JP2013136209A - Ink ribbon, and thermal transfer system using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer system which can prevent printed character information or image information from being leaked even when an ink ribbon including a post-chelate dye is used, and can reuse a wind-up portion from the ink ribbon subjected to ink transferring, and to provide an ink ribbon used in the same.SOLUTION: An ink ribbon includes a base material layer, an ink layer provided on one surface of the base material layer, and a back surface layer provided on the surface opposite to the one surface of the base material layer on which the ink layer is provided. The back surface layer is patterned with at least two layers wherein the transfers of the ink of the ink layers are different.

Description

  The present invention relates to an ink ribbon, and more specifically, thermal transfer capable of preventing leakage of printed character information and image information and reusing a take-up portion from an ink ribbon after ink transfer. The present invention relates to an ink ribbon used in a system.

  2. Description of the Related Art Transfer systems that print information such as characters and images on a transfer medium such as a card using an ink ribbon are widely used. The ink ribbon has a ribbon (base material layer) extending in a strip shape, a sublimation ink layer formed on the ribbon and containing a sublimation dye, and a hot-melt ink layer containing a pigment and the like. . In printing using an ink ribbon, ink is transferred to a transfer medium in a pattern corresponding to a desired image to be printed. In this case, a portion of the ink ribbon that has been ink-transferred has a portion of the ink that has been removed due to transfer to the transfer target, in a pattern corresponding to the printed image. Therefore, it is possible to specify a printed image from the ink ribbon that has been ink-transferred. Therefore, when printing information to be concealed such as ID information such as a face photograph or address on an object to be transferred using an ink ribbon, it is necessary to pay attention to the handling of the ink ribbon after ink transfer.

  In order to cope with such a problem, for example, in Japanese Patent Application Laid-Open No. 2008-49663, thermal transfer in which the outermost ink ribbon wound around the winding unit is bonded to the ink ribbon positioned inside the outermost ink ribbon. A system has been proposed. According to the thermal transfer system described in Patent Document 1, it is possible to integrate the ink ribbon that has been transferred onto the winding unit, and thereby print the character information that has been printed from the ink ribbon that has been transferred to the ink. And image information can be prevented from leaking.

JP 2008-49663 A

  However, in the thermal transfer system described in Patent Document 1, since the winding unit is integrated with the ink-transferred ink ribbon wound around the winding unit, the ink transferred after being wound around the winding unit. When the ink ribbon is discarded, the winding unit is also discarded. For this reason, the winding unit cannot be used repeatedly, which increases the cost for processing the ink ribbon after ink transfer.

  For the above problems, the present applicant can prevent leakage of printed character information and image information, and enables reuse of the take-up portion from the ink ribbon after ink transfer. A thermal transfer system is proposed. That is, in a thermal transfer system that transfers ink to a transfer target using an ink ribbon having a base material layer and an ink layer, the ink layer is formed on the ink layer by performing thermal transfer again from the base material side of the used ink ribbon. A thermal transfer system was proposed to make it impossible to identify the pattern of the printed image.

  In the above-described novel thermal transfer system, the present inventors actively transfer the ink of the ink layer to the back layer of the ink ribbon to be used, and pattern the back layer so that the ink transferability is different. Thus, it has been found that it is possible to more effectively prevent the printed character information and image information from leaking from the used ink ribbon. The present invention is based on such knowledge.

  Accordingly, an object of the present invention is to provide a thermal transfer system capable of preventing leakage of printed character information and image information from an ink ribbon and reusing a take-up unit from an ink ribbon that has been ink-transferred. It is to provide an ink ribbon used for it.

The ink ribbon according to the present invention is provided on a surface opposite to the surface of the base material layer, the ink layer provided on one surface of the base material layer, and the surface of the base material layer provided with the ink layer. An ink ribbon comprising a back layer,
The back layer is patterned into at least two layers having different ink transfer properties of the ink layer.

  In the ink ribbon according to the present invention, the first back layer is made of a first resin composition containing a polyvinyl butyral resin and / or a polyvinyl acetal resin and an isocyanate curing agent, and the second back layer is made of the above-mentioned The first resin composition may not be included.

  In the ink ribbon according to the present invention, the polyvinyl butyral resin and / or the polyvinyl acetal resin of the first resin composition and the isocyanate curing agent have a molar equivalent ratio of the isocyanate group of the curing agent to the hydroxyl group in the resin ( -NCO / -OH) may be blended at a ratio of 0.3 or more.

  In the ink ribbon according to the present invention, the ink layer of the ink ribbon includes a post chelate dye, and the first back layer includes a metal ion-containing compound capable of forming a chelate complex with the post chelate dye. Also good.

A thermal transfer system according to another aspect of the present invention is a thermal transfer system for transferring ink to a transfer medium using the ink ribbon.
A delivery section for delivering the ink ribbon;
A first transfer that is disposed on the downstream side of the delivery unit and has a first heating body provided on the back layer side of the ink ribbon, and transfers the ink in the ink layer of the ink ribbon to the transfer target. Equipment,
A winding unit that is disposed on the downstream side of the first transfer device and winds up the ink ribbon after ink transfer;
A second transfer device provided in the vicinity of the winding unit, and having a second heating body for heating the ink ribbon after ink transfer from the back layer side,
In the second transfer device, the ink is transferred from the ink layer of the ink ribbon to the back layer of the ink ribbon located inside the ink ribbon by being heated by the second heating body. Is.

  In the thermal transfer system according to the present invention, in the winding unit, the ink ribbon is wound so that the back layer of the ink ribbon is positioned outside the ink layer, and the second heating body is the outermost ink ribbon. May be heated from the outside.

  In the thermal transfer system according to the present invention, the second heating element may be a roll-shaped heating element.

  In the thermal transfer system according to the present invention, in the first transfer device, the ink of the ink layer of the ink ribbon is transferred to the transfer target in a first pattern, and in the second transfer device, the second heating is performed. Heated by the body, the ink in the ink layer of the outer ink ribbon may be transferred to the back layer of the inner ink ribbon in a second pattern different from the first pattern.

  In the thermal transfer system according to the present invention, the second heating body may have protrusions arranged in a predetermined pattern on the outer periphery.

  In the thermal transfer system according to the present invention, the second heating body may be a thermal print head.

  According to the present invention, since the back surface layer of the ink ribbon is patterned into at least two layers having different ink transfer properties, the second transfer device starts from the outer peripheral side of the transferred ink ribbon wound around the winding portion. When heated by the second heating body, the ink of the outer layer ink ribbon moves to the back layer side of the inner layer ink ribbon, and a light and dark pattern is formed due to the difference in ink transferability, and the ink of the outer layer ink ribbon Since a light and shade pattern is also formed on the layer, it is possible to prevent identification of ID information printed on the transfer target.

