JP2000343842A - Thermal transfer ribbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-color metallic luster thermal transfer ribbon with which recording can be done with a multicolor metallic luster and also a high positioning accuracy on condition that a single thermal transfer ribbon be used. SOLUTION: In the thermal transfer ribbon having at least a peelable anchor layer, a metal vapor-deposited layer and an adhesive layer formed on one of the faces of a base material film, the peelable anchor layer contains a heat- sensitive coloring matter which is decolorized by high energy heating, and colored printing takes place under a color developing state by an interaction between a coloring compound and a color developing agent in the peelable anchor layer, when the printing is performed by low energy heating. During the high energy heated printing, a decoloring agent preferentially dissolves either of the color developing agent or the coloring dissolves either of the color developing agent or the coloring compound in the peelable anchor layer when an ink composition is melted and stops the color developing process due to the interaction between the coloring compound and the color developing agent. Thus the color phase printing of the metallic vapor-deposited layer itself takes place in a decoloring state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer ribbon for obtaining a recorded matter of an image such as a character having a metallic luster or a pattern by a thermal transfer recording method. In particular,
The present invention relates to a thermal transfer ribbon capable of two-color printing with metallic luster represented by two colors of gold and silver.

[0002]

2. Description of the Related Art Conventionally, a hot stamping method is well known as a method for obtaining a printed material having metallic luster. However, in printing by the hot stamping method,
Since it is necessary to create a stamp made of metal or the like that has the same shape as the characters or patterns to be printed, it is uneconomical and difficult to print a small number of copies. Has been required to form fine halftone dots on a stamp by precision processing.

In recent years, a thermal transfer recording method using a thermal head and a thermal transfer ribbon has become widespread, and such a method is suitable for printing a small number of copies and can easily print a halftone image by area gradation. It has been expected that if this method is used, it is possible to obtain a printed matter having a small number of copies and a metallic gloss in halftone expression. Therefore, for example, Japanese Patent Application Laid-Open No. 63-30288 and Japanese Patent Application Laid-Open No. 1-2570
Japanese Patent Publication No. 82 attempts to perform thermal transfer with a thermal head using a transfer foil used in a conventional hot stamping method. These transfer foils, on the base film, a release layer,
A vapor deposition anchor layer, a metal vapor deposition layer, a configuration in which an adhesive layer is sequentially laminated, or in such a configuration, the vapor deposition anchor layer has the function of a release layer and the release layer is omitted, and on the base film, a vapor deposition anchor layer, It had a configuration in which a metal deposition layer and an adhesive layer were sequentially laminated.

[0004]

In order to perform multi-color printing using one thermal transfer ribbon, recording is performed by a thermal head for each color in a form in which a plurality of colors are applied in a face-sequential manner on the thermal transfer ribbon. Was performed to transfer each color to an object to be transferred, thereby obtaining a multicolor record. Such a multi-color record,
There has been a demand for a hue having metallic luster, which has been studied. However, in the case of a thermal transfer ribbon provided with a metal deposition layer, for example, when multiple colors of hues having metallic luster are separately applied, the coating surface coated with different colors is deposited on the entire surface. However, there is a problem that the positioning cannot be performed because of the failure. That is, there is a disadvantage that multicolor recording of a hue having metallic luster cannot be performed using one thermal transfer ribbon. Therefore, the present invention improves and solves the above-mentioned problems, and prints a print record having a multi-color metallic luster on a condition of using one thermal transfer ribbon with a good positional accuracy and excellent metallic luster. It is an object to provide a glossy thermal transfer ribbon.

[0005]

Means for Solving the Problems In order to achieve the above object, the present invention relates to a thermal transfer ribbon provided with at least a release anchor layer, a metal deposition layer, and an adhesive layer on one surface of a substrate film. The release anchor layer contains a heat-sensitive dye that is decolorized by high-energy heating. When printing with low-energy heat, colored printing is performed in the release anchor layer according to the color development state. When printing with high-energy heating, the release anchor layer is used. In the decolored state, printing of the hue of the metal deposition layer itself is performed. Further, on one surface of the substrate film, at least, in a thermal transfer ribbon provided with a release anchor layer, a metal deposition layer, and an adhesive layer, the release anchor layer contains a heat-sensitive dye that develops color by heating with high energy, During the heating printing of energy, the hue of the metal deposition layer itself is printed in the non-colored state in the peeling anchor layer, and during the printing of high energy, the colored printing due to the coloring state is performed in the peeling anchor layer. Features.

