JPH08118832A - Heat transfer ribbon - Google Patents

Abstract

PURPOSE: To improve greatly fixing property and durability of an image to be formed by sublimation type heat transfer recording at the time of performance of the sublimation type heat transfer recording and hot-melt type heat transfer recording with one ribbon. CONSTITUTION: A heat transfer ribbon IA is constituted by providing a sublimation ink layer 3 which is an ink layer containing sublimation or heat dispersion dyes and the dyes are transferred to a transferred body from the ink layer by heating, a hot-melt transfer ink layer 4 comprised of hot-melt ink which is molten and transferred to the transferred body through heating and a heat transfer laminated layer 5 which is molten and transferred to the transferred body through heating. Cationic dyes which are made into a hydrophobic state is caused to be contained into the sublimating ink layer 3 and an interlaminar compound which can fix and hold the cation which is made into the hydrophobic state is caused to be contained into the heat transfer laminated layer 5.

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 capable of performing sublimation type thermal transfer recording and thermal melting type thermal transfer recording with one ink ribbon.

[0002]

2. Description of the Related Art Conventionally, an object to be transferred such as photographic paper and an ink ribbon are superposed and heated selectively according to an image signal by using a heating means such as a thermal head or a laser.
A thermal transfer recording method in which a dye is transferred from an ink ribbon to a transfer target to form an image is widely used. As a thermal transfer recording method, a thermal melting type thermal transfer recording method in which an ink layer of an ink ribbon is formed from a binder resin such as a thermoplastic resin and a dye or a pigment, and the ink layer is transferred to a transfer target by thermal melting, and an ink layer There is known a sublimation-type thermal transfer recording method in which a sublimable or thermal diffusible dye such as a disperse dye is used as the dye, and the thermally diffusible dye is transferred to a transfer target by sublimation or thermal diffusion. Among these, the sublimation type thermal transfer recording method is
Since it is possible to obtain a full-color image having gradation depending on the heating energy, it has been attracting attention as a technique for hard-copying images of video cameras, televisions, computer graphics and the like.

However, the image formed by the sublimation type thermal transfer recording method is inferior in fixing property to the image formed by the heat melting type thermal transfer recording method due to resublimation of a sublimable or heat diffusible dye. Therefore, the sublimation type thermal transfer recording method, as in the case of recording character information or bar code information on cards such as ID cards, prepaid cards, and credit cards,
This is unsuitable when recording a binary image requiring high contrast.

Therefore, when both a gradation image such as a photographic image and a binary image requiring a high contrast are formed on cards, the photographic image is sublimation type thermal transfer recording. And a binary image is formed by a thermal fusion type thermal transfer recording method. In order to easily perform the sublimation type thermal transfer recording and the heat melting type thermal transfer recording in this case, the ink layer for the sublimation type thermal transfer recording and the ink layer for the heat melting type thermal transfer recording are formed on one ink ribbon. There has been proposed a thermal transfer ribbon which is alternately and repeatedly provided in the length direction of the ribbon (Claims of Japanese Patent Publication No. 5-28996).

[0005]

However, a conventional ink ribbon provided with both an ink layer for sublimation type thermal transfer recording and an ink layer for heat melting type thermal transfer recording is used for photographic images and binary images on cards and the like. When an image is formed, the stability of the image formed by the ink layer for heat-melting type thermal transfer recording can be secured, but the fixability of the image formed by the ink layer for sublimation type thermal transfer recording is still insufficient, It has also been desired to improve image fastness such as plasticizer resistance and chemical resistance.

The present invention is intended to solve the problems of the prior art as described above, and in performing sublimation type thermal transfer recording and thermal melting type thermal transfer recording with one ink ribbon,
The fixability and fastness of images formed by sublimation thermal transfer recording are greatly improved, and both the images formed by sublimation thermal transfer recording and the images formed by hot melt thermal transfer recording have excellent fixability and fastness. The purpose is to have

[0007]

The present inventor uses a hydrophobized cationic dye as a dye to be used in an ink layer for sublimation type thermal transfer recording to form a transfer image on a transfer target, and forms a transfer image on the transfer image. It was found that the image fastness is remarkably improved by laminating a laminate layer composed of an intercalation compound which fixes and holds the hydrophobic cation dye by an ion exchange reaction. Further, when a binder resin used in an ink layer for hot-melt type thermal transfer recording is used as a binder resin for such a laminate layer, and the laminate layer is thereby provided with a thermal transfer property, the thermal transfer laminate layer is It was also found that thermal transfer can be performed from the ink ribbon to the transfer target similarly to the ink layer for heat-melt thermal transfer recording. Further, an infrared absorber or an ultraviolet absorber, that is, the visible region is substantially visible, which allows the transferred image to be located below the heat transferable laminate layer in the transferred material to be seen through from the heat transferable laminate layer. Although it is transparent to the infrared absorption agent or ultraviolet absorption agent having absorption in the infrared or ultraviolet region in the thermal transfer laminate layer,
The heat transferable laminate layer can be used not only as a layer for enhancing the image fastness of a transfer image formed with a hydrophobic cationic dye, but also as a layer for forming a transfer image having absorption in the infrared or ultraviolet region. The inventors have found out what can be done and have completed the present invention.