FIG. 3 is a schematic cross-sectional view of an ink ribbon according to an embodiment of the present invention. The cross-sectional schematic diagram of the ink ribbon by another embodiment of this invention. The cross-sectional schematic diagram of the ink ribbon by another embodiment of this invention. The perspective view of the ink ribbon by another embodiment of this invention. 1 is a schematic diagram illustrating a thermal transfer system according to an embodiment of the present invention. FIG. 6A is a diagram of the ink ribbon 13 after a part of the post-chelate dye inks 12Y, 12M, and 12C is transferred to the transfer target body 14 in the first pattern, as viewed from the ink layer 12 side. FIG. 6B is a diagram illustrating the transfer target 14 onto which the post-chelate dye ink 12a of the ink ribbon 13 has been transferred in the first pattern. FIG. 7A is a cross-sectional view taken along the line V-V of the ink-transferred ink ribbon 13 shown in FIG. 6A, and FIG. 7B shows a part of the hot-melt ink 12BK. FIG. 4 is a cross-sectional view of the ink ribbon 13 after it has been transferred to the transfer target 14 in a first pattern. In embodiment of this invention, sectional drawing of the ink ribbon heated by the 2nd heating body from the outermost peripheral surface of the transferred ink ribbon wound up by the winding-up part. FIG. 9 is an enlarged cross-sectional view of a part of the transferred ink ribbon 13 in contact with the second heating body 23 shown in FIG. 8. In the embodiment of the present invention, the state in which the sublimation dye ink and the heat-meltable ink in the ink layer of the outer ink ribbon migrate to the back layer of the inner ink ribbon in a predetermined pattern. The figure which shows other embodiment of the 2nd heating body at the time of seeing the 2nd transcription | transfer apparatus of FIG. The figure which showed a mode that the sublimation dye ink and the heat-meltable ink of the ink layer of an outer side ink ribbon transfer to the back surface layer of an inner side ink ribbon by a 2nd heating body shown in FIG. The figure which shows the ink layer of an outer side ink ribbon after sublimation dye ink and a heat-meltable ink transfer to the back surface layer of an inner side ink ribbon by the 2nd heating body shown in FIG. The figure which shows the ink layer of an outer side ink ribbon after sublimation dye ink and a thermomeltable ink transfer to the back surface layer of an inner ink ribbon by the 2nd heating body by other embodiment.

<Ink ribbon>
An ink ribbon according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an ink ribbon according to an embodiment of the present invention. The ink ribbon 13 according to the present invention includes a base material layer 10, an ink layer 12 provided on one surface of the base material layer 10, and a surface opposite to the surface of the base material layer 10 on which the ink layer 12 is provided. And the back layer 11 includes at least a first back layer 11a and a second back layer 11b, each having a different transferability of ink from the ink layer 12, and the first back surface 11 includes The layer 11a and the second back surface layer 11b have a configuration patterned in a predetermined pattern.

  In the ink ribbon according to an embodiment of the present invention, the ink layer 12 may be a hot-melt ink layer containing a hot-melt ink and / or a sublimation dye ink layer containing a sublimation dye or a post-chelate dye. When the ink layer 12 is composed of a heat-meltable ink layer, as shown in FIG. 2, a release layer 26 is provided between the base material layer 10 and the heat-meltable ink layer 12BK as the layer structure of the ink ribbon. It may be. In addition, as shown in FIG. 3, the sublimation dye ink layer has a structure in which a layer containing a yellow dye (Y), a layer containing a magenta dye (M), and a layer containing a cyan dye (C) are provided in the surface order. In the case where the sublimation dye ink layer is provided, the adhesive layer 27 may be provided between the base material layer 10 and the sublimation dye ink layers 12Y, 12M, and 12C. Further, when printing of character information such as characters and format printing and printing of image information such as a face image are continuously performed, as shown in FIG. 4, each ink layer (BK, Y, M, C) described above is used. ) May be provided in the surface order. Hereinafter, each layer constituting the ink ribbon according to the present invention will be described.

  The base material layer 10 is a layer for supporting the ink layer 12 to be described later, and can be used without limitation as long as it has a conventionally known degree of heat resistance and strength. For example, polyethylene terephthalate film, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane, acetic acid Examples thereof include cellulose derivatives such as cellulose, resin films such as polyethylene film, polyvinyl chloride film, nylon film, polyimide film, and ionomer film.

  The base material layer generally has a thickness of about 0.5 to 50 μm, preferably about 3 to 10 μm.

  The base material layer may be subjected to an adhesion treatment on one side or both sides as necessary. When the dye ink for forming the dye layer is formed on the base material, it is preferable to perform an adhesion treatment because the wettability and adhesiveness of the coating liquid are likely to be insufficient. Examples of the above-mentioned adhesion treatment include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, grafting treatment, etc. The reforming technique can be applied as it is. Two or more of these treatments can be used in combination.

  The ink layer 12 is formed by applying and drying a coating liquid obtained by dissolving or dispersing a sublimation dye, a post-chelate dye, or a heat-meltable ink in an appropriate binder or vehicle on the substrate layer 10 described above. The For example, an ink layer is formed by applying a coating liquid on one surface of a base material layer and drying by a known means such as a gravure printing method, a screen printing method, a reverse roll coating printing method using a gravure plate, etc. can do.

  As the sublimation dye, any of the dyes conventionally used in known thermal transfer sheets can be used in the present invention and is not particularly limited. These dyes include methines such as diarylmethane, triarylmethane, thiazole and merocyanine, indoaniline, azomethine such as acetophenone azomethine, pyrazoloazomethine, imidazole azomethine and pyridone azomethine, xanthene and oxazine. Cyanomethylene, thiazine, azine, acridine, benzeneazo, and pyridoneazo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo represented by dicyanostyrene and tricyanostyrene Azo, such as disazo, spiropyran, indolinospiropyran, fluoran, rhodamine lactam, naphthoquinone, anthraquinone, quinophthalone It is.

As the post-chelating dye, conventionally known dyes can be used. For example, JP-A-59-78893, 59-109349, Japanese Patent Application Nos. 2-213303, 2-214719, and 2-203742. And cyan, magenta and yellow dyes capable of forming at least bidentate chelates as described in US Pat. A preferred sublimable dye capable of forming a chelate can be represented by the following general formula.
X1-N = N-X2-G
(In the formula, X1 represents an aromatic carbocyclic ring in which at least one ring is composed of 5 to 7 atoms, or a group of atoms necessary for completing a heterocyclic ring, and is a carbon bonded to an azo bond. At least one of the adjacent positions of the atom is a nitrogen atom or a carbon atom substituted with a chelating group, and X2 is an aromatic heterocyclic ring or an aromatic group in which at least one ring is composed of 5 to 7 atoms Represents a carbocyclic ring, and G represents a chelating group.)

  An ink can be prepared by dissolving or dispersing the above-described sublimation dye or post-chelate dye in an appropriate binder. The binder is not particularly limited, and conventionally known binders can be used. Furthermore, conventionally known various additives can be appropriately added to the ink layer.

  The hot-melt ink used in the present invention comprises a colorant and a vehicle, and various additives are added as necessary. As the colorant, among organic or inorganic pigments or dyes, those having a color density required as a recording material and not discolored by light, heat, temperature or the like are preferable. In addition, a substance that develops color when heated or a substance that develops color when brought into contact with a substance applied to the transfer medium can also be used. In addition to cyan, magenta, yellow, black and the like, various colorants can be used as the colorant. The vehicle is mainly composed of a wax, and in addition, a mixture of a wax and a drying oil, resin, mineral oil, cellulose, rubber derivatives, or the like is used. The heat-meltable ink layer made of heat-meltable ink can contain a heat conductive material in order to give good heat conductivity and melt transferability. Examples of such heat conductive materials include carbonaceous materials such as carbon black, aluminum, copper, tin oxide, molybdenum disulfide, and the like.

  Next, the back layer 11 of the ink ribbon 13 according to the present invention will be described. The back layer has a function of improving heat resistance so that the ink ribbon is not deformed by heat at the time of thermal transfer, and also improving running performance of the thermal print head at the time of thermal transfer to suppress sticking and the like. The back layer can be generally formed by applying and drying a binder resin to which a lubricant, a surfactant, inorganic particles, organic particles, a pigment and the like are added. In the present invention, the back layer is patterned into at least two layers having different ink migration properties (also called dyeing properties). Although it does not restrict | limit especially as patterning, For example, as shown in FIG. 1 etc., the back surface layer from which dyeing property differs can be provided alternately.