[0006] The heat-sensitive dye which is decolored by heating contains three components of a color former, a color developer and a decolorant. In the ink composition in which the three components are dispersed in a binder, a low-energy heating is performed. At the time of printing, the color developing state of the interaction between the color developing compound and the color developing agent, and at the time of high-energy heating printing, the decoloring agent is used when the ink composition is melted. It preferably has a property of dissolving preferentially. In addition, the heat-sensitive dye that forms a color by heating includes two components of a color former and a developer, and at the time of high-energy heating printing, in a color development state of the interaction between the color developer and the developer, It is preferable that a non-colored state is obtained in which no color is formed due to the interaction between the color former and the color developer during the heating printing with low energy.

[0007]

According to the present invention, there is provided a thermal transfer ribbon in which at least one release anchor layer, a metal deposition layer and an adhesive layer are provided in this order on one surface of a base film, and the release anchor layer is decolorized by heating with high energy. When printing with low energy, colored printing is performed in the release anchor layer during heating printing with low energy. Hue printing is performed. That is, the heat-sensitive dye that is decolorized by heating contains three components of a color former, a color developer, and a decolorant. At the time of low-energy heating printing, the ink in which the three components are dispersed in a binder is used. In the composition, the release anchor layer, the metal deposition layer, and the adhesive layer are transferred to the transfer target, and the release anchor layer becomes a colored state due to the interaction between the color former and the developer, and the release anchor is printed on the printed matter. Combined with the transparent effect of the metal color of the metal deposition layer under the layer, for example,
If the color of the release anchor layer is red-yellow and the metal vapor deposition layer is silver, these are combined to form a gold colored print. On the other hand, at the time of high-energy heating printing, in the above-mentioned three components in the release anchor layer, when the ink composition melts, the color erasing agent preferentially dissolves one of the developer and the coloring compound, The color development due to the interaction between the color-forming compound and the developer is stopped, the release anchor layer is in a decolored state, and the hue of the metal color itself of the underlying metal deposition layer is printed in a substantially transparent state.

Further, the present invention provides a thermal transfer ribbon having at least a release anchor layer, a metal deposition layer, and an adhesive layer provided in this order on one surface of a substrate film, by heating the release anchor layer with high energy. Contains a heat-sensitive dye that develops color.When heating with low energy, the release anchor layer is in a non-colored state, is almost transparent, and the hue of the metal color itself of the metal deposition layer below is printed, and high energy is printed. At the time of heating printing, in the release anchor layer, for example, two components of a color developing compound and a developer are in a color-developed state, and the printed matter is transparent to the metal color of the metal deposition layer below the release anchor layer. For example, if the color of the peeling anchor layer is red-yellow and the metal deposition layer is silver, for example, these are combined to form a gold colored print.

[0009]

Next, embodiments of the present invention will be described in detail. The thermal transfer ribbon of the present invention has a configuration in which at least a release anchor layer, a metal deposition layer, and an adhesive layer are provided on one surface of a base film in this order from the base film side. Then, a heat-resistant layer can be provided on the other surface of the base film. Further, the thermal transfer ribbon of the present invention can be provided with a release layer between the base film and the release anchor layer, if necessary.

(Substrate film) As the substrate film,
The material is not particularly limited as long as it is resistant to heating of the thermal head during thermal transfer recording and has desired heat conductivity, mechanical strength, and the like, and known materials used for conventional thermal transfer ribbons and the like can be used. For example, there are plastic films such as polyester, polypropylene, polystyrene, cellophane, cellulose acetate, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyimide, etc., condenser paper, papers such as paraffin paper, non-woven fabrics and the like. It may be what you did. The thickness of the base film is appropriately adjusted in view of its mechanical strength, thermal conductivity and the like, but is usually preferably about 2 to 25 μm.

(Peeling Anchor Layer) The peeling anchor layer is a layer that forms the outermost surface of a recorded material by transferring all or a part of it in the thickness direction from the thermal transfer ribbon to the object to be transferred during transfer recording by cohesive failure. It is. It is preferable that the cohesive force at the time of recording is low so that the foil at the time of printing is good. The release anchor layer enables separation of the base film and the metal deposition layer, provides a base for metal deposition, protects the metal deposition layer from heat during transfer, and realizes a metal luster. Things. Further, after the transfer printing, transfer to the transfer receiving body together with the metal vapor deposition layer, it is located on the metal vapor deposition layer and is in close contact with the metal vapor deposition layer, and becomes one component of the recorded matter,
It also functions as a protective layer for improving the mechanical and chemical strength of the metal deposition layer such as abrasion and corrosion.

