JP2019093696A - Thermal melt transfer type ink ribbon - Google Patents

Abstract

To provide a thermal melt transfer type ink ribbon which is excellent in environment storage performance under high temperature environment, and is excellent in printing quality such that planer peeling hardly occurs on a printed image when printing is performed under high temperature environment.SOLUTION: A thermal melt transfer type ink ribbon 1 has a heat resistant lubricant layer 3 provided on one surface of a base material film 2 and has a transfer control layer 4 and an ink layer 5 laminated in this order on the other surface, in which the ink layer contains at least a colorant and a thermoplastic resin having a glass transition point of 50°C or higher and 110°C or lower, and the transfer control layer contains 50 mass% or more of fine particles formed of a high density polyethylene wax having a melt peak temperature measured by a differential scanning calorimetry of 110°C or higher and 135°C or lower and a temperature difference between the melt peak temperature and an extrapolated melt-starting temperature of 10.0°C or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermal melting transfer ink ribbon excellent in environmental preservation performance and print quality under a high temperature environment.

  A thermal melting transfer ink ribbon provided with an ink layer containing at least a colorant such as a pigment and a binder such as various waxes and resins on a substrate film is used by being loaded in a thermal transfer printer and used in a factory or a distribution warehouse. It is widely used for printing text information and bar codes on various types of slips, product tags, and labels for physical distribution management.

  The thermal transfer printer is easy to carry because the size of the printer itself is compact as compared with an office printer such as a laser printer, and the heat transfer printer has a simple structure, so it is hard to break down, etc. The use in various environments is assumed. For example, it may be actually used in an environment with low temperature such as a cold area or a non-air-conditioned place in winter, or in an environment with high temperature such as a tropical area or a non-air-conditioned place in summer.

  Even in such an environment where the air temperature is particularly high, even if the heat melting transfer type ink ribbon is stored in a wound state for a long time, the heat of the outside air temperature and the pressure of the wind cause the ink layer and the heat resistant slippery property. There have been problems with environmental preservation performance such as a blocking phenomenon in which layers adhere to each other, and deterioration in printing quality due to softening and deformation of the ink layer and the transfer control layer.

  In addition, when a thermal transfer printer is loaded with a thermal melting transfer ink ribbon and printing is performed continuously, the heat generated during printing is stored in the thermal head, and the printing quality is said to be called surface peeling due to the heat. Although this phenomenon occurred, the phenomenon of surface peeling tended to occur more easily in a high temperature environment.

  To explain the surface peeling, as shown in FIG. 2, the surface peeling was formed unevenly in the form of a scale on the opposite side of the direction of conveyance of the printing medium 6 of the printing image portion 7a originally intended to be formed. While the printed image portion 7 a refers to the printed image portion 7 b and the printed image portion 7 a is firmly transferred and adhered to the print medium 6, the surface peeled portion 7 b is usually adhered to the print medium 6. I did not. When this surface peeling occurs, when printing such as character information, the appearance is not only bad in appearance but when the condition is severe, characters can not be recognized, and when printing such as a barcode, a bar code reading error occurs. In addition to problems with print quality such as the following problems, problems such as contamination of the medium to be printed and the surrounding environment may also occur due to removal and scattering of the planar peeled portions.

  The normal printing mechanism performed by the thermal transfer printer will be described. As shown in FIG. 3, the print medium 6 and the thermal melting transfer ink ribbon 1 are sandwiched between the thermal head 8 and the platen roll 9 of the thermal transfer printer and pressure-bonded. The printer is set in the thermal transfer printer as it is. At the time of printing, the transfer control layer 4 and the ink layer 5 in the portion where the print image is formed are heated and softened / melted by the thermal head 8, and they penetrate or wet the surface portion of the print medium 6 After that, the thermal melting transfer ink ribbon 1 and the printing medium 6 are peeled off at a timing when it is cooled and solidified to a certain extent, so that a printing image including the transfer control layer 4 and the ink layer 5 is transferred and formed on the printing medium 6 .

  During normal printing, only the transfer control layer 4 and the ink layer 5 between A and B in FIG. 3 are heated by the thermal head 8 to soften and melt, and the transfer control layer 4 and the base having the weakest adhesive strength Delamination occurs near the interface with the material film 2, and only the transfer control layer 4 and the ink layer 5 between A and B in FIG. 3 are transferred to the printing medium 6, ie, the original part of 7a in FIG. Only the print image portion which is to be formed is formed.

  However, at the time of printing where planar peeling occurs, although the thermal head 8 heats only between A and B in FIG. A state in which at least a part of the transfer control layer 4 on the side closer to the base film 2 between B and C in FIG. 3 is softened and melted by the heat, but the outermost layer of the ink layer 5 is not softened and melted And a printed image portion originally intended to be formed when the softened and melted ink layer 5 between A and B and the transfer control layer 4 solidify when the heat melting transfer type ink ribbon 1 and the print medium 6 are peeled off. A portion of the transfer control layer 4 and the ink layer 5 between B and C in FIG. 3 is transferred as a printed image 7b which is a planar peeling portion in a manner of being pulled by the printed image 7a. The portion of the print image 7b is transferred by being pulled by force to the portion of the print image 7a, and since the transfer control layer 4 and the ink layer 5 between B and C in FIG. 3 are mechanically broken by force. In addition, as shown in FIG. 2, the fractured surface is very unevenly formed, and the ink layer 5 in this portion is transferred to the transfer medium 6 because it is not softened / melted. Not glued. Since the printed image 7b peeled off in this manner is not a portion originally intended for print formation and is not adhered to the medium to be transferred 6, the problem of print quality and the problem of contamination as described above are cause.