  The dyeing property of the back layer can be adjusted by changing the above components, the types of binder resins, the types of lubricants, surfactants, and the like, and the amounts added. For example, as a binder resin, polyester resin, polyacrylate resin, polyvinyl acetate resin, polyurethane resin, styrene acrylate resin, polyacrylate resin, acrylonitrile styrene resin, polyacrylamide resin, polyamide resin, Polyamideimide resin, polyether resin, polystyrene resin, polyethylene resin, polypropylene resin, polyolefin resin, vinyl resins such as polyvinyl chloride resin and polyvinyl alcohol resin, cellulose resin, hydroxyethyl cellulose resin, cellulose acetate resin, etc. Cellulose resin, polyvinyl acetal resin such as polyvinyl acetoacetal resin and polyvinyl butyral resin, non-curable type such as silicone modified resin and long chain alkyl modified resin Examples include fats and polyol resins that are cured by crosslinking with a curing agent. By combining these and using as a binder resin, two types of back layers having different dyeing properties as described above can be patterned. .

  In particular, when a heat-meltable ink layer is provided as the ink layer, a polyvinyl butyral resin and / or a polyvinyl acetal resin cured with an isocyanate curing agent as a binder resin having low dyeability of the heat-meltable ink. Can be mentioned. In particular, the polyvinyl butyral resin and / or polyvinyl acetal and the isocyanate curing agent are used in such a ratio that the molar equivalent ratio (-NCO / -OH) of the isocyanate group of the curing agent to the hydroxyl group in the resin is 0.3 or more. The blended binder resin has extremely low dyeability of the hot-melt ink. Therefore, such a binder resin having a very low dyeability is used as the first back layer, and as the second back layer, another binder resin having a high dyeability of the hot-melt ink or a mole of -NCO / -OH is used. By using a polyvinyl butyral resin and / or a binder resin containing a polyvinyl acetal and an isocyanate curing agent at a blending ratio such that the equivalent ratio is less than 0.3, the transferability of the ink from the ink layer is different. One back layer and a second back layer can be formed. Examples of other resins having high dyeability of heat-meltable ink include those that are not curable among the above-mentioned resins, such as acrylonitrile styrene resin, polymethyl methacrylate resin, polyamideimide resin, and polyamide silicone resin. .

  The dyeability of the back layer can also be adjusted by the melting point of the lubricant added to the binder resin. As the lubricant contained in the back layer, phosphate surfactants, silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, polyethylene wax, montan wax, fatty acid amide, fatty acid ester, and polyvalent alkyl phosphate Metal soap, metal soap such as metal salt of alkyl carboxylic acid, long chain aliphatic compound, low molecular weight polypropylene, block copolymer of ethylene oxide and propylene oxide, condensate of fatty acid salt and polyether compound, perfluoroalkyl Derived from ethylene oxide adduct, long-chain alkylsulfonic acid sodium salt, sorbitan acid ester compound, reaction product of higher alcohol and / or higher amine with isocyanate, polyolefin and ethylenically unsaturated carboxylic acid or its ester anhydride Ink layers composed of sublimable dye inks can be used by adding a lubricant having a melting point of 125 ° C. or lower to a binder resin. The dyeing property of the sublimable dye ink from can be increased. Examples of the lubricant having a melting point of 125 ° C. or lower include silicone oil, phosphate ester, polyethylene wax, zinc stearate and the like. On the other hand, when a binder resin not containing a lubricant as described above or a resin binder containing a lubricant having a melting point exceeding 125 ° C. is used, a back layer having a low dyeing property of a sublimable dye ink can be formed. Therefore, by using a resin binder having a low dyeing property of the sublimable dye ink as the first back layer and using a resin binder having a high dyeing property of the sublimation dye ink as described above as the second back layer. The first back surface layer and the second back surface layer, each having different ink transfer properties from the ink layer, can be formed.

  In addition, when a phosphate ester surfactant or polyethylene wax is added to the resin binder, the dyeing property of the sublimation dye ink or the hot-melt ink to the back layer is lowered. For example, by forming the back layer using a resin binder containing 20% by mass or more of a lubricant, it is possible to effectively suppress the transfer of the ink to the back layer.

  Furthermore, when a metal soap such as a polyvalent metal salt of an alkyl phosphate ester or a metal salt of an alkyl carboxylic acid is added to the resin binder, the dyeing property to the back layer of the sublimation dye ink is lowered, while the hot-melt ink The dyeing property with respect to the back layer becomes higher. Therefore, by using the resin binder having the above-described type and blending amount of the lubricant adjusted, the first back layer and the second back layer are separately applied to each other, so that the transferability of the ink from the ink layer is different from each other. And a second back layer can be formed.

  In addition, the back layer may contain inorganic or organic fine particles in order to provide lubricity during printing and non-printing. Examples of the inorganic fine particles include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, and oxides such as silica. Inorganic fine particles such as graphite, nitrate and boron nitride. Organic fine particles include acrylic resin, Teflon (registered trademark) resin, silicone resin, lauroyl resin, phenol resin, acetal resin, polystyrene resin, nylon resin, etc., or crosslinked resin obtained by reacting these with a crosslinking agent. Examples thereof include fine particles.

Furthermore, in this invention, the metal ion containing compound which can form a chelate complex with the above-mentioned post chelate dye may be contained in the back layer. As such a metal ion-containing compound, conventionally known compounds can be used, and inorganic or organic salts and metal complexes of divalent and polyvalent metals belonging to Groups 2 and 8 to 12 are preferably used. Can be used. For example, the following general formula containing Ni ²⁺ , Cu ⁺ , Co ²⁺ , Cr ²⁺ and Zn ²⁺ :
[M (Q1) k (Q2 ) m (Q3) n] p + p (L -)
(In the formula, M represents a metal ion, Q1, Q2, and Q3 each represent a coordination compound capable of coordination with the metal ion represented by M, L represents a counter anion that can form a complex, and k Represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. In these, the complex represented by the above general formula is tetradentate or hexadentate. Or a complex represented by the number of ligands of Q1, Q2 and Q3, and p represents 1, 2 or 3.

  Moreover, a metal soap can also be used as a compound which can form a chelate complex with a post-chelate dye. Particularly preferred specific examples of the metal soap include polyvalent metal salts of alkyl phosphates, polyvalent metal salts of fatty acids, metal salts of alkyl carboxylic acids, and the like.

  In order to pattern two or more back layers having different dyeing properties, the above-mentioned components are dissolved or dispersed in an appropriate solvent such as acetone, methyl ethyl ketone, toluene, xylene, etc. This is formed on a base material sheet by a conventional appropriate printing method such as a gravure coater, a roll coater, or a wire bar, or a coating method. For example, when applying a back layer coating solution using a gravure coater, use a gravure plate to print the other back layer coating solution intermittently with an interval between which one back layer coating solution is applied. To do. Next, by performing an intermittent printing of one back layer coating liquid with an interval between the other back layer coating liquid applied, desired patterning can be performed, but is not limited thereto, For example, various well-known methods can be applied, such as printing with one back layer coating solution on the entire surface without any gaps and then printing the other back layer coating solution with a gap from the top. After apply | coating a back surface layer coating liquid on a base material, the back surface layer patterned as shown in FIG. 1 can be formed by heating and drying to the temperature of 30 to 80 degreeC. The back layer has a thickness of 0.5 to 5 μm, preferably 1 to 2 μm. When the film thickness is less than 0.5 μm, the effect as the heat resistant slipping layer is not sufficient, and when it is more than 5 μm, heat transfer from the thermal head to the dye layer is deteriorated and the print density is lowered.