[0012] In the thermal transfer ribbon of the present invention, the release anchor layer has a lower energy and a higher energy during heating printing.
The release anchor layer is in a decolored or colored state, and is roughly classified into the following two types. One is that the release anchor layer contains a heat-sensitive dye that is decolored by high-energy heating, and when printing with low energy heating, colored printing is performed in the release anchor layer due to the color development state, and when printing with high energy heating. In this case, the hue of the metal deposition layer itself is printed in the decolored state in the release anchor layer. The other is that the release anchor layer contains a heat-sensitive dye that develops color when heated with high energy, and during low-energy heating printing, the hue of the metal deposition layer itself is printed in a non-colored state in the release anchor layer. During high-energy heating printing, colored printing is performed in the release anchor layer by a color-developing state.

First, the case where the release anchor layer contains a thermosensitive dye which is decolorized by heating with high energy will be described. The heat-sensitive dye that is decolorized by heating contains three components of a color former, a developer, and a decolorant. In the ink composition in which the three components are dispersed in a binder, low-energy heating is performed. At the time of printing, the color developing state of the interaction between the color developing compound and the color developing agent, and at the time of high-energy heating printing, the decoloring agent is used when the ink composition is melted. It has the property of dissolving preferentially and is in a decolored state in the release anchor layer. The coloring compound and the developer used here are in a color-developed state by heating at a low energy, and at a low energy of, for example, about 0.2 mJ / dot due to the interaction between the coloring compound and the developer. It is necessary to select a material that is in a colored state. However, when heating at a high energy of, for example, about 0.4 mJ / dot, the color erasing agent preferentially dissolves one of the color developer and the color developing compound when the ink composition is melted. No color development occurs between the color compound and the color developer.

Here, the color-forming compound is a precursor of a dye, and the color-developing agent is a compound for coloring the color-forming compound by interaction with the color-forming compound such as transfer of electrons. The coloring agent is a compound having a property of preferentially dissolving either the color developing compound or the color developing agent at the time of melting. When these three components coexist, they take two states, a color development state and a color erasing state. In one state, the coloring compound and the developer within the range of the equilibrium solubility are not colored because the coloring compound and the developer are present in excess of the equilibrium solubility of the decoloring agent, but the equilibrium solubility is reduced. This is the state of color development as a result of the interaction of the excess amount of the color former and the developer. The other condition is that the decoloring agent takes up a large amount of the coloring compound or the developing agent beyond the equilibrium state, and the decoloring state as a result of reduced interaction of the coloring compound or the developing agent. is there.

Assuming that the decoloring agent has a property of preferentially dissolving the color developing agent at the time of melting, at room temperature, each phase of the color developing compound, the color developing agent and the color decoloring agent is phase-separated. The colored state is close to the equilibrium state, and in this state, the color-forming compound and the color developer are brought into a colored state as a result of interaction. When the developer in this state is heated to a temperature equal to or higher than the melting point, the color developer is preferentially dissolved in the melted color erasing agent and interacts with the color developing compound, resulting in a color erasing state. When the three components in the molten state are rapidly cooled, the decoloring agent becomes amorphous by taking in an amount of the developer exceeding the equilibrium solubility and becomes colorless at room temperature. Although this colorless state is not an equilibrium state, it has a sufficiently long life if it is lower than the glass transition point, and does not easily transition from an amorphous state to an equilibrium state even at a temperature higher than the glass transition temperature.

Examples of the coloring compound include leuco auramines, diaryl phthalides, polyaryl carbinols, acyl auramines, aryl auramines, rhodamine B lactams, indolines, spiropyrans,
Electron-donating organic compounds such as fluorans.

