breaking elongation (ASTM D 638-61T).
That is, in the transfer recording method of the present method, when the glass transition temperature and melting point or softening point of the film forming material forming the barrier layer are lower than the numerical limit range of the present invention, heat resistance is not satisfied, and the barrier property is not satisfied. The layer is easily softened or melted by the heat energy converted by the photothermal conversion substance. At the same time, its mechanical strength is also lowered, so that it is remarkably stretched or broken by a physical action due to the volume expansion of the gas, that is, a strong pressing force. Therefore, the gas is not barriered by the barrier layer and directly reaches the ink layer, so that the above-mentioned various problems in the color superposition characteristics and the uniformity of the image density occur. Further, for the purpose of increasing the mechanical strength, if the tensile rupture strength of the barrier layer is made too large, the pressing effect of the gas is impaired, and as a result, the ink cannot be pressed against the image receiving sheet, It is difficult to apply it to rough paper, which is one of the characteristics of transfer recording media. That is, in order to obtain excellent transferred image quality, the barrier layer is required to have mechanical strength and elasticity suitable for the pressing force of the gas.

The transfer recording medium of the present invention has a glass transition temperature (DSC method) of 50 ° C. or more, a melting point (DSC method) or a softening point (JIS K 2531 ring and ball method) of 150 ° C. as a film forming substance forming a barrier layer.
The barrier layer contains at least one kind of the above film-forming substance, and the tensile breaking strength of the barrier layer (ASTM D 638-61T),
Tensile elongation at break (ASTM D 638-61T) is 500 to 2500 kg / c each
m ^2, since it is set to be within a range 30 to 150% gas generated by photolysis is present between the intermediate layer and between the barrier layer and / or the support and the intermediate layer ,
It is not released directly to the ink layer surface. Therefore, the heat transferable ink is pressed against the surface of the image receiving sheet through the barrier layer having excellent heat resistance and mechanical strength, so that the transferred ink surface forms a highly smooth surface. In the subsequent transfer of ink, the non-transfer surface is a smooth surface, so that the contact area is remarkably increased, and uniform and high-concentration reliable transfer becomes possible. The barrier layer constituting the transfer recording medium of the present invention can drastically improve the basic requirements in color transfer recording, that is, subtractive color mixing, non-transfer ink trapping, and density unevenness. it can.

<Example> Hereinafter, the present invention will be described in detail with reference to examples, but the present examples do not limit the present invention. It should be noted that all compounding parts are parts by weight.

Example 1 [Formation of light reflection layer] A roughened layer having a layer thickness of 6 μm, in which silica (SiO ₂ ) having an average particle size of 5 μm was contained on a light transmissive support made of a polyethylene terephthalate film having a thickness of 12 μm. And an aluminum vapor-deposited layer of about 500 Å on the roughened layer to provide a light reflection layer that can be removed by discharge breakdown recording.

Add glass beads to the above mixture and use an attritor.
After dissolution and dispersion treatment for 100 minutes, this was used as an intermediate layer paint. Next, the coating material was applied onto the surface of the polyethylene terephthalate opposite to the side where the above-mentioned light reflecting layer was provided by using a wire bar so that the coating thickness after drying was 2.0 μm to form an intermediate layer. The drying condition was 100 ° C. for 2 minutes.

After stirring and dissolving the above mixed solution for 100 minutes, this was used as a barrier layer coating material. Next, the coating material was applied onto the intermediate layer using a wire bar so that the coating thickness after drying was 3.0 μm to form a barrier layer. The drying conditions are
It was 2 minutes at 100 ° C.

[Formation of thermal transfer ink layer] The respective mixtures (A), (B), (C) and (D) were melt-mixed at 95 ° C. and then stirred with a homomixer for 60 minutes to obtain a heat-meltable 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 was applied on the intermediate layer by hot melt coating so that the ink was formed into a frame-sequential shape along the width direction of the support as shown in FIG. 5 (a), and the thickness of each layer was 3.5 μm. Coating to form a thermal transfer ink layer, Y, M,
A transfer recording medium having C and BK ink layers was obtained.

After that, the light reflection layer surface of the transfer recording medium and the print head surface of an ordinary discharge breakdown recording device and the platen applied pressure of 700 g
/ cm ² into close contact with, at a head applied voltage 45V, and recording image information in the gradation pattern by the character pattern, a solid pattern, and dither method. After that, the thermal transfer ink layer surface of the yellow transfer recording medium and the image receiving sheet were brought into close contact with each other. Subsequently, using a xenon flash device (FX-150, manufactured by Ideal Science Co., Ltd.), flash light was entirely irradiated from the light reflecting layer side. At this time, the adhesion between the thermal transfer ink layer surface and the image receiving sheet surface was adjusted to a constant value of 100 g / cm ² , and the flash energy was 13 mJ / mm ² . The image-receiving sheet has bond surface with Beck smoothness of 4 to 6 seconds, copy paper of 50 to 60 seconds, and 300.
Four types of heat transfer paper for ~ 320 seconds and OHP sheets for 10,000 seconds or more were used.