  In the ink ribbon according to the present invention, a release layer 26 may be provided between the base material layer 10 and the hot-melt ink layer 12BK, as shown in FIG. By providing a release layer, the ink melted at the time of thermal transfer can be easily peeled off from the base material, and after the character information is recorded on the transfer target, the recorded portion is made slippery to improve the scratch resistance. Can do. As the release layer, a thermoplastic resin having a melting point or softening point in the range of 50 to 150 ° C., particularly 60 to 120 ° C., or a mixture of two or more thermoplastic resins and having the above temperature range is preferably used. it can. For example, an acrylic resin, silicone resin, fluororesin, various resins modified with silicone or fluorine, and conventionally known ones mainly composed of wax can be used. In addition to thermoplastic resins, if necessary, higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol and eicosanol, etc. Higher alcohols; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate and myricyl stearate; amides such as acetamide, propionamide, palmitate amide, stearamide and amide wax; and stearylamine, behenyl Higher amines such as amine and partimylamine may be added. These additive components may be used alone or in combination of two or more. Moreover, in order to adjust peelability, you may contain surfactant, A polyoxyethylene chain containing compound is mentioned as a suitable surfactant. Furthermore, inorganic or organic fine particles (metal powder, silica gel and the like) and oils (linseed oil mineral oil and the like) can be added. From the viewpoint of thermal conductivity, the thickness of the release layer is 0.05 to 2.0 μm, preferably 0.1 to 1.0 μm.

  Further, an adhesive layer (not shown) may be provided on the heat-meltable ink layer 12BK to improve the adhesion between the heat-meltable ink layer 12BK and the transfer target 14. This adhesive layer is mainly composed of a thermoplastic elastomer that softens and exhibits adhesiveness by heating the first heating body (thermal print head or the like), and prevents blocking when the resulting ink ribbon is wound into a roll. Therefore, an antiblocking agent can be added, such as waxes, higher fatty acid amides, esters and salts, fluororesin and inorganic powders. Examples of thermoplastic elastomers include ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid ester copolymer (EEA), polyester resin, polyethylene, polystyrene, polypropylene, polybutene, petroleum resin, vinyl chloride resin, vinyl chloride. -Vinyl acetate copolymer, polyvinyl alcohol, vinylidene chloride resin, methacrylic resin, polyamide, polycarbonate, polyvinyl formal, polyvinyl butyral, acetyl cellulose, nitrocellulose, polyvinyl acetate, polyisobutylene, ethyl cellulose or polyacetal. Examples of the wax to be added include microcrystalline wax, carnauba wax, and paraffin wax. In addition, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, polyester wax, partially modified wax, fatty acid ester, fatty acid amide, etc. Wax.

  For the adhesive layer, a coating solution in which a thermoplastic elastomer and an additive are dissolved or dispersed in an appropriate solvent is used as a conventionally known hot melt coat, hot lacquer coat, gravure direct coat, gravure reverse coat, knife coat, air coat, It can be formed by a method such as roll coating. The thickness of the adhesive layer is about 0.05 to 2.0 μm, preferably 0.1 to 1.0 μm.

  Further, as shown in FIG. 3, the ink ribbon according to the present invention is provided with an adhesive layer 27 between the base material layer 10 and the sublimation dye ink layers 12Y, 12M, and 12C, and the base material layer 10 and the sublimation dye. Adhesiveness with the ink layers 12Y, 12M, and 12C may be improved. When the above-described dye ink for forming the sublimable dye ink layers 12Y, 12M, and 12C is formed on the base material 10 and formed on the base material, the wettability and adhesiveness of the coating liquid are insufficient. It's easy to do. Therefore, as the adhesive layer, the corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, and the like on the surface of the substrate 10 A known resin surface modification treatment such as grafting treatment may be performed, or an adhesive (primer) may be applied. As the adhesive, conventionally known ones can be used, for example, polyester resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, Polyether resins, polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyvinyl pyrrolidone and modified products thereof, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral Organic materials such as silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicion bakumaite, etc.), aluminum silicate, silica Magnesium, magnesium carbonate, magnesium oxide, and inorganic materials such as colloidal inorganic pigment ultrafine particles such as titanium oxide.

<Thermal transfer system>
Next, the thermal transfer system according to the present invention using the above-described ink ribbon will be described. As described above, the ink ribbon 13 includes the base material layer 10, the ink layer 12, and the back layer 11. However, in order to facilitate understanding of the invention, the ink layer 12 and the back layer are illustrated in the following drawings. 11, the base material layer 10 provided between the first and second members is omitted. FIG. 5 is a schematic diagram illustrating a thermal transfer system according to an embodiment of the present invention. As shown in FIG. 5, the thermal transfer system 1 that transfers the ink 12 a to the transfer target 14 using the ink ribbon 13 in a desired pattern, a sending unit 16 that sends the ink ribbon 13 in the direction indicated by the arrow R ₁ , and a sending unit 16 and the first transfer device 17 disposed downstream of, is arranged downstream of the first transfer device 17, a winding portion 21 for winding the ink ribbon 13 already ink transfer in the direction indicated by the arrow R _2, And a second transfer device 22 that is provided in the vicinity of the winding unit 21 and that heats the ink ribbon 13 that has been ink-transferred from the back layer 11 side. As shown in FIG. 5, the ink ribbon 13 is conveyed along a plurality of guide rolls 15. Here, the winding unit 21 and the second transfer device 22 shown in FIG.

  As shown in FIG. 5, the first transfer device 17 includes a platen roll 19 that supports the transfer target 14 and a first heating provided so as to face the platen roll 19 with the ink ribbon 13 and the transfer target 14 interposed therebetween. It has a body 18, for example a thermal print head. As shown in FIG. 5, the first heating body 18 is provided on the back layer 11 side of the ink ribbon 13. The first heating body 18 heats the ink 12a of the ink layer 12 of the ink ribbon 13 in a predetermined pattern (first pattern) corresponding to the ID information, whereby the ink 12a of the ink layer 12 of the ink ribbon 13 is heated. The image is transferred to the transfer target 14 in the first pattern. When character information such as an address and name is recorded as ID information, an ink ribbon provided with a heat-meltable ink layer as shown in FIG. 2 or FIG. 4 is used, and a face photograph is used as ID information. In the case of recording, etc., an ink ribbon having a sublimable dye ink layer as shown in FIGS. 3 and 4 is used.

  FIG. 6A is a diagram showing a case where the ink ribbon 13 after a part of the post-chelate dye inks 12Y, 12M, and 12C is transferred to the transfer target 14 in the first pattern is viewed from the ink layer 12 side. FIG. 6B is a diagram illustrating the transfer target 14 on which the post-chelate dye ink 12a of the ink ribbon 13 is transferred in the first pattern. 7A is a cross-sectional view taken along the line VV of the ink ribbon 13 to which ink has been transferred shown in FIG. 6A, and FIG. 7B is a diagram of one of the hot-melt ink 12BK. FIG. 4 is a cross-sectional view of the ink ribbon 13 after a portion is transferred to the transfer target 14 in a first pattern.