Specific examples of the color-forming compound include crystal violet lactone, malachite green lactone, 2-anilino-6- (N-cyclohexyl-N-methylamino) -3-methylfluoran, and 2-anilino-
3-methyl-6- (N-propylamino) fluoran,
3- [4- (4-phenylaminophenyl) aminophenyl] amino-6-methyl-7-chlorofluoran, 2
-Anilino-6- (N-methyl-N-isobutylamino) -3-methylfluoran, 2-anilino-6- (dibutylamino) -3-methylfluoran, 3-chloro-
6- (cyclohexylamino) fluoran, 2-chloro-6- (diethylamino) fluoran, 7- (N, N-
Dibenzylamino) -3- (N, N-diethylamino)
Fluoran, 3,6-bis (diethylamino) fluoran-γ- (4′-nitroanilino) lactam, 3-diethylaminobenzo [a] -fluoran, 3-diethylamino-6-methyl-7-aminofluoran, 3-diethylamino- 7-xylidinofluoran, 3- (4-diethylamino-2-ethoxyxenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3 -(1-
Ethyl-2-methylindol-3-yl) phthalide,
3-diethylamino-7-chloroanilinofluoran,
3-diethylamino-7,8-benzofluoran, 3,
3-bis (1-n-butyl-2-methylindole-3
-Yl) phthalide, 3,6-dimethylethoxyfluoran, 3,6-diethylamino-6-methoxy-7-aminofluoran, DEPM, ATP, ETAC, 2- (2
-Chloroanilino) -6-dibutyldinofluoran, crystal violet carbinol, malachite green carbinol, N- (2,3-dichlorophenyl) leuco auramine, N-benzoyl auramine, rhodamine B lactam, N-acetyl auramine, N-phenyl auramine, 2- (phenyliminoethanedylidene)-
3,3-dimethylindoline, N, 3,3-trimethylindolinobenzosubiropyran, 8'-methoxyN,
3,3-trimethylindolinobenzosubiropyran, 3
-Diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-methoxyfluoran, 3
-Dielamino-6-benzyloxyfluoran, 1,
2-benzo-6-diethylaminofluoran, 3,6-
Di-p-toluidino-5-dimethylfluoran, phenylhydrazide-γ-lactam, 3-amino-5-methyl-fluoran and the like. These can be used alone or in combination of two or more kinds.

Examples of the color developer which is a component of the ink composition used in the present invention include phenols, phenol metal salts,
Carboxylic acid metal salts, benzophenones, sulfonic acids,
Acid compounds such as sulfonates, phosphoric acids, metal phosphates, acid phosphates, metal acid phosphates, phosphorous acid, metal phosphites, and the like, and again, alone or in combination of two or more. Then, they can be mixed and used.

The decoloring agent used in the present invention is preferably as amorphous and colorless and transparent. For this reason, the molecular weight is large, the melting enthalpy change of the crystal per weight is small,
It is desirable that the compound has a small maximum crystal growth rate. Those having a nearly spherical and bulky molecular skeleton such as a steroid skeleton are preferred. Further, the higher the affinity of the color developer for the color erasing agent, the higher the solubility of the color developer, and for example, a compound having an alcoholic hydroxyl group is suitable. From the viewpoint of the stability of the three components in the decolored state, those having a glass transition temperature of the decoloring agent of room temperature (25 ° C.) or higher, more preferably 50 ° C. or higher are more preferable. The glass transition temperature is preferably 150 ° C. or lower. Decoloring agents satisfying these are (a) a sterol product, (b) cholic acid, lithocholic acid, testosterone, and cortisone, and derivatives thereof, and (c) a 5-membered ring or more having one or more hydroxyl groups. Is a non-aromatic cyclic compound.

Specific examples of the sterol processed product (a) include cholesterol, stigmasterol, pregnenolone, methylandrostenediol, estradiol benzoate, epiandrostene, stenolone, β
-Sitosterol, pregnenolone acetate, β-cholestenol, 5,16-pregnadien-3β-ol-20-one, 5α-pregnene-3β-ol-2
0-one, 5-pregnene-3β, 17-diol-2
0-one 21-acetate, 5-pregnene-3β,
17-diol-20-one 17-acetate, 5-
Pregnene-3β, 21-diol-20-one 21
-Acetate, 5-pregnene-3β, 17-diol diacetate, locogenin, tigogenin, esmilagenin, hecogenin, diosgenin and derivatives thereof. These can be used alone or in combination of two or more kinds. Among them, those suitable for obtaining a stable decolored state include methylandrostenediol, hecogenin, locogenin, tigogenin, diosgenin, and esmilagenin.

(B) Specific examples of cholic acid, lithocholic acid, testosterone, and cortisone, and derivatives thereof, include cholic acid, cholic acid methyl ester,
Examples include lithocholic acid, lithocholic acid methyl ester, hydroxycholic acid, hydroxycholic acid methyl ester, testosterone, methyltestosterone, 11α-hydroxymethyltestosterone, and hydrocortisone. Among them, those having two or more hydroxyl groups are particularly preferable.