Thereafter, the yellow transfer recording medium and the image receiving sheet were separated and separated by a 180 ° peeling method to obtain a yellow transfer image on the image receiving sheet.

After that, the heat transferable ink surface of the magenta transfer recording medium recorded in a pattern corresponding to the yellow ink surface was brought into close contact. Subsequently, in the same manner as in the case of the yellow color, after the light irradiation, peeling and separation were performed to perform subtractive color mixing. Subsequently, the thermal transfer ink surface of the cyan transfer recording medium recorded in a pattern corresponding to the transfer ink surface was brought into close contact. Subsequently, similarly, after light irradiation, peeling and separation were performed to perform subtractive color mixture to obtain a color image.

Example 2 A transfer recording medium of the present invention was obtained in the same manner as in Example 1 except that the following release layer was set between the light transmissive support and the intermediate layer, and the barrier layer was changed to the following. . The transfer recording method was also performed in the same manner.

Glass beads were added to the above mixed solution and dispersed for 100 minutes with an attritor, and this was used as a release layer coating material. Next, the coating material was applied on the surface of the polyethylene terephthalate film of the light transmissive support using a wire bar so that the coating thickness after drying was 0.5 μm to form a release layer. The drying condition was 100 ° C. for 3 minutes.

In order to obtain a barrier layer coating composition having the above composition, first, dichloroethane and polyarylate resin are heated with a water bath or the like at about 70 ° C., and dissolved by stirring for 100 minutes, and then gradually stirred with toluene. Was added and the mixture was further cooled to room temperature to obtain a barrier layer paint. Next, the coating material was applied onto the intermediate layer by a reverse coating method so that the coating pressure after drying was 3.0 μm to form a barrier layer. The drying condition was 100 ° C. for 2 minutes.

Example 3 An example except that a light-reflecting layer was provided on a light-transmitting support and the following intermediate layer, first barrier layer, and second barrier layer were sequentially provided on the other surface thereof, as in Example 1. A transfer recording medium of the present invention was obtained in the same manner as in 1. The transfer recording method was also performed in the same manner.

Add glass beads to the above mixture and use an attritor.
After dissolution and dispersion treatment for 100 minutes, this was used as an intermediate layer paint. Next, the coating material was applied onto the surface of the polyethylene terephthalate opposite to the side where the above-mentioned light reflecting layer was provided by using a wire bar so that the coating thickness after drying was 2.0 μm to form an intermediate layer. The drying condition was 100 ° C. for 2 minutes. Then, it was cured at 40 ° C. for 3 days.

The mixed solution was placed in a flask equipped with a stirrer and a ball cooler and stirred at a temperature of 60 ° C. for 200 minutes for dissolution treatment, and this was used as a first barrier layer paint. Next, the coating material 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. The drying condition is 100
It was 2 minutes at ° C.

The above mixed solution was heated at about 70 ° C. in a water bath or the like and stirred for 100 minutes to dissolve it, and then the second barrier layer coating material was obtained. Next, the coating material was applied onto the first intermediate layer by a reverse coating method so that the coating thickness after drying was 3.0 μm to form a second barrier layer. Drying condition is 100 ℃
It was 2 minutes.

Example 4 A transfer recording medium of the present invention was obtained according to the following procedure.

In the same manner as in Example 1, a light reflective layer was provided on the light transmissive support, and a release layer having the following composition was set on the other surface.

For the peeling layer, glass beads are added to the above mixed solution, and the mixture is subjected to dispersion / dissolution treatment for 300 minutes with an attritor, and this is used as a peeling layer paint, and the coating thickness after drying with a wire bar is 0.5 μm. Is formed by coating.

Next, the intermediate layer and the barrier layer were set by the following method.

First, an intermediate layer solution having the same composition as in Example 1 was applied to one side of a barrier layer made of an ultrathin polyethylene terephthalate film having a glass transition temperature of 70 ° C. and a melting point of 260 ° C. and having a thickness of 2.6 μm. Next, the surface of the intermediate layer on the barrier layer and the release layer surface set as described above are overlapped,
Linear pressure 4kg / cm, speed 5m / min between rollers heated to 50 ℃
And passed through for bonding. As a result, an intermediate layer and a film-shaped barrier layer were sequentially laminated on the release layer.

Hereinafter, the thermal transfer ink layer is set in the same manner as in Example 1,
A transfer recording medium of the present invention was obtained. The transfer recording method was also performed in the same manner.

Example 5 A transfer recording medium of the present invention was obtained in the same manner as in Example 1 except that a polyethylene terephthalate support having a thickness of 6 μm and provided with no roughening layer and aluminum vapor deposition layer was used. .

On the other hand, a negative mask sheet was obtained by recording image information in the same manner as in Example 1 only on the sheet provided with the light reflection layer, which was used as the support in Example 1. 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 superposed, and at the same time, the image receiving sheet was brought into close contact with the heat transferable ink surface. Thereafter, in the same manner as in Example 1, a color transfer image was obtained by repeating transfer and peeling of the yellow color, the magenta color and the cyan color on the surface of the image receiving sheet.