  When the post-chelate dye inks 12Y, 12M, and 12C are used, the ink layers 12Y, 12M, and 12C in the ink ribbon 13 to which the ink has been transferred are transferred as shown in FIGS. 6 (a) and 7 (b). The dye concentration is lower than the portion 12a in which the post-chelate dye remains in the ink layer without being transferred to the body 14, and the portion 12a in which the sublimation dye remains because a part of the post-chelate dye has migrated. Portion 12b (a portion corresponding to ID information such as a face photograph printed on the transfer body 14). The portion 12b where the dye concentration is low corresponds to the first pattern in the first heating body 18 described above.

  When the heat-meltable ink 12BK is used, the ink layer 12BK in the ink ribbon 13 to which the ink has been transferred is not transferred to the transfer target 14, as shown in FIG. Is the portion 12a remaining in the ink layer, and the portion 12b in which the ink has been removed due to the transfer of the heat-meltable ink 12BK (character ID information such as name and address printed on the transfer body 14). The portion corresponding to The ink missing portion 12b corresponds to the first pattern in the first heating body 18 described above.

  As shown in FIGS. 7A and 7B, the pattern of the portion where the dye concentration is low and the ink missing portion (12b) in the ink ribbon 13 to which ink has been transferred is the same as that in the first heating body 18 described above. It corresponds to one pattern. For this reason, based on the pattern of the part 12b, it becomes possible to specify ID information such as a face photograph printed on the transfer object 14 and character ID information such as an individual's name and address.

  As shown in FIG. 6B, the transferred object 14 formed with an image using a post-chelate dye as the ink is subjected to thermal transfer and then heated by the first heating element 18 to be transferred. The metal ion-containing compound in the image receiving layer (not shown) reacts with the transferred post-chelate dye to form a chelate complex, whereby a desired color is developed. For example, when a cyan dye is used, the color before the chelate complex is formed may be a color close to magenta (red). The metal ion-containing compound in the receiving layer of the transfer target may move to the ink ribbon side during the first pattern transfer by the first heating body. In this case, a part of the post-chelate dye has transferred. The metal ion-containing compound may migrate to the portion 12b where the dye concentration is low. In this case, the transferred metal ion-containing compound reacts with the post-chelate dye in the ink layer to form a chelate complex, so that the portion develops color. Therefore, the portion 12b where the dye concentration is low, and the post-chelate dye However, the color is different from the portion 12a remaining in the ink layer. Therefore, when a post-chelate dye ink is used as a sublimation dye ink, ID information such as a face photograph printed on the transfer target 14 and character ID information such as an individual's name and address are used from a used ink ribbon. It becomes easier to specify. The thermal transfer system according to the present invention can solve the above problems. Details will be described below.

Next, the winding device 20 of the thermal transfer system 10 will be described in detail with reference to FIG. As described above, the winding device 20 is provided in the vicinity of the roll-shaped winding unit 21 that winds up the ink ribbon 13 that has been subjected to ink transfer, and the winding unit 20, and the ink ribbon 13 that has been subjected to ink transfer is disposed on the back surface layer 11. And a second transfer device (winding device transfer device) 22 for heating from the side. Among the second transfer device 22 includes a second heating element 23 made from a heater roll form, support mechanism for rotatably supported in the direction of a second heating member 23 in the arrow R ₃ (not shown) , Including.

In the winding unit 21, the outer diameter of the roll body constituted by the ink ribbon 13 wound by the winding unit 21 increases as the winding proceeds. To accommodate the increased outer diameter of such a roll member, the second heating member 23 does not support mechanism (illustrated so as to be movable in the (direction shown in FIG. 7 by the arrow D ₁₎ radially of the roll body ). Further, by supporting the second heating body 23 by such a support mechanism, the second heating body 23 is moved to the arrow when the winding drive is stopped or when the heating by the second heating body 23 is unnecessary. is moved in the D ₁ direction, it is possible to arbitrarily stop the contact with the ink ribbon 13 that is wound around the winding portion 21.

  Further, even if the outer diameter of the roll body constituted by the ink ribbon 13 wound by the winding portion 21 changes, the heating body always comes into sliding contact with the outermost surface of the ink ribbon 13 with a constant contact pressure. A suspension mechanism (not shown) may be provided.

  As shown in FIG. 8, in the winding unit 21 of the present embodiment, the ink ribbon 13 is wound so that the back layer 11 of the ink ribbon 13 is positioned outside the ink layer 12. As shown in FIG. 6, in the present embodiment, the ink ribbon 13 positioned on the outermost periphery among the ink ribbons 13 wound around the winding unit 21 is referred to as the outer ink ribbon 13A, and the outer ink ribbon 13A. The ink ribbon 13 wound around the winding portion 21 on the inner side and adjacent to the outer ink ribbon 13A is referred to as an inner ink ribbon 13B.

  Next, how the ID information such as a face image can be prevented from leaking from the used ink ribbon by the thermal transfer system of the present invention will be described with reference to FIGS. FIG. 9 is an enlarged cross-sectional view of a part of the ink transferred ink ribbon 13 in contact with the second heating body 23 shown in FIG. 8, and FIG. 10 shows that the ink in the ink layer of the outer ink ribbon is the inner ink. It is the figure which showed a mode that it transferred to the back layer of a ribbon. In FIG. 9, in the ink layer 12 of the used ink ribbon 13, the portion where the sublimation dye ink remains in the ink layer is 12a (YMC), and a part of the sublimation dye ink is transferred to the transfer object. The portion where the dye concentration is low due to the migration is 12b (YMC). Further, the portion where the heat-meltable ink 12BK remains in the ink layer is 12a (BK), and the portion where the ink is removed because the heat-meltable ink 12BK has moved to the transfer target is 12b. (BK).

  In addition, when the ink ribbon 13 is wound around the winding unit 21, the wound ink ribbon 13 is actually curved along the roll surface of the winding unit 21, but in FIGS. For convenience, the ink ribbon 13 is drawn ignoring the curved state. In FIGS. 9 and 10, the outer ink ribbon 13A is pressed by the second heater 23, and a part of the ink 12a of the ink layer 12 of the outer ink ribbon 13A is pressed against the base material layer 10 of the inner ink ribbon 13B. For convenience of explanation, a slight gap is drawn between the outer ink ribbon 13A and the inner ink ribbon 13B for convenience. However, the present invention is not limited to this, and the outer ink ribbon 13A and the inner ink ribbon 13B may be in contact with each other without any gap.

  When the ink-transferred ink ribbon 13 taken up by the take-up portion 21 is heated by the second heating body 23 from the back layer side of the ink ribbon 13A on the outermost peripheral surface, the ink of the ink ribbon 13A on the outer side is heated. Heat is also transmitted to the layers. As a result, the ink moves from the ink layer 12 of the outer ink ribbon 13A to the back layer of the inner ink ribbon 13B. At this time, since the back layer 11 of the inner ink ribbon 13B is patterned into a portion 11a having a low dyeing property and a portion 11b having a high dyeing property, the inner layer of the ink layer 12 of the outer ink ribbon 13A The portion of the ink ribbon 13B that is in contact with the back layer 11b (the portion with high dyeing properties) is the portion where more ink has moved to the back layer 11b and is in contact with the back layer 11a (the portion with low dyeing properties). Has less ink transfer to the back layer 11a. By the way, the ink layer 12 of the used ink ribbon has a portion (corresponding to 12b (BK) and 12b (YMC)) transferred to the transfer target as described above, and other portions (12a (BK) and 12b). (Corresponding to (YMC)), there is a difference in the density of ink (the remaining amount of ink). Therefore, when the portion of the used ink ribbon 13A where the sublimable dye ink or the heat-meltable ink still remains in the ink layer 12 contacts the back layer 11 of the inner ink ribbon 13B, the back layer 11 is dyed. The ink in the ink layer 12 of the outer ink ribbon 13A is transferred to the back layer 11 of the inner ink ribbon 13B according to the difference in property.