(C) Examples of the non-aromatic cyclic compound having five or more rings having one or more hydroxyl groups include alicyclic monohydric alcohols (for example, cyclododecanol) and alicyclic monohydric alcohols. Dihydric alcohols (for example, 1,4-cyclohexanediol, 1,2-cyclohexanediol,
1,2-cyclododecanediol), saccharides and derivatives thereof (eg, glucose and saccharose), and alcohols having a cyclic structure (eg, 1,2,5,6-diisopropylidene-D-mannitol).

In the above description, the color erasing agent (b) has a very high compatibility with the color developing agent at the time of melting as compared with the color erasing agent (a), and does not easily cause phase separation even when the three components are solidified. . (C)
The decolorizing agent has a high affinity with the decoloring agent of (a), and hardly causes phase separation even after solidification.

Next, the case where the release anchor layer contains a thermosensitive dye which develops a color by heating with high energy,
explain. As the heat-sensitive coloring material that develops color by heating, various conventionally known heat-sensitive coloring materials can be used. That is, it is composed of a color former (color developing compound), a color developer, a sensitizer, a storage stabilizer, and a binder resin, and the two components of the color former and the developer become colored during high-energy heating printing. Thus, at the time of low-energy heating printing, the coloring compound and the color developing agent are not colored, and are in a non-colored state. The two components of the color former and the developer, which are heat-sensitive dyes that develop color when heated with high energy, are the same as described above. Examples of the sensitizer include P-benzyldiphenyl, 2-benzyloxynaphthalene and the like. Examples of the storage stabilizer include a hindered phenol-based antioxidant and the like. However, the two components of the color former and the developer used here develop color by heating with high energy,
The interaction between the color former and the developer, for example, 0.4 m
It is necessary to select a material that starts color development with a high energy of about J / dot. And, for example, 0.2mJ
Heating at a low energy of about / dot does not cause color development between the color former and the color developer.

The above-mentioned color-forming compound, developer and decolorant 3
The composition ratio of each component of the release anchor layer coating liquid, that is, the ink composition containing the component type and the two-component type of the color former and the color developer, is such that the color former is 1 part by weight relative to the developer. 0.1 to 10 parts by weight of a coloring agent, more preferably 1 to 2 parts by weight
Parts by weight. When the amount of the developer is less than 0.1 part by weight, color development is insufficient, and when the amount exceeds 10 parts by weight, it is difficult to sufficiently reduce the interaction between the two. The decoloring agent is used in an amount of 1 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 1 part by weight of the color former. If the amount is less than 1 part by weight, it is difficult to cause a state change between the color-developed state and the decolored state, and if it exceeds 200 parts by weight, the coloration of the ink becomes insufficient. The solvent of the release anchor layer ink composition is preferably water, but an organic solvent can be used. When an organic solvent is used, the color former, the color developer, and the decolorant may be dispersed using a surfactant, but it is more preferable to disperse them by microencapsulation. Also, a coloring compound, a developer,
And the ratio of the decoloring agent in the ink composition is 0.1 to 10
%, Preferably less than 0.1% by weight.
It is difficult to obtain a sufficient print density, and if it exceeds 10% by weight, the viscosity of the ink composition may become excessive and printing may be difficult. Further, it is preferable that the color-forming compound, the color developer, and the color erasing agent dispersed in the solvent are submicron-order particles that do not include particles of 10 μm or more.

The release anchor layer contains the above-described coloring compound, color developer, and / or decoloring agent, and a binder for binding them. The material of the binder of the release anchor layer is not particularly limited as long as it has transparency enough to allow the metallic gloss of the metal deposition layer to be seen through. Such materials include, for example, alkyd resins, phenolic resins, polyimides, epoxy resins, urethane resins, thermosetting resins such as unsaturated polyester resins, polyethylene,
Olefinic resins such as polypropylene, acrylic resins such as polymethyl methacrylate and polyacrylamide,
Styrene resins such as polystyrene, polyvinyl resins such as polyvinyl chloride and polyvinyl acetate, polyoxymethylene,
Examples include thermoplastic resins such as polyether resins such as polyphenylene oxide, polyvinyl butyral resins, nitrocellulose resins, and ethyl cellulose resins. Among these resins, it is preferable to use a resin having a relatively low molecular weight and a low cohesive force, from the viewpoints of heat resistance, releasability from the base film side, adhesion with the metal vapor deposition layer, foil breakability during printing, and the like. preferable.