That is, the present invention is, as a first invention, an ink layer containing a sublimable or heat diffusible dye on the same surface of a sheet-like substrate, and the ink layer is transferred from the ink layer to a transfer target by heating. The sublimable ink layer to which the dye is transferred, the heat-melt transferable ink layer that is melt-transferred to the transfer target by heating, and the heat transferable laminate layer that is melt-transferred to the transfer target by heating are provided. The thermal transfer ribbon is characterized in that the ink layer contains a hydrophobizing cationic dye, and the thermal transferable laminate layer contains an intercalation compound capable of fixing and holding the hydrophobizing cation by an ion exchange reaction.

As a second aspect of the present invention, there is provided an ink layer containing a sublimable or heat diffusible dye on the same surface of a sheet-shaped substrate, which is transferred from the ink layer to a transfer-receiving member by heating. A sublimable ink layer to which the dye is transferred, and a heat transferable laminate layer that is melt-transferred to a transfer target by heating are provided, the sublimable ink layer contains a hydrophobic cationic dye, and the heat transferable laminate layer is A thermal transfer ribbon comprising an intercalation compound capable of fixing and retaining a hydrophobizing cation by an ion exchange reaction, and an infrared absorber or an ultraviolet absorber having a substantially transparent visible region and having an absorption in the infrared or ultraviolet region. I will provide a.

Hereinafter, the present invention will be described in detail.

FIG. 1 shows a thermal transfer ribbon 1A of the first invention.
A plan view (the same figure a) and a cross-sectional view (the same figure (b)) of one mode
Is. In each drawing, the same reference numerals represent the same or equivalent constituent elements. In this thermal transfer ribbon 1A, a sublimable ink layer 3 of each color of yellow Y, magenta M, and cyan C, a thermal melt transferable ink layer 4, and a thermal transferable laminate layer 5 are provided on the same surface of the sheet-shaped substrate 2. It is repeatedly provided.

Here, the sheet-shaped substrate 2 can be constructed in the same manner as the sheet-shaped substrate of the conventional ink ribbon, for example, polyester film such as PET, polyimide film, polyamide film such as nylon, condenser paper and the like. Papers can be used. The thickness is usually preferably 3 to 20 μm.

The sublimable ink layer 3 is an ink layer used at the time of sublimation type thermal transfer recording, and is characterized by containing a hydrophobic cationic dye as a dye. Conventionally, a disperse dye or the like has been generally used as a dye to be contained in an ink layer for sublimation thermal transfer recording, but it is not practically sufficient in terms of transfer sensitivity, image hue and light resistance. In contrast, the use of hydrophobized cationic dyes makes it possible to improve these.

That is, cations are known as dyes having unique sharpness, high colorability, and high light resistance.
Since it is hydrophilic in itself, it is difficult to uniformly and stably disperse it in the binder resin used in the sublimable ink layer 3. Therefore, in the present invention, a hydrophobized cationic dye which is hydrophobized by exchanging a counter ion such as halogen of the cationic dye with an organic anion is used.

As such a hydrophobized cationic dye,
The dyes described in paragraphs [0009] to [0015] of the claims of JP-A-6-40172 can be used. That is, the yellow dye has the formula (1)

[0016]

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group and an aralkoxy group. Group, an alkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, and Z ⁻ is a counter ion), and a counter ion of the diazacarbocyanine-based cationic dye of Hydrophobized cationic dyes obtained by exchanging with organic anions can be used. Here, examples of the cationic dye before being exchanged with the organic anion include C.I. I. Basic Yellow
28, 51 and the like and the dyes described in Japanese Examined Patent Publication No. 47-4881.

Other yellow dyes include C.I. I. Ba
Hydrophobized cationic dyes obtained by exchanging the counterions of the sic Yellow 21, 36, 67 or 73 cationic dyes with organic anions can be used.

The magenta dye is represented by the formula (2)

[0019]

Embedded image (In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group or an aralkyl. A group, an aralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, or R ²⁴ and R ²⁵ may be linked to each other to form a ring. Often, Z ⁻ is a counterion) and a hydrophobized cationic dye obtained by exchanging the counterion of the hemicyanine-based cationic dye with an organic anion can be used. Here, examples of the cationic dye before being exchanged with the organic anion include C.I. I. Basic Red 13,
14, C.I. I. Basic Violet 7, 16,
C. I. 48025, 48030, etc., USP3379
723, Japanese Patent Publication No. 34-694, Japanese Patent Publication No. 40-19
Examples thereof include dyes described in Japanese Patent Publication No. 951, Japanese Patent Publication No. 45-28024, Japanese Patent Publication No. 50-7087, Japanese Patent Publication No. 50-149723, and the like.

The cyan dye is represented by the formula (3a) or (3
b)

[0021]

Embedded image (In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ ,
R ³⁸ , R ³⁹ , R ³¹⁰ , R ³¹¹ and R ³¹² are independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group or an aralkoxy group. , An alkenyl group,
An alkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acyl group, which may be substituted, and R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁷ and R ³⁸ , R ³⁹ and R ³¹⁰ , R ³¹⁰ and R ³¹¹ and R ³¹¹ and R ³¹² may be linked to each other to form a ring, and Z ⁻ is a counterion), and a counterion of the oxazine-based cationic dye
Hydrophobized cationic dyes obtained by exchanging with organic anions can be used. Here, examples of the cationic dye before being exchanged with the organic anion include C.I. I.
Basic Blue 3, 6, 10, 12, 49, 7
5, 87, 95, 96, 101, 104, 107, 10
8, 114, 122, 124, 141, 151, 15
5, C.I. I. 51015 etc. and Japanese Patent Publication No. 45-25788
No. 47-13638, BP13565 /
90, BP18623 / 90, USP2741605,
USP494838, FP211035, GP6236
7, GP63238, GP68557, GP6855
8, dyes described in GP69820, GP71250 and the like can be mentioned.