Example 6 A transfer recording medium of the present invention was obtained in the same manner as in Example 2 except that a polyethylene terephthalate support having a thickness of 6 μm and not provided with a roughening layer and an aluminum vapor deposition layer was used. .

On the other hand, an image receiving sheet was brought into close contact with the heat transferable ink layer surface of the transfer recording medium. Subsequently, a 25 watt argon ion laser was used as a light source, and a laser beam of 10 μm was irradiated from the side of the polyethylene terephthalate support while scanning it in the form of an image based on an electric signal. A color transfer image was obtained by repeating transfer and peeling by irradiating laser light corresponding to each color for yellow, magenta and cyan.

Comparative Example 1 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 1 except that the barrier layer was not provided.

Comparative Example 2 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 1 except that the barrier layer was changed to the following.

After stirring the above mixed solution for 30 minutes, this was used as a barrier layer paint. Next, the coating material was applied onto the intermediate layer using a wire bar so that the coating thickness after drying was 3.0 μm to form a barrier layer. The drying conditions are 100 ℃ and 2
Minutes.

Comparative Example 3 A transfer recording medium for comparison and transfer recording were carried out in the same manner as in Example 2 except that the barrier layer was changed to the following.

After stirring the above mixed solution for 10 minutes, this was used as a barrier layer paint. Next, the coating material was applied onto the intermediate layer using a wire bar so that the coating thickness after drying was 3.0 μm to form a barrier layer. The drying conditions are 100 ℃ and 2
Minutes.

When the image quality obtained from each of the examples and comparative examples was evaluated, as shown in Table 1, excellent image quality was obtained for a wide range of image receiving papers. The image evaluations shown in Table 1 are all based on visual judgment by visual inspection and magnified photographs, and fine line transfer portion printing failure, breakage, blurring, and solid transfer at the time of cyan color overlapping which is the transfer of the third color. White spots in the section,
Various characteristics including solid unevenness and gradation were evaluated. The evaluation criteria are as follows.

◎ ... The above characteristics are not problematic, and the solid Macbeth reflection density is 1.5 or more. ○ ... One of the above characteristics has a problem and the degree is not remarkable. There is a problem, and the degree is comparatively conspicuous. X ... Problems with three or more of the above characteristics, and the degree is remarkable. <Effects of the Invention> The transfer recording medium barrier layer of the present invention having the above-mentioned characteristics solves the problem of trapping of non-transferred ink when the transfer recording medium and the image receiving sheet are peeled off, and at the same time, the distribution of light energy, or Even if the irradiation is performed twice, there is no density unevenness, and a uniform color transfer density can be obtained. As a result, excellent subtractive color mixing is possible when transferring colors, and image information can be sent to a wide variety of image receiving sheets, from highly smooth image receiving sheets (including OHP) to extremely low smoothness bond sheets. Faithful color transfer is now possible.

[Brief description of the drawings]

FIG. 1 is a sectional view of a conventional transfer recording medium, FIG. 2 is a view showing a conventional transfer recording system, and FIGS. 3 (a) to 3 (d) are
The figure which shows the structural example of the transfer recording medium of this invention, FIG.
~ (D) is a diagram showing another configuration of the transfer recording medium of the present invention,
5 (a) and 5 (b) are plan views of a monochromatic color thermal transferable ink layer according to the present invention provided in a surface sequential manner, and FIGS. 6 and 7 are transfer recording methods used in the present invention. FIG. 7 is a diagram showing a transfer step in FIG. 1 ... Light transmissive support, 2 ... Light reflecting layer, 3 ... Photothermal conversion layer, 4 ... Thermal transfer ink layer, 5 ... Image receiving sheet, 6
...... Xenon flash lamp, 7 ...... flash light, 8 ...... transfer image, 9 ...... intermediate layer, 10 ...... first barrier layer, 11 ......
Second barrier layer, 12 ... Barrier layer, 13 ... Release layer, 14
...... Transparent base material, 15 ...... Mask sheet, 16 ...... Focusing lens, 17 ...... Heat melting part or heat sublimation part, 18 ...... Laser light

Claims (4)

(57) [Claims] 1. A barrier layer in a transfer recording medium, comprising an intermediate layer containing a photodegradable compound and a photothermal conversion substance, a barrier layer and a heat transferable ink layer, which are sequentially provided on one surface of a light transmissive support. Contains at least one film-forming substance having a glass transition temperature of 50 ° C. or higher and a melting point or softening point of 150 ° C. or higher, and the tensile breaking strength (based on ASTM D 638-61T) of the barrier layer. Elongation at break (ASTM D
(Based on 638-61T) is 500 to 2500 kg / cm ² , 30 to 150% respectively
The transfer recording medium is characterized by being within the range. 2. The transfer recording medium according to claim 1, further comprising a light reflecting layer which is removable by discharge breakdown recording on the other surface of the support. 3. The transfer recording medium according to claim 1, wherein the barrier layer is composed of a single layer. 4. The barrier layer comprises 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. The transfer recording medium according to claim 1 or 2, wherein the barrier layer is provided so as to be in contact with the intermediate layer.