The thickness of the release anchor layer is usually set in the range of about 0.1 to 20 g / m ^{2 in} terms of coating amount. Further, for example, for the purpose of coloring the metal vapor-deposited layer with aluminum or the like, a colorant of cyan, magenta, yellow, black, or another color with a known dye or pigment or the like is in a range that does not affect the transparency of the release anchor layer. And can be mixed. If the thickness is less than 0.1 g / m ^2, it does not function as a release anchor layer, and if it exceeds 20 g / m ² , the foil breakage at the time of printing becomes poor and halftone recording becomes difficult.

(Release Layer) The thermal transfer ribbon of the present invention may have a release layer between the base film and the release anchor layer, if necessary. The peeling layer is a layer that forms the outermost surface of a printed material by transferring all or a part of the peeling layer due to cohesive failure in the thickness direction from the thermal transfer ribbon to the transfer-receiving body side during transfer recording. In the case of partial transfer or full transfer, it is preferable that the cohesive force at the time of recording is low so that the foil breakage at the time of printing is good. Alternatively, the layer may not transfer at all. In short, the release layer allows the thermal transfer ribbon to peel off at the release layer or at a surface adjacent to the release layer, thereby enabling separation of the substrate film and the metal deposition layer. As the release layer,
For example, carnauba wax, paraffin wax, microcrystalline wax, ester wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, partially modified Various waxes such as wax, fatty acid ester, and fatty acid amide are used.

As the release layer, a resin other than the above-mentioned wax can be used as long as the releasability from the substrate film or the like is appropriate, and only the resin or a mixture of the above-mentioned wax and the resin may be used. . Examples of such a resin include rubber resins such as polyisoprene rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, acrylate resin, polyvinyl ether resin, polyvinyl acetate resin, and vinyl chloride-vinyl acetate copolymer type. Resins, polystyrene resins, polyester resins, polyamide resins, polyimide resins, polychlorinated olefin resins, polycarbonate, polyvinyl butyral resins, and the like. Release layer thickness is 0.05 in coating amount
To 10 g / m ² approximately, preferably not providing ^two degrees 0.2 to 3 g / m. In the case of 0.05 g / m ² , a uniform ink layer cannot be obtained due to the problem of film forming property, and the function as a release layer is not performed. Further, when the coating amount exceeds 10 g / m ² , the foil breakage at the time of printing is reduced, and the coating may not be used.

(Metal Deposition Layer) The metal deposition layer was formed by metallizing a metal such as aluminum, zinc, tin, chromium, gold, silver or the like, or an alloy such as brass under vacuum such as vacuum deposition and sputtering. It is a metal thin film layer.
When the thickness of the metal deposition layer is usually in the range of 100 to 1000 °, preferably 200 to 600 °, it is sufficient to obtain a metallic luster. If it is too thin, it does not reflect visible light to the extent that a glossy feeling can be obtained, and if it is too thick, foil breakage during printing deteriorates and it is uneconomical.

(Adhesive Layer) As the adhesive layer, waxes such as microcrystalline wax, carnauba wax, paraffin wax, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer Or a mixture thereof. The thickness of the adhesive layer is 0.1
About 10 g / m ² . If the thickness of the adhesive layer is too small, sufficient adhesive strength cannot be obtained, resulting in poor sensitivity. On the other hand, if the thickness of the adhesive layer is too large, excessive energy is required to melt the adhesive layer, and the foil breakage is undesirably reduced.

(Heat-Resistant Layer) Further, a heat-resistant layer can be provided on the other surface of the substrate film in order to prevent sticking of the thermal head and to improve slipperiness. The heat-resistant layer is formed by suitably using a binder resin to which a slip agent, a surfactant, inorganic particles, organic particles, a pigment and the like are added. Binder resin used for the heat-resistant layer, for example, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose resin such as nitrified cotton, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal , Polyvinylpyrrolidone, acrylic resin, polyacrylamide, acrylonitrile-vinyl copolymer such as styrene copolymer, polyester resin, polyurethane resin,
Silicone-modified or fluorine-modified urethane resin,
can give. Among these, several reactive groups, for example, using those having a hydroxyl group, as a crosslinking agent,
It is preferable to use a crosslinked resin in combination with a polyisocyanate or the like. The thickness of the heat-resistant layer is sufficient as long as it can perform functions such as fusion prevention and lubricity.
About 3 μm.