The organic anions serving as counterions of these dyes are described in paragraphs [0017] to [0024] of JP-A-6-40172.
It can be an ion of an anionic surfactant. That is, (1) Carboxylic acid anions (1a) Soap (RCOO ⁻ ) (1b) N-acyl amino acid (RCON-COO ⁻ ) (1c) Alkyl ether carboxylic acid (RO (C ₂ H ₄
O) _n COO ⁻ ) (2) Sulfonic acid anions (2a) Alkylsulfonic acid (RSO ₃ ⁻ ) (2b) Alkylbenzenesulfonic acid (Formula (4))

[0023]

[Chemical 4] (2c) Alkylnaphthalenesulfonic acid (Formula (5))

[0024]

Embedded image (2d) sulfosuccinic acid (formula (6))

[0025]

[Chemical 6] (2e) α-olefin sulfonic acid (2f) N-acyl sulfonic acid (-CON-SO ₃ ⁻ ) (3) Sulfate ester anions (3a) Sulfated oil (3b) Alkylsulfate (ROSO ₃ ⁻ ) (3c) Alkyl ether sulfuric acid (RO (C ₂ H ₄ O) _n
SO ₃ ⁻ ) (3d) Alkyl aryl ether sulfuric acid (formula (7))

[0026]

[Chemical 7] (3e) Alkylamido sulfuric acid (RCONH-OS
O ₃ ⁻ ) (4) Phosphate ester anions (4a) Alkyl phosphoric acid (formula (8), (9))

[0027]

Embedded image (4b) Alkyl ether phosphoric acid (formula (10), (1
1))

[0028]

[Chemical 9] (4c) Alkylaryl ether phosphate In the above organic anion, R, Ra and Rb preferably have 5 to 2 carbon atoms in view of availability and cost.
0 is a linear or branched alkyl or alkenyl group.

Among such organic anions, (2
d) a sulfosuccinate anion such as diethylhexylsulfosuccinate anion, (2b) an alkylbenzenesulfonate anion such as dodecylbenzenesulfonate anion, (3b) an alkylsulfate anion such as laurylsulfate anion or a soap anion of (1a). It can be preferably used.

If desired, the sublimable ink layer 3 of the thermal transfer ribbon of the present invention may contain a dye other than the above-described hydrophobic cation dye.

The sublimable ink layer 3 may be the same as the conventional sublimation type thermal transfer recording ink layer except that it contains a hydrophobic cationic dye as a dye. For example, the sublimable ink layer 3 can be formed by uniformly mixing a dye and a binder resin holding the dye. Here, the binder resin is butyral resin,
Polyvinyl alkyl acetal resin, cellulose ester resin, cellulose ether resin, urethane resin, polyester resin, polyacetic acid resin and the like can be used.

If desired, the sublimable ink layer 3 may contain other components such as a hydrophobic polymer binder, a melting temperature adjusting agent, a plasticizer, a solvent and a binder.

The sublimable ink layer 3 is formed by applying an ink layer-forming composition obtained by mixing the above components to a predetermined area on the sheet-shaped substrate 2 with a wire bar coater or the like. can do. The thickness is usually 0.
The thickness is preferably 5 to 5.0 μm.

On the other hand, the heat-melt transferable ink layer 4 is an ink layer used at the time of heat-melt type heat transfer, and like the conventional ink layer for heat-melt type heat transfer recording, a coloring agent such as a dye or a pigment, and a transfer agent. It may be formed from a binder resin which is sometimes heat-melted. In this case, as the binder resin, butyral resin, polyvinyl alkyl acetal resin, cellulose ester resin, cellulose ether resin, urethane resin, polyester resin, polyacetic acid resin or the like can be used. Further, as the colorant, carbon black or other various pigments can be used. further,
The heat-melt transferable ink layer 4 may contain an infrared absorber or an ultraviolet absorber. When the heat-melt transferable ink layer 4 contains an infrared absorber or an ultraviolet absorber, the heat transfer of the heat-melt transferable ink layer 4 causes an image such as a barcode having absorption in the infrared or ultraviolet region to be covered. It is preferable because it can be formed on a transfer body. In addition, the heat-melt transferable ink layer 4 may contain various additives such as a melting temperature adjusting agent, a plasticizer, a solvent, and a binder.

The hot-melt transferable ink layer 4 is prepared by mixing the above components to prepare an ink layer-forming composition, which is then applied to a predetermined area on the sheet-shaped substrate 2 by a wire bar coater or the like. Can be applied to form. The thickness is preferably 0.5 to 5.0 μm.