  For example, as shown in FIG. 10, in the portion 12a (BK) where the heat-meltable ink of the outer ink ribbon 13A remains, the portion of the inner ink ribbon 13B that is in contact with the back layer 11b having high dyeing property is The hot-melt ink moves to the back layer 11b side (12a ′ (BK)), and the ink layer side becomes an ink missing portion 12a ″ (BK). On the other hand, in the portion 12a (BK) where the heat-meltable ink remains, the portion 12a (BK) that is in contact with the back layer 11a having low dyeing property is the heat-meltable ink toward the back layer 11 side of the inner ink ribbon. Does not migrate.

  Further, in the portion having a high concentration of the sublimation dye ink (that is, the portion other than the portion where the image is formed) 12a (YMC), the portion in contact with the back layer 11b having a high dyeing property of the inner ink ribbon 13B is Then, the sublimation dye ink moves to the back layer 11b side (12a ′ (YMC)), and the ink layer side becomes an ink missing portion 12a ″ (YMC). On the other hand, in the portion where the density of the sublimation dye ink is low (ie, corresponding to the image-formed portion) 12b (YMC), the portion in contact with the back layer 11b having high dyeing property of the inner ink ribbon 13B is the back surface. The sublimation dye ink moves to the layer 11b side (12b ′ (YMC)), and the ink layer side becomes an ink missing portion 12b ″ (YMC). Therefore, in the ink layer of the used ink ribbon, the density difference corresponding to the patterning of the back surface layer 11 is present in the portion of the transferred body where the image is not formed (the portion where the image or characters are not transferred to the transferred body). At the same time, the ink missing part (the part where the image, characters, etc. are transferred to the transfer medium) also has a difference in density corresponding to the inging in the pattern of the back surface layer 11. As a result, it is impossible to specify ID information such as a face photograph printed on the transfer target 14 from the ink ribbon by visual recognition.

  By the way, when the ink moves from the ink layer 12 of the outer ink ribbon 13A to the back layer of the inner ink ribbon 13B, depending on the patterning method of the back layer, the ink ribbon may change depending on the density of the ink transferred to the back layer. It is also assumed that ID information such as a face photograph printed on the transfer object 14 can be specified. In the present invention, as a preferred embodiment, the back layer contains a metal ion-containing compound capable of forming a chelate complex with a post-chelate dye contained in the ink layer. As described above, the post-chelate dye does not develop the same color of the ink layer color (cyan, magenta, yellow) and the color after the dye dye reacts with the metal ion-containing compound, and has a completely different color. There is a case. Therefore, when the metal ion-containing compound is contained on the back layer side having high dyeing property, the ink transferred to the back layer exhibits a color development different from that of other portions. As a result, in addition to the light and shade difference caused by the difference in the dyeing property of the back layer, the color tone is also different, and ID information such as a face photograph printed from the ink ribbon to the transfer target 14 is further identified by visual recognition. It becomes impossible.

  Next, a preferred embodiment of the second heating body 23 of the second transfer device 22 will be described in detail with reference to FIGS. 11 and 12. 11 is a view showing another embodiment when the second heating body 23 of FIG. 8 is viewed from the direction indicated by the arrow V, and FIG. 12 is a view showing the second heating body 23 and the ink ribbon 13 shown in FIG. It is sectional drawing along the IX-IX line. As shown in FIGS. 11 and 12, the second heating body 23 includes protrusions 23a arranged in a predetermined pattern (second pattern) on the outer periphery thereof. For this reason, as shown in FIG. 12, when the outer ink ribbon 13A is heated and pressed from the outer side (back surface layer 11 side) by the protrusion 23a of the second heating body 23, it remains in the ink layer 12 of the outer ink ribbon 13A. A part of the ink 12a is transferred onto the back layer 11b having the higher dyeing property of the inner ink ribbon 13B in the second pattern. The temperature of the second heating body 23 is such that the phenomenon that the ink 12a of the ink layer 12 of the outer ink ribbon 13A is melted over the entire region and the outer ink ribbon 13A and the inner ink ribbon 13B are bonded to each other does not occur. Is set low.

  Here, the second pattern in the protrusion 23 a of the second heating body 23 is set to be different from the first pattern (image pattern to be transferred to the transfer target) in the first heating body 18. For this reason, by transferring a part of the inks 12a (BK) and 12a (YMC) remaining in the ink layer 12 of the outer ink ribbon 13A to the back layer 11b having the higher dyeing property of the inner ink ribbon 13B. In addition, the pattern of the ink missing portion 12b including the first pattern corresponding to the ID information such as characters and images in the ink layer 12 of the outer ink ribbon 13A can be more completely destroyed. By adding such a disturbance pattern (second pattern) to the used ink ribbon, the ID information printed on the transfer target 14 is further specified based on the pattern of the ink missing portion 12b of the used ink ribbon. Can be prevented. Although the case where the second pattern includes a plurality of lines extending in a direction parallel to the conveyance direction of the ink ribbon 13 is shown, the present invention is not limited to this, and the second pattern is the first pattern in the first transfer device 17. Any pattern that can appropriately destroy one pattern (image) can be used.

  FIG. 13 shows the outer ink ribbon after the ink is transferred from the ink layer of the outer ink ribbon 13A to the back layer 11 of the inner ink ribbon 13B using the second heating body 23 as described above. It shows an ink layer. Of the ink layer corresponding to the portion where the image is not formed on the transfer target, the portion that is pressed by the protrusion 23a of the second heating body and is in contact with the back layer 11 is 2 in accordance with the dyeing property of the back layer. Seed shades (12a (YMC) and 12a ′ (YMC)) occur. Further, since the ink is not transferred to the back layer 11 in the portion that is not pressed by the protrusion 23a, light and shade are not generated. Similarly, the portion where the ink is removed is pressed by the protrusion 23a of the second heating body, and the portion in contact with the back layer 11 has two types of shades (12b (YMC) and 12b ′) according to the dyeing property of the back layer. (YMC)) occurs, but the portion that is not pressed by the protrusion 23a is not shaded. As described above, since the ink layer of the ink ribbon forms a more complicated pattern by using the second heating body 23 having the protrusion 23a, the transferred object is based on the pattern of the ink missing portion. It is possible to prevent the ID information printed on the image from being specified.

  Up to now, the heating roll or the heating roll having the protrusions has been exemplified and described as the second heating body 23, but it is needless to say that a heating means such as a thermal print head similar to the first heating body can be used. For example, a more complicated pattern can be formed by using a thermal print head that can heat an arbitrary place. For example, by heating the used ink ribbon in a pattern in which arbitrary characters or the like are randomly arranged, a disturbance pattern as shown in FIG. 14 can be applied, so that the ID information is specified from the used ink ribbon. Can be prevented more reliably.