As described above, in the thermal transfer ribbon of the present invention, in order to form a release anchor layer, an adhesive layer, or a heat-resistant layer on a substrate film, the constituent materials of the layer are dissolved in a solvent such as an organic solvent. Alternatively, it can be formed as a dispersed coating liquid by a conventionally known gravure coat, gravure reverse coat, roll coat, knife coat, or any other known coating means. In the case of a layer mainly composed of wax, coating means such as hot melt coating and hot lacquer coating can also be used. The thermal transfer ribbon configured as described above can be used as a transfer foil of a conventional hot stamping method, but the characteristic as that capable of performing thermal transfer of a fine pattern is a character or pattern as a thermal transfer ribbon used in a conventionally known thermal head. And more in the field of printing and recording images such as
A hue having two metallic lusters can be imparted to these images. Further, as a density gradation expression method, an intermediate density can be reproduced by expressing the density gradation by the size of the area of the transfer portion according to the size of the halftone dot, that is, by using the area gradation. In addition, as a method of the area gradation, a screen pattern or the like known in the printing field using a grain, a brick pattern, or the like can be used in addition to a halftone dot.

[0034]

The present invention will be described more specifically with reference to examples and comparative examples. In the text, "part" or "%" means
Unless otherwise specified, it is based on weight. (Example 1) A polyethylene terephthalate film having a thickness of 9 µm was used as a base film, and a heat-resistant layer having a thickness of 0.2 g / m ² (a coating amount when dried, the same applies hereinafter) made of silicone-modified polyester was used on one surface. On the other surface, a release anchor layer having the following composition was formed at a thickness of 0.5 g / m ² , and a 300 ° -thick aluminum metal deposition layer was further formed on the release anchor layer by a vacuum deposition method. An adhesive layer having the following composition and a thickness of 1 g / m ² was formed on the vapor deposited layer by a coating method to obtain a thermal transfer ribbon of Example 1.

Composition of release anchor layer Coloring compound: PSD-HR (manufactured by Nippon Soda Co., Ltd.) 1 part Color developer: α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-- Isopropylbenzene 1 part Decoloring agent: Prognenolone 20 parts Binder: Styrene-methacrylic acid copolymer 20 parts Solvent: Water 58 parts

Adhesive layer composition 60 parts carnauba wax 30 parts polyester resin

Example 2 A thermal transfer ribbon of Example 2 was prepared in the same manner as in Example 1 except that the composition of the release anchor layer of the thermal transfer ribbon of Example 1 was changed to the following composition. Separation anchor layer composition A solution, B solution, C solution, D solution and a 1% solution of polyvinyl alcohol shown below were prepared. 55 parts of A solution, 115 parts of B solution,
80 parts of liquid, 24 parts of liquid D, polyvinyl alcohol 1%
A mixture obtained by mixing 80 parts of the solution was used as a coating liquid. Solution A: Orange 100 (manufactured by Yamada Chemical Industry) 10 parts Methyl cellulose 5% aqueous solution 5 parts Water 40 parts The above was pulverized by a sand mill until it became 0.2 μm.

Solution B: 30 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone 5 parts of a 5% aqueous solution of methylcellulose 5 parts 80 parts of water The above was pulverized by a sand mill until it became 0.2 μm.

Solution C: 1,2-di (3-methylphenoxy) ethane 20 parts Methylcellulose 5% aqueous solution 5 parts Water 55 parts The above was pulverized by a sand mill until it became 0.2 μm.

Solution D: methacrylic glycidyl ester 30 parts Styrene-acrylic copolymer resin 20 parts Methyl cellulose 5% aqueous solution 5 parts Water 55 parts The above was pulverized by a sand mill to 0.2 μm.

Using the thermal transfer ribbon of each of the above-described examples and a mirror-coated paper as the transfer object, the thermal transfer ribbon and the transfer object are superimposed on each other to form a 150 dpi manufactured by Kyocera Corporation.
Using a line type head thermal head of 0.2
Printing was performed by applying low energy of mJ / dot and high energy of 0.4 mJ / dot in different patterns.

(Evaluation Results) When recording was performed under the above printing conditions using the thermal transfer ribbon produced in Example 1,
With one thermal transfer ribbon, two colors of metallic luster hues with good positional accuracy and excellent metallic luster, that is, a gold print in a low-energy heated print section and a silver print in a high-energy heated print section. Obtained. Furthermore, when recording was performed under the above printing conditions using the thermal transfer ribbon produced in Example 2, two thermal hues of two colors having good positional accuracy and excellent metallic gloss were obtained with one thermal transfer ribbon. That is, a printed matter having a silver color was obtained in the low-energy heating printing section and a gold color was obtained in the high-energy heating printing section.