The thermal transfer laminate layer 5 is a layer which is thermally transferred onto the transfer target and is superimposed on the transfer image formed by using the sublimable ink layer 3. This thermal transfer laminate layer 5
Is characterized by containing an intercalation compound capable of fixing and holding the hydrophobizing cation contained in the sublimable ink layer 3 by an ion exchange reaction. By laminating the thermal transferable laminate layer 5 containing such an intercalation compound with the transfer image formed by using the sublimable ink layer 3, the hydrophobic cationic dye forming the transfer image is
Since it is fixed to the intercalation compound by ion exchange, it is possible to remarkably improve the fixability and fastness of the transferred image.

As such an intercalation compound, Japanese Patent Application Laid-Open No. Hei 4 (1998)
Examples thereof include compounds described in Japanese Patent Publication No. 299183. For example, a clay-based intercalation compound having an ion exchange ability, for example, a montmorillonite group mineral represented by the following formula (1) can be preferably exemplified:

[0038]

_{Embedded image} (X, Y) _{2 to 3} Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (I) (wherein X is Al, Fe (III), Mn (III) ) Or Co (III), Y is Mg, Fe (II), M
n (II), Ni, Zn or Li, Z is Si or Al, W is K, Na or Ca, H ₂ O is interlayer water, and m is an integer).

Specific examples of the montmorillonite group mineral represented by the formula (I) include montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, and alumini, depending on the combination of X and Y and the difference in the number of substitutions. Examples thereof include natural products and synthetic products such as ambidelite, nontronite, aluminian nontronite, saponite, aluminian saponite, hexitolite, and sauconite. The OH group in the formula (I) substituted with a halogen atom such as fluorine can also be used.

In addition to the montmorillonite group mineral of the formula (I), examples of the cation-exchangeable clay-based intercalation compound include mica group minerals such as sodium silicic mica, sodium teniolite and lithium teniolite.

In the above-mentioned intercalation compound, it is desirable to secure a sufficient distance between the intercalation compounds so that the cationic dye easily enters the intercalation layer and the ion exchange reaction is easily carried out. It is desirable to make the layers hydrophobic so that they can be easily dispersed in a lipophilic (hydrophobic) binder resin. For this purpose, it is preferable to previously ion-exchange the cation-exchangeable alkali metal cation or alkaline earth metal cation of the intercalation compound with an organic cation that is ion-exchangeable with the cationic dye and has a lipophilic group. Preferable examples of such an organic cation include a quaternary ammonium ion having an alkyl group having 8 or more carbon atoms and a substituted phosphonium ion.

The blending amount of the intercalation compound is such that the sublimable ink layer 3
10 to 90% by weight of the heat transferable laminated layer 5 from the viewpoint of improving the fixability of the transfer image formed by using the heat transferable laminated layer 5 and securing the transferability of the heat transferable laminated layer 5 itself.
It is preferable that

The thermal transfer laminate layer 5 is preferably made by dispersing the above-mentioned intercalation compound in a binder resin similar to the binder resin forming the hot melt transfer ink layer 4. As a result, the thermal transfer laminate layer 5 can be thermally transferred to the transfer target similarly to the thermal melt transfer ink layer 4.

In addition, the visible light region is substantially transparent so that the transferred image, which is located under the thermal transfer laminate layer 5 on the transfer target, can be seen through from the thermal transfer laminate layer. However, the thermal transfer laminate layer 5 may contain an infrared absorber or an ultraviolet absorber having absorption in the infrared or ultraviolet region. When the thermal transfer laminate layer 5 contains such an infrared absorber or an ultraviolet absorber, the thermal transfer of the thermal transfer laminate layer 5 transfers an image such as a barcode having absorption in the infrared or ultraviolet region. It is preferable because it can be formed in the body. Examples of such infrared absorbers include Kayasorb IR-750 and IR IR manufactured by Nippon Kayaku Co., Ltd.
-820, IRG-002, IRG-003, I
RG-022, IRG-023, CY-2, CY
-4, the same CY-9, the same CY-20, etc. can be illustrated. Examples of the ultraviolet absorber include benzophenone-based and benzotriazole-based ultraviolet absorbers.

In addition to the above, the heat transferable laminated layer 5 may include a lubricant such as silicone oil, a coloring material such as dye, and the like, if necessary.
Various additives such as a plasticizer and a filler can be contained. However, as described above, the thermal transferable laminate layer 5 is a layer that is superimposed on the transferred image formed by using the sublimable ink layer 3 to improve the fixability and fastness of the transferred image. The layer 5 preferably has transparency so that the transferred image can be seen through when the transferred image is arranged on the lower surface thereof.

The thermal transfer laminate layer 5 is an intercalation compound,
Other components can be mixed to prepare a composition for forming an ink layer, and the composition can be formed by coating the composition on a predetermined area on the sheet-shaped substrate 2 with a wire bar coater or the like. It is preferable that the thickness is usually 0.5 to 20 μm.

As shown in FIG. 3, the thermal transfer laminate layer 5 has a release layer 5a provided on the sheet-like base material 2.
And the intercalation compound-containing fixing layer 5b formed by using the intercalation compound described above. In this case, since the release layer 5a becomes a layer that is peeled from the sheet-shaped base material 2 and transferred to the transfer target body at the time of thermal transfer and forms the outer surface of the transfer target body, it has a releasability from the sheet-shaped base material 2. It is preferable to use a resin excellent in plasticizer resistance, chemical resistance, scratch resistance, etc. so that the surface of the transferred material can be protected well. Also,
The release layer 5a does not necessarily need to contain the above-mentioned intercalation compound, but may contain it, and may further contain various lubricants and fillers.