  In the thermal transfer system of the present invention, as described above, the ink-transferred ink ribbon 13 taken up by the take-up unit 21 of the take-up device 20 is heated from the outside in the second pattern by the second transfer device 22. The A series of ink-transferred ink ribbons 13 are taken up by the take-up unit 21 and heated from the outside with the second pattern 25 by the second transfer device 22, and then the ink ribbon 13 is removed from the take-up unit 21. Discarded. At this time, no adhesion treatment is performed between the ink ribbons 13 wound on the winding unit 21, for example, between the outer ink ribbon 13 </ b> A and the inner ink ribbon 13 </ b> B. It can be easily removed from the winding unit 21. Therefore, the winding unit 21 can be used repeatedly. Accordingly, it is possible to reduce the cost for processing the ink ribbon 13 that has been ink-transferred, compared to the case where the winding unit 21 is discarded together with the ink ribbon 13 that has been ink-transferred.

  As described above, an ink ribbon having a back layer patterned into at least two layers having different ink transfer properties of the ink layer is applied to the thermal transfer system including the second transfer device as described above. As a result, it is possible to prevent identification of the first pattern in the first transfer device 17, that is, the ID information printed on the transfer target 14, from the ink ribbon 13 to which ink has been transferred. Further, as the second heating body of the second transfer device, a roll-shaped heating body having protrusions arranged in a predetermined pattern on the outer periphery or a thermal print head is used to transfer the disturbance pattern to the ink. Since it can be applied to the finished ink ribbon 13, it is possible to further prevent the ID information printed on the transfer medium 14 from being specified based on the pattern of the ink missing portion 12b.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, unless otherwise specified, parts or% is based on mass.

Preparation of ink ribbon First, coating liquids 1 to 6 for the back layer having the following composition were prepared.
<Back layer coating liquid 1>
・ Polyvinyl butyral resin (hydroxyl value 16% by mass) 30 parts (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
110 parts of polyisocyanate (Bernock D750-45, solid content 45% by mass, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Phosphate surfactant 15 parts (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Talc (Microace L-3, manufactured by Nippon Talc Kogyo Co., Ltd.) 5 parts ・ Methyl ethyl ketone 400 parts ・ Toluene 400 parts (molar equivalent ratio (—NCO / —OH) = 1.87)

<Back layer coating liquid 2>
Polymethylmethacrylate resin 11.1 parts (BR-85, manufactured by Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Elitel UE-3200, manufactured by Unitika Ltd.)
・ Zinc stearyl phosphate 5.7 parts (LBT-1830, manufactured by Sakai Chemical Co., Ltd.)
-Melamine aldehyde condensate 2.9 parts (Eposter S, manufactured by Nippon Shokubai Chemical Co., Ltd.)
・ Toluene 0.6 parts ・ MEK 9.4 parts

<Back layer coating liquid 3>
-Polyvinyl butyral resin (hydroxyl value 20% by mass) 6.00 parts (# 3000-4, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Polyisocyanate (solid content: 100% by mass, NCO = 17.3% by mass) 8.00 parts (Bernock D750-45, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Zinc stearyl phosphate (LBT-1830 refinement, Sakai Chemical Industry Co., Ltd.) 3.00 parts ・ Zinc stearate (SZ-PF, Sakai Chemical Industry Co., Ltd.) 3.00 parts ・ Filler (Microace P) -3, manufactured by Nippon Talc Kogyo Co., Ltd.) 1.50 parts ・ Polyethylene wax (melting point: 110 to 118 ° C., average particle size: 10 μm) 3.00 parts (Polywax 3000, manufactured by Toyo Petrolite Co., Ltd.)
・ Methyl ethyl ketone 12.58 parts ・ Toluene 62.92 parts (Molar equivalent ratio (—NCO / —OH) = 1.21)

<Back layer coating liquid 4>
・ Polyvinyl butyral resin 30 parts (ESREC BX-1, Sekisui Chemical Co., Ltd.)
・ 55 parts of polyisocyanate (Bernock D750-45, solid content 45% by mass, manufactured by Dainippon Ink & Chemicals, Inc.)
・ 33 parts of phosphate ester surfactant (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Talc (Microace L-3, manufactured by Nippon Talc Kogyo Co., Ltd.) 6 parts ・ Methyl ethyl ketone 400 parts ・ Toluene 400 parts (molar equivalent ratio (—NCO / —OH) = 0.93)

<Back layer coating liquid 5>
-Polyamideimide resin (solid content 25%) 13 parts (HR-15ET, manufactured by Toyobo Co., Ltd.)
Polyamideimide silicone resin (solid content 25%) 13 parts (HR-14ET, manufactured by Toyobo Co., Ltd.)
・ Silicone oil (solid content: 100%) 0.7 part (KF965-100, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Zinc stearyl phosphate (solid content: 100%) 2.6 parts (LBT-1870 refining, Sakai Chemical Industry Co., Ltd.)
-Zinc stearate (GF-200, manufactured by NOF Corporation, solid content 100%) 2.6 parts-Talc (Microace P-3, manufactured by Nippon Talc Co., Ltd., solid content 100%) 2.6 parts-Ethanol 32. 8 parts ・ Toluene 32.7 parts

<Back layer coating liquid 6>
Polyvinyl acetal resin (hydroxyl value: 12% by mass) 51.0 parts (SREC KS-1 manufactured by Sekisui Chemical Co., Ltd.)
Polyisocyanate (NCO = 17.3% by mass) 14.0 parts (Bernock D750, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Zinc stearyl phosphate 10.0 parts (LBT-1830 purification, Sakai Chemical Industry Co., Ltd.)
・ Zinc stearate 10.0 parts (SZ-PF manufactured by Sakai Chemical Industry Co., Ltd.)
・ Filler 5.0 parts (MICRO ACE P-3 Nippon Talc Industry Co., Ltd.)
-10.0 parts of polyethylene wax (Polywax 3000 manufactured by Toyo Adre Co., Ltd.)
・ Methyl ethyl ketone 200 parts ・ Toluene 100 parts (molar equivalent ratio (—NCO / —OH) = 0.26)

Arbitrary two kinds of the coating solution for the back layer obtained above were combined on the one surface of the base sheet of the polyethylene terephthalate film having a thickness of 6 μm and subjected to easy adhesion in the combination shown in Table 1 below. The back layer was formed by coating and drying so that the disturbance pattern was patterned to 1.0 g / m ^{2 in} terms of minutes and drying. Also, on the other surface of the substrate (the surface that is easily treated), the yellow dye layer coating liquid 1, the magenta dye layer coating liquid 1, the cyan dye layer coating liquid 1, and the heat-meltable black ink having the following composition: By applying the layer coating liquid in this order in order of 1.0 g / m ^{2 in} terms of solid content, and drying, yellow, magenta, cyan and black ink ribbons of four colors can be obtained. Obtained. Moreover, in Example 5 of Table 1, the yellow dye layer coating liquid 2, the magenta dye layer coating liquid 2, and the cyan dye layer coating having the following composition were formed on the other surface (easy adhesion treatment surface) of the substrate. By applying the coating solution 2 and the coating solution for the heat-meltable black ink layer in this order in order of 1.0 g / m ^{2 in} terms of solid content, and drying, yellow, magenta, cyan A black four-color ink ribbon was obtained.