[0043]

As described above, according to the present invention, in a thermal transfer ribbon having at least a release anchor layer, a metal deposition layer and an adhesive layer provided in this order on one surface of a base film, the release anchor layer Contains a heat-sensitive dye that is decolored by high-energy heating, and during low-energy heating printing, colored printing is performed by a color-developed state in the release anchor layer.
At the time of high energy heating printing, the hue of the metal deposition layer itself is printed in a decolored state in the release anchor layer. That is, the heat-sensitive dye that is decolorized by heating contains three components of a color former, a developer, and a decolorant. In low-energy heating printing, the three components are dispersed in a binder. With the composition, the release anchor layer, the metal deposition layer, and the adhesive layer are transferred to the transfer target, and the interaction between the color former and the color developer causes the release anchor layer to become colored. On the other hand, at the time of high energy heating printing, the above 3
In the component, when the decoloring agent melts the ink composition, one of the color developer and the color developing compound is preferentially dissolved to stop the color development due to the interaction between the color developing compound and the color developing agent, The release anchor layer is in a decolored state, and the hue of the metal color itself of the underlying metal deposition layer is printed in a substantially transparent state.

According to the present invention, in a thermal transfer ribbon having at least a release anchor layer, a metal deposition layer and an adhesive layer provided in this order on one surface of a substrate film, the release anchor layer is heated by high energy. Contains a heat-sensitive dye that develops color.When heating with low energy, the release anchor layer is in a non-colored state, is almost transparent, and the hue of the metal color itself of the metal deposition layer below is printed, and high energy is printed. During the heating printing, the two components of the coloring compound and the developer are colored in the release anchor layer, and colored printing is performed.

Continued on the front page F term (reference) 2C068 AA02 AA06 AA15 BB01 BB04 BB08 BB18 BB27 BB33 BC03 BC12 BC24 BD17 BD27 BD35 BD37 2H111 AA01 AA26 AA31 BA02 BA03 BA06 BA09 BA52 BA53 BA55 BA74 BA76

Claims (7)

[Claims] In a thermal transfer ribbon provided with at least a release anchor layer, a metal deposition layer, and an adhesive layer on one surface of a base film, a heat-sensitive dye which is decolored by high-energy heating is provided in the release anchor layer. When printing with low energy, colored printing is performed in the release anchor layer during heating printing with low energy, and during high energy heating printing, the color is decolored in the peeling anchor layer, and the hue of the metal deposition layer itself is printed. A thermal transfer ribbon characterized by being performed. 2. A thermal transfer ribbon having at least one release anchor layer, a metal deposition layer, and an adhesive layer on one surface of a base film, wherein the release anchor layer contains a heat-sensitive dye that develops color by heating with high energy. However, at the time of low-energy heating printing, the hue of the metal deposition layer itself is printed in a non-colored state in the peeling anchor layer, and at the time of high-energy heating printing, colored printing due to the coloring state is performed in the peeling anchor layer. A thermal transfer ribbon characterized by being transferred. 3. The heat-sensitive dye which is decolorized by heating as described above,
In an ink composition containing three components of a color former, a color developer and a decolorant, and the three components dispersed in a binder, the interaction between the color former and the developer during low-energy heating printing is performed. In a color-developing state of action, the decoloring agent has a property of preferentially dissolving one of the developer and the coloring compound when the ink composition is melted during high energy heating printing. Item 4. The thermal transfer ribbon according to Item 1. 4. The thermal transfer ribbon according to claim 3, wherein the decoloring agent is a sterol compound. 5. The thermal transfer ribbon according to claim 3, wherein the decoloring agent is at least one selected from cholic acid, lithocholic acid, testosterone, cortisone, and derivatives thereof. 6. The thermal transfer ribbon according to claim 3, wherein the decoloring agent is a 5-membered or more non-aromatic cyclic compound having at least one hydroxyl group. 7. The heat-sensitive dye that develops color by heating as described above,
It contains two components, a color former and a color developer, and in the state of color development of the interaction between the color former and the color developer during high-energy heating printing, and with the color former during low-energy heating printing. 3. The thermal transfer ribbon according to claim 2, wherein the thermal transfer ribbon is in a non-colored state in which no interaction with a color developer is developed.