As shown in FIG. 3, when the thermal transfer laminate layer 5 has a laminated structure of a release layer 5a and an intercalation compound-containing fixing layer 5b, the thickness of the release layer 5a is 0.5.
10 μm, and the fixing layer 5b containing the interlayer compound is 2 to 10 μm.
It is preferably set to μm.

In FIG. 1, on the sheet-shaped base material 2,
The sublimable ink layer 3, the heat-melt transferable ink layer 4, and the heat-transferable laminated layer 5 for each color of yellow Y, magenta M, and cyan C are repeatedly arranged in this order. The arrangement mode of each layer is not limited to this, and may be an arbitrary arrangement mode. Further, as the sublimable ink layer, the heat-melt transferable ink layer, and the heat-transferable laminated layer, a plurality of types can be provided as needed. For example, the thermal transfer laminate layer has the function of improving the fixability of the transfer image formed by the sublimable ink layer as described above.
In addition to such an original function, a thermal transfer laminate layer that also functions well as a dye-receptive layer so that a transferred image can be favorably formed by a sublimable ink layer even when the transfer target has no dye-receptive layer In addition to the original function, it is possible to provide both the thermal transfer laminate layer and the thermal transfer laminate layer which favorably provide the surface protection function such as chemical resistance and scratch resistance of the formed transferred image.

Further, in the present invention, a sublimable ink layer,
The fact that the heat-melt transferable ink layer and the heat-transferable laminated layer are provided on the same surface of the sheet-shaped substrate means that these layers are provided substantially on the same surface of the sheet-shaped substrate. . That is, on one surface of the sheet-like base material 2,
It suffices that the sublimation ink layer, the heat-melt transfer ink layer and the heat-transfer laminate layer are arranged in the length direction or the width direction of the heat transfer ribbon. Therefore, although not shown in FIG. 1, all the layers of the sublimable ink layer 3, the heat-melt transferable ink layer 4, and the heat-transferable laminate layer 5 and the sheet-like base material 2, or any one of the layers and the sheet. In order to improve the adhesiveness between the base material 2 and the base material 2 if necessary,
A primer layer can be provided.

Further, the sublimable ink layer 3 of the sheet-shaped substrate 2
A heat resistant slipping layer (not shown) may be provided on the surface opposite to the above to improve the running property of the thermal transfer ribbon in the printer.

The thermal transfer ribbon 1A as described above can be used in a commercial thermal transfer printer. For example, polyester, cellulose ester, urethane, epoxy,
A sublimable ink layer 3 is superposed on a transfer target having a dye receiving layer made of a resin such as vinyl chloride-vinyl acetate, and the sublimable ink layer 3 is heated by a thermal head or the like according to an image such as a video signal. By selectively heating with a means, the dye is transferred from the sublimable ink layer 3 to the transfer target by sublimation or thermal diffusion to form a transfer image. Next, the heat-melt transferable ink layer 4 and the transfer target are superposed, and this is also selectively heated according to image information to transfer the heat-melt transferable ink layer 4 to the transfer target, thereby transferring the transfer image. Form. Furthermore, the thermal transfer laminate layer 5
Solid transfer is performed so as to cover at least the transfer image formed using the sublimable ink layer 3. By using the thermal transfer ribbon 1A in this manner, for example, as shown in FIG. 4, the gradation image 7 formed by using the sublimable ink layer 3 on the transfer target 6 and the thermal melting transferable ink A binary image 8 formed using layer 4 and a laminate layer 9 formed using thermal transfer laminating layer 5 to cover both images can be formed.

In the use of this thermal transfer ribbon 1A, when the dye receiving layer is not formed on the transfer receiving material, the heat transferable laminating layer 5 is thermally transferred to the transfer receiving material in advance and the sublimable ink is formed thereon. It is preferred to use Layer 3 to form the transferred image. In this case, the thermal transfer laminate layer 5 may be thermally transferred again onto the transferred image, if necessary.

FIG. 2 shows a thermal transfer ribbon 1B of the second invention.
It is a top view of one mode. Also in this thermal transfer ribbon 1B, the sublimable ink layer 3 of each color of yellow Y, magenta M, and cyan C and the thermal transfer laminate layer 5 are repeatedly provided on the same surface of the sheet-shaped base material 2. This point This is similar to the thermal transfer ribbon 1A shown in FIG. But,
The difference from the thermal transfer ribbon 1A shown in FIG. 1 is that the thermal melt transferable ink layer 4 is not formed. Also,
The thermal transfer laminate layer 5 of the thermal transfer ribbon 1B includes, in addition to the intercalation compound, an infrared absorber or an ultraviolet absorber that is substantially transparent in the visible region but has absorption in the infrared or ultraviolet region, that is, a transfer target. In the above, an infrared absorbing agent or an ultraviolet absorbing agent which allows the transferred image located under the heat transferable laminate layer to be seen through from the heat transferable laminate layer is contained as an essential component. As such an infrared absorbing agent or an ultraviolet absorbing agent, the same infrared absorbing agent or ultraviolet absorbing agent that can be optionally contained in the thermal transfer laminate layer 5 of the thermal transfer ribbon 1A shown in FIG. 1 is used. It is possible to use, and more specifically, those exemplified above as the infrared absorber or the ultraviolet absorber can be used.