<Yellow dye layer coating solution 1>
Disperse dye (holon brilliant yellow-S-6GL) 5.5 parts Binder resin 4.5 parts (polyvinyl acetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 0.1 part (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Coating liquid 1 for magenta dye layer>
Disperse dye (MS Red G) 1.5 parts Disperse dye (Macrolex Red Violet R) 2.0 parts Binder resin 4.5 parts (Polyvinylacetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 0.1 part (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Cyan dye layer coating solution 1>
-Disperse dye (Kayaset Blue 714) 4.5 parts-Binder resin 4.5 parts (Polyvinylacetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 0.1 part (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Yellow dye layer coating solution 2>
-Yellow dye (compound Y-1 of the following formula) 3.0 parts
・ 5.5 parts of polyvinyl acetal (Denkabutyral KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Methyl ethyl ketone 70.0 parts ・ Toluene 20.0 parts

<Magenta dye layer coating solution 2>
-Magenta dye (compound M-1 of the following formula) 3.0 parts
・ 5.5 parts of polyvinyl acetal (Denkabutyral KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.)
・ Methyl ethyl ketone 70.0 parts ・ Toluene 20.0 parts

<Cyan dye layer coating solution 2>
-3.0 parts of cyan dye (compound C-1 of the following formula)
・ 5.6 parts of polyvinyl acetal (Denkabutyral KY-24, manufactured by Denki Kagaku Kogyo Co., Ltd.)
-Polymethylmethacrylate modified polystyrene 1.0 part (Rededa GP-200, manufactured by Toa Gosei Chemical Co., Ltd.)
・ 0.5 parts of urethane-modified silicone oil (Diaroma SP-2105, manufactured by Dainichi Seika Kogyo Co., Ltd.)
・ Methyl ethyl ketone 70.0 parts ・ Toluene 20.0 parts

<Coating liquid for heat-meltable black ink layer>
・ Carnauba wax 1 part ・ Ethylene vinyl acetate copolymer 1 part (EV40Y, manufactured by Mitsui DuPont Chemical Co., Ltd.)
・ Carbon black 3 parts ・ Phenol resin (Tamanol 521, Arakawa Chemical Co., Ltd.) 5 parts ・ Methyl ethyl ketone 90 parts

<Printing conditions>
The ink ribbons of Examples 1 to 7 and Comparative Examples 1 and 2 obtained as described above were set in a card printer (SP75plus, manufactured by Nippon Data Card Co., Ltd.), and the substrate sheet having an image receiving layer was obtained. By printing a pattern imitating ID information, an ink ribbon having an ink missing portion was produced. Next, in the barcode printer (zebra140Xiii, manufactured by Zebra Co., Ltd.), set the ribbon for printing the barcode on the portion where the ribbon for printing the barcode is set so that the ink ribbon A is heated from the back layer side. The ink ribbon B having the ink missing portion is set to the portion where the barcode printing label is set so as to be heated from the back layer side, and the two ink ribbons having the same kind of ink missing portion are set. Heated in a superposed state. Thereafter, it was examined how much ink on the ink ribbon A had transferred to the back layers 1 and 2 of the ink ribbon A. The evaluation criteria for ink migration (dyeability) were as follows.
1: Both sublimable dye ink (YMC) and heat-meltable black ink (BK) migrated 2: Only heat-meltable black ink (BK) migrated 3: Only sublimable dye ink (YMC) migrated 4: Neither sublimation dye ink (YMC) nor hot-melt black ink (BK) migrated

In addition, the visibility of the ink ribbon B was evaluated. The evaluation criteria were as follows.
A: It was very difficult to read ID information from the ink ribbon for both the sublimable dye ink ribbon (YMC) and the heat-meltable black ink ribbon (BK). O: Sublimable dye ink ribbon (YMC) and It was difficult to read the ID information from the ink ribbon in both of the hot-melt black ink ribbon (BK). Δ: Either the sublimable dye ink ribbon (YMC) or the hot-melt black ink ribbon (BK) It was difficult to read the ID information from the ink ribbon. X: Both the sublimable dye ink ribbon (YMC) and the heat-meltable black ink ribbon (BK) could read the ID information from the ink ribbon.

The evaluation results were as shown in Table 2 below.

  As is clear from the evaluation results in Table 2, it was confirmed that the ID information could be prevented from leaking from the ink ribbon by the thermal transfer system using the ink ribbon according to the present invention. In particular, in the ink ribbon using the post-chelate dye as the sublimation dye ink (Example 5), both the sublimation dye ink ribbon (YMC) and the hot-melt black ink ribbon (BK) receive the ID information from the ink ribbon. It can be seen that reading is very difficult and the effect of preventing information leakage is higher.

DESCRIPTION OF SYMBOLS 1 Thermal transfer system 10 Base material layer 11 Back layer 12 Ink layer 12a, 12a 'Ink 12b, 12b' Ink omission part 13 Ink ribbon 13A Outer ink ribbon 13B Inner ink ribbon 14 Transfer object 15 Guide roll 16 Sending part 17 First transfer Apparatus 18 1st heating body 19 Platen roll 20 Winding apparatus 21 Winding part 22 2nd transfer apparatus 23 2nd heating body 23a Protrusion part 24 Support roll 25 Guide roll 26 Peeling layer 27 Adhesive layer

Claims (10)

A base material layer, an ink layer provided on one surface of the base material layer, and a back surface layer provided on a surface opposite to the surface on which the ink layer of the base material layer is provided. An ink ribbon,
The back layer includes at least a first back layer and a second back layer, each of which has different ink transfer properties from the ink layer,
The ink ribbon according to claim 1, wherein the first and second back layers are patterned in a predetermined pattern.   The first back layer is composed of a first resin composition containing a polyvinyl butyral resin and / or polyvinyl acetal resin and an isocyanate curing agent, and the second back layer does not contain the first resin composition. The ink ribbon according to claim 1.   The polyvinyl butyral resin and / or polyvinyl acetal resin of the first resin composition and the isocyanate curing agent have a molar equivalent ratio (-NCO / -OH) of the isocyanate group of the curing agent to the hydroxyl group in the resin of 0. The ink ribbon according to claim 2, wherein the ink ribbon is blended at a ratio of 3 or more.   The ink layer of the ink ribbon comprises a post-chelate dye, and the first back layer comprises a metal ion-containing compound capable of forming a chelate complex with the post-chelate dye. ink ribbon. In the thermal transfer system which transfers ink to a material to be transferred using the ink ribbon according to any one of claims 1 to 4,
A delivery section for delivering the ink ribbon;
A first transfer that is disposed on the downstream side of the delivery unit and has a first heating body provided on the back layer side of the ink ribbon, and transfers the ink in the ink layer of the ink ribbon to the transfer target. Equipment,
A winding unit that is disposed on the downstream side of the first transfer device and winds up the ink ribbon after ink transfer;
A second transfer device provided in the vicinity of the winding unit, and having a second heating body for heating the ink ribbon after ink transfer from the back layer side,
In the second transfer device, the ink is transferred from the ink layer of the ink ribbon to the back layer of the ink ribbon located inside the ink ribbon by being heated by the second heating body. , Thermal transfer system. In the winding unit, the ink ribbon is wound so that the back layer of the ink ribbon is positioned outside the ink layer,
The thermal transfer system according to claim 5, wherein the second heating body heats the outermost ink ribbon from the outside.   The thermal transfer system according to claim 5 or 6, wherein the heating body is a roll-shaped heating element. In the first transfer device, the ink of the ink layer of the ink ribbon is transferred in a first pattern to the transfer object,
In the second transfer device, the ink of the ink layer of the outer ink ribbon is transferred to the back layer of the inner ink ribbon in a second pattern different from the first pattern when heated by the second heating body. The thermal transfer system according to claim 5 or 6.   The thermal transfer system according to claim 8, wherein the second heating body has protrusions arranged in a predetermined pattern on an outer periphery.   The thermal transfer system according to claim 8, wherein the second heating body is a thermal print head.