It should be noted that without forming the heat-melt transferable ink layer,
The thermal transfer laminate layer 5 can have the same structure as the thermal transfer ribbon 1A shown in FIG. 1 except that the infrared absorbent or the ultraviolet absorbent as described above is contained as an essential component. For example, a sublimable ink layer. A primer layer is provided between both the sheet 3 and the heat transferable laminate layer 5 and the sheet-like base material 2 or between any one of them and the sheet-like base material 2 in order to improve the adhesiveness between the two. be able to. Further, a heat resistant slipping layer can be provided on the surface of the sheet-shaped substrate 2 opposite to the sublimable ink layer 3 and the like.

This thermal transfer ribbon 1B can be used in a commercial thermal transfer printer like the thermal transfer ribbon 1A shown in FIG. 1 except that the thermal melting transferable ink layer is not transferred. For example, the sublimable ink layer 3 is formed by superposing the sublimable ink layer 3 and the transferred material having the dye receiving layer.
Is selectively heated by a heating means such as a thermal head according to an image such as a video signal to form a gradation image 7. Next, the thermal transfer laminate layer 5 is solidly thermally transferred so as to cover the image 7. At this time, the transfer image of the heat transferable laminated layer 5 is formed by selectively heating the heat transferable laminated layer 5 according to image information. By using the thermal transfer ribbon 1B in this way, for example, as shown in FIG.
A gradation image 7 formed by using the sublimable ink layer 3 on
And a laminate layer 9a formed by using the thermal transfer laminate layer 5 so as to cover the gradation image 7, and a binary image 9b formed also by using the heat transfer laminate layer 5.
Can be formed. Note that this binary image 9b
Is usually difficult to read with the naked eye, but will be well read with an ultraviolet or infrared reader.

[0057]

According to the thermal transfer ribbon of the first aspect of the present invention, since the sublimable ink layer and the heat-melt transferable ink layer are formed on one ink ribbon, the gradation by the sublimable ink layer is transferred to the transfer target. It is possible to form both an image and a binary image with the heat-melt transferable ink layer.

In this case, since the sublimable ink layer contains the hydrophobic cation dye, it is possible to form a clear gradation image. Furthermore, this thermal transfer ribbon has
Since a thermal transferable laminate layer composed of an intercalation compound capable of fixing and holding the hydrophobic cationic dye by an ion exchange reaction is provided, the thermal transferable laminate layer is thermally transferred to a transfer target, and the thermal transferable laminate layer is thermally transferred to form a laminated layer. , By overlaying on the image with the hydrophobized cationic dye formed by thermal transfer of the sublimable ink layer,
It is possible to remarkably improve the fixing property and the fastness of the image.

Also in the thermal transfer ribbon of the second invention,
Since the sublimable ink layer containing the hydrophobic cationic dye and the thermal transferable laminate layer containing the intercalation compound are formed, the sublimable ink layer can fix a high-definition gradation image on the transfer target. Therefore, it is possible to form with good robustness. Further, since the heat transferable laminated layer contains an infrared absorbent or an ultraviolet absorbent which is substantially transparent in the visible region but has absorption in the infrared or ultraviolet region, the heat transferable laminated layer Thermal transfer allows the formation of binary images that are readable by infrared or ultraviolet readers.

[0060]

EXAMPLES The present invention will be specifically described below based on examples.

Example 1 A PET film having a thickness of 6 μm was prepared as a sheet-shaped substrate. Further, the following compositions were prepared as the sublimable ink layer composition, the hot-melt transferable ink layer composition and the thermal transferable laminate layer composition, respectively. And P
A coil bar was used to apply the composition for a sublimable ink layer, the composition for a hot-melt transferable ink layer or the composition for a thermal transferable laminate layer (A) onto one surface of the ET film, and as shown in FIG. Thermal transfer ribbon (sublimable ink layer thickness 1 μm,
A heat-melt transferable ink layer thickness of 2 μm and a heat-transferable laminated thickness layer of 3 μm) were prepared. [Composition for sublimable ink layer] Polyvinyl butyral 1 part by weight Hydrophobized cationic dye (* 1) 1 part by weight MEK / toluene (1/1 weight ratio) 50 parts by weight Here, (* 1) color hydrophobized cationic dye As the dye, a cyan dye, a magenta dye or a yellow dye obtained as described below was used.

Cyan-color hydrophobizing cationic dye: oxazine-based cationic dye (Hodogaya Chemical Co., Ltd., AIZ
3 g of EN Catillon Pure Blue 5GH) was dissolved in 200 cc of water, and 100 cc of a 20 wt% dodecylbenzenesulfonic acid aqueous solution was added dropwise to this solution. Next, the organic phase was extracted from this mixed solution with chloroform, the solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 50 ° C. to obtain about 4 g of a cyan hydrophobized cationic dye.

Magenta Hydrophobic Cationic Dye: Obtained by hydrophobizing a magenta cationic dye (Cation Brilliant Pink BH, Hodogaya Chemical Co., Ltd.) with dodecylbenzenesulfonic acid in the same manner as above.

Yellow Hydrophobic Cationic Dye: A yellow cationic dye (Cation Yellow RLH manufactured by Hodogaya Chemical Co., Ltd.) was obtained by hydrophobizing it with dodecylbenzenesulfonic acid in the same manner as above. [Composition for hot-melt transferable ink layer] Carbon black (Mikuni pigment Co., Ltd., MHI black) 20 parts by weight Acrylic resin (Asahi Kasei Co., Ltd., 560F) 60 parts by weight Vinyl acetate resin (Sekisui Chemical Co., Ltd. Co., Ltd., C-3) 10 parts by weight Plasticizer (Mitsubishi Kasei Co., Ltd., D-160) 10 parts by weight [The composition for thermal transfer laminate layer (A)] Clay (Coop Chemical Co., Ltd., Lucen) Tight SS-1) 40 parts by weight PVC-vinyl acetate resin (VAF, Union Carbide Co., Ltd.) 50 parts by weight Silicone oil (KF-6003, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight Obtained thermal transfer ribbon Using a printer (CVP-M3 manufactured by Sony Corp.), a transfer image was first formed with a sublimable ink layer on a PVC sheet having a thickness of 150 μm. The heat transferable laminate layer was heat transferred onto it. As a result, a transparent and glossy laminate layer was formed on the transferred image.

In order to examine the chemical resistance of the transferred image covered with the laminate layer, the PVC sheet was immersed in toluene for 1 minute. As a result, no bleeding or leakage of the image was observed. For comparison, after forming a transfer image using the sublimable ink layer, the same chemical resistance was examined for those in which the thermal transfer laminate layer was not thermally transferred. As a result, the transferred image disappeared.

Further, using the heat-melt transferable ink layer of the obtained heat transfer ribbon, P
Images of letters and plaid were formed on the VC sheet.
As a result, a binary image having absorption in the infrared region could be formed. The contrast of this binary image is very high. When the reflection density was measured with a Macbeth TR-924, the reflection density of the transferred portion was 2.0 and the reflection density of the non-transferred portion was 0.06. .

Example 2 As the heat transferable laminate layer composition, the following heat transferable laminate layer composition (B) was prepared in addition to the heat transferable laminate layer composition (A) of Example 1 and used. And then P
Example 1 was repeated except that the second thermal transferable laminate layer was also formed on the ET film, and the thermal transfer ribbon (sublimable ink layer thickness 1 μm, thermal melt transferable ink layer thickness 2 μm, thermal transferable laminate layer thickness 3 μm, second A heat transferable laminated layer having a thickness of 3 μm) was prepared. [Composition (B) for thermal transfer laminate layer] Acrylic resin (Asahi Kasei Co., Ltd., 720V) 70 parts by weight Clay (Cope Chemical Co., Ltd., Lucentite SS-1) 10 parts by weight Synthetic silica (Nippon Silica) Co., Ltd., E-220A) 10 parts by weight Silicone oil (Toray Dow Corning Silicone Co., Ltd., SF84 27) 10 parts by weight A card-like PVC plate as a transfer body on which no dye receiving layer is formed. (Thickness 250 μm) was prepared. Then, with respect to this transferred material, first, the heat transferable laminate layer of the obtained heat transfer ribbon (heat transferable laminate layer composition (A)
From a printer (Machires Co., Ltd.,
Thermal transfer was performed using a printing tester), and then a transfer image was formed using the sublimable ink layer thereon. This allows
It was possible to form a transferred image having excellent definition and fixability. Further, a second heat transferable laminate layer (a layer formed from the heat transferable laminate layer composition (B)) was laminated on the transfer image by heat transfer. As a result, the glossiness and abrasion resistance of the image are increased, and the image fixing property is remarkably improved.

Example 3 A PET film having a thickness of 6 μm was prepared as a sheet-shaped substrate. Further, the same composition for sublimable ink layers as in Example 1 was prepared, and a composition having the following composition was prepared as a composition for thermal transfer laminate layer. Then, the composition for a sublimable ink layer or the composition for a heat transferable laminate layer is applied to one surface of the PET film using a coil bar, and a thermal transfer ribbon as shown in FIG. 2 (sublimable ink layer thickness 1 μm, A heat transferable laminate layer having a thickness of 6 μm) was prepared. [Composition for thermal transfer laminate layer] Acrylic resin (Asahi Kasei Co., Ltd., 560F) 60 parts by weight Clay (Cope Chemical Co., Ltd., Lucentite SS-1) 30 parts by weight Infrared absorber (Nippon Kayaku Co., Ltd.) , IPG-002) 10 parts by weight Using the obtained thermal transfer ribbon, a printer (printing tester manufactured by Machires Co., Ltd.) was used, and a P having a thickness of 250 μm was used.
First, a transfer image was formed on the VC sheet with the sublimable ink layer, and the heat transferable laminate layer was heat transferred onto the transfer image. As a result, a transparent and glossy laminate layer was formed on the transferred image. Further, a bar code image was formed on the transfer target by thermally transferring the heat transferable laminate layer.

In order to examine the chemical resistance of the transferred image covered with the laminate layer, the imaged PVC sheet was immersed in toluene for 1 minute. As a result, no bleeding or leakage of the image was observed. For comparison, after forming a transfer image using the sublimable ink layer, the same chemical resistance was examined for those in which the thermal transfer laminate layer was not thermally transferred. As a result, the transferred image disappeared.

The bar code image formed on the PVC sheet could be read by a sensor having a sensitivity in the infrared region.

Example 4 As a thermal transferable laminate layer composition, the following composition (C) for thermal transferable laminate layer (fixing layer containing intercalation compound) and composition (D) for thermal transferable laminate layer (release layer) were used. Also prepared. Then, in forming the heat transferable laminate layer on the PET film, after forming the primer layer on the PET film, first, the composition (D) for the heat transferable laminate layer (release layer) is applied to release the film, and the release property is improved. A heat transferable laminate layer (release layer) (thickness 2 μm) having excellent scratch resistance is formed, and a heat transferable laminate layer (intercalation compound-containing fixing layer) is formed thereon.
Composition (C) was applied to form a thermal transferable laminate layer (intercalation compound-containing fixing layer) (thickness 2 μm), and a thermal transferable laminate layer having a two-layer structure was formed. The sublimable ink layer and the heat-melt transferable ink layer were formed in the same manner as in Example 1. [Composition (C) for thermal transfer laminate layer (fixing layer containing intercalation compound)] Vinyl chloride-vinyl acetate (VAGF, Union Carbide Co., Ltd.) 50 parts by weight Clay (Cope Chemical Co., Lucentite SS) -1) 50 parts by weight [Composition (D) for thermal transfer laminate layer (release layer)] Cellulose resin (manufactured by Eastman Kodak Co., CAB551-0.01) 90 parts by weight Silicone oil (Toray Doukoning Co., Ltd.) Silicone Co., Ltd., SF8427) 5 parts by weight Silica (Nippon Silica Industry Co., Ltd., E200A) 5 parts by weight Using the obtained thermal transfer ribbon, transfer to a PVC sheet having a thickness of 150 μm in the same manner as in Example 1. An image was formed. As a result, a transfer image covered with a transparent laminate layer was formed on the PVC sheet by thermal transfer of the heat transferable laminate layer having a two-layer structure.

In order to examine the chemical resistance of the transferred image covered with this laminate layer, the PVC sheet was immersed in toluene for 1 minute. As a result, no bleeding or leakage of the image was observed. For comparison, the chemical resistance was similarly examined for the thermal transfer laminate layer which was not thermally transferred after the transfer image was formed using the sublimable ink layer.
As a result, in the case where the transfer image was not covered with the laminate layer, the transfer image due to the sublimable ink layer disappeared.

[0073]

According to the present invention, when sublimation type thermal transfer recording and heat melting type thermal transfer recording are carried out by one ink ribbon, an image formed by sublimation type thermal transfer recording and an image formed by heat melting type thermal transfer recording are formed. Both can be formed with good fixability and fastness.

[Brief description of drawings]

FIG. 1 is a plan view (FIG. 1A) and a cross-sectional view (FIG. 1B) of a thermal transfer ribbon of the present invention.

FIG. 2 is a plan view of a thermal transfer ribbon according to another aspect of the present invention.

FIG. 3 is a cross-sectional view of a heat transferable laminate layer portion of the heat transfer ribbon of the present invention.

FIG. 4 is a cross-sectional view of an image formed using the thermal transfer ribbon of the present invention.

FIG. 5 is a cross-sectional view of an image formed using the thermal transfer ribbon of the present invention.

[Explanation of symbols]

 1A, 1B Thermal transfer ribbon 2 Sheet-shaped substrate 3 Sublimable ink layer 4 Thermal melting transferable ink layer 5 Thermal transferable laminating layer 5a Thermal transferable laminating layer (release layer) 5b Thermal transferable laminating layer (interlayer compound-containing fixing layer) 6 Transferred material 7 Gradation image 8 Binary image 9, 9a Laminate layer 9b Binary image

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Claims (5)

[Claims] 1. An ink layer containing a sublimable or heat-diffusible dye on the same surface of a sheet-shaped substrate, the sublimable ink layer transferring the dye from the ink layer to a transfer medium by heating. A heat-melt transferable ink layer that is melt-transferred to a transfer target by heating and a heat-transferable laminate layer that is melt-transferred to the transfer target by heating are provided, and the sublimable ink layer contains a hydrophobic cationic dye. The thermal transfer laminate layer contains an intercalation compound capable of fixing and holding a hydrophobizing cation by an ion exchange reaction. 2. The heat transferable laminate layer has a laminated structure of a release layer provided on a sheet-shaped substrate and an intercalation compound-containing fixing layer provided on the release layer. Thermal transfer ribbon. 3. The thermal transfer ribbon according to claim 1, wherein the thermal melt transferable ink layer or the thermal transferable laminate layer contains an infrared absorber or an ultraviolet absorber. 4. An ink layer containing a sublimable or heat-diffusible dye on the same surface of a sheet-like substrate, the sublimable ink layer transferring the dye from the ink layer to a transfer medium by heating. A heat transferable laminate layer that is melt-transferred to a transfer target by heating is provided, the sublimable ink layer contains a hydrophobizing cation dye, and the heat transferable laminate layer fixes the hydrophobizing cation by an ion exchange reaction. A thermal transfer ribbon comprising: an intercalation compound that can be held; and an infrared absorber or an ultraviolet absorber that is substantially transparent in the visible region and has absorption in the infrared or ultraviolet region. 5. The thermal transfer according to claim 4, wherein the thermal transferable laminate layer has a laminated structure of a release layer provided on the sheet-shaped substrate and an intercalation compound-containing fixing layer provided on the release layer. ribbon.