  In order to solve the problems as described above, for example, Patent Document 1 discloses a method in which a color material containing a coloring material, a heat melting material, a thermoplastic material, and a surfactant is coated on a support. In the thermal transfer recording medium, when all the constituent materials have a melting point of 40 ° C. or higher, the transfer sensitivity does not decrease, the blocking resistance is excellent, and good print quality can be exhibited even under a high temperature environment. Have been described.

  Further, in Patent Document 2, a primer layer in a thermal transfer recording medium is composed of a wax and a thermoplastic resin incompatible with the wax, and a resin which does not melt the thermoplastic resin due to the residual heat of the thermal head is used. According to the matter, it is described that it is possible to prevent surface peeling of a recorded image and to impart high abrasion resistance to the recorded image.

  However, in the case of the heat-melt transfer type ink ribbon as shown in Patent Document 1, for example, even if the melting point of the constituent material is 45 ° C., the constituent material starts melting at a temperature slightly lower than the melting point, and so on. Even in environmental preservation under an environment of 40 ° C., it may not be possible to reliably prevent the occurrence of blocking phenomenon or deterioration of printing quality, and such a hot-melt transfer type ink ribbon naturally has a temperature of 50 ° C. In environmental preservation under the environment, it was hardly possible to prevent the blocking phenomenon and the like.

  Further, if a heat melting transfer type ink ribbon as shown in Patent Document 2 is used, it is effective in preventing surface peeling of a printed image due to thermal head heat storage at the time of printing in a normal temperature environment of a room temperature of about 25 ° C. However, due to the fact that the thermal storage temperature of the thermal head is higher in a high temperature environment with a temperature of 40 ° C, the surface peeling of the printed image is effective depending on the conditions of the added amount of wax used for the primer layer and the melting point. Could not be prevented. When the primer layer is thus composed of mutually incompatible materials and the melting point or softening point of the thermoplastic resin to be used as the adhesive is very high, the primer layer and the base film are printed at the time of printing. Since the adhesive force does not decrease so much and remains relatively strong, it is difficult to cause surface peeling, but it is difficult to transfer the print image which was originally intended to be formed, such as thin spots etc. Print quality problems tend to occur.

JP-A-63-3995 Unexamined-Japanese-Patent No. 2003-182254

  The present invention has been made in view of such a situation, and is excellent in environmental preservation performance under high temperature environment, and in printing quality in which surface peeling is unlikely to occur in a printed image when printing is performed under high temperature environment. It is a main object to provide an excellent heat melting transfer type ink ribbon.

The first problem to be solved by the present invention is to provide a thermal melting and transfer type ink ribbon excellent in environmental preservation performance under high temperature environment. As a result of the present inventor's investigation in order to solve this subject, by containing a thermoplastic resin having a glass transition temperature of 50 ° C. or more and 110 ° C. or less at least in the ink layer, the ink can be stored in the environment at least at 50 ° C. It turned out that the softening and deformation of the layer itself hardly occur. Next, as a result of examining the transfer control layer by the present inventor, the transfer control layer contains 50% by mass or more of fine particles of high density polyethylene wax, and further starts melting at the highest possible temperature among the high density polyethylene wax. as a result of selecting only objects, and limited to a differential scanning calorimetry melting peak temperature measured by the measuring method (JIS K7121 _{(T pm} in Figure 4)) 135 ℃ 110 ℃ or more of high density polyethylene wax, and further melting peak temperature By limiting the temperature difference of the extrapolation melting start temperature (JIS K 7121 (T _{im in} FIG. 4) to within 10.0 ° C., the transfer control layer itself is completely softened / deformed in an environmental preservation test at a temperature of 50 ° C. I found it was not. The present inventor uses the ink layer and the transfer control layer as described above in combination to prevent blocking phenomenon and softening / deformation of the ink layer and transfer control layer even when stored at high temperature of at least 50 ° C. It has been found that it is possible to obtain a hot-melt transfer type ink ribbon excellent in environmental preservation performance under a high temperature environment in which a decrease in print quality caused by the above hardly occurs.

  The second problem to be solved by the present invention is to provide a heat melting transfer ink ribbon excellent in printing quality in which surface peeling is unlikely to occur in a printed image even when printing is performed in a high temperature environment. . As a result of the present inventors' investigation to solve this problem, the melting peak temperature measured by differential scanning calorimetry in the transfer control layer is 110 ° C. or more and 135 ° C. or less, and the temperature of the melting peak temperature and the extrapolation melting start temperature When continuous printing was performed in a high temperature environment with a temperature of 40 ° C. by storing 50 mass% or more of fine particles made of high density polyethylene wax having a difference of 10.0 ° C. or less, heat was stored between B and C in FIG. Even if the temperature of the thermal head rises to 60 ° C., the fine particles of high density polyethylene wax contained in the transfer control layer do not soften or melt at all, so the adhesion of the interface between the transfer control layer and the base film is completely It has been found that it does not decrease and as a result prevents the occurrence of planar peeling. In addition, as a result of using the fine particles of high density polyethylene wax, the inventors of the present invention have made the state change of the transfer control layer extremely large in the portion heated and melted normally by the thermal head and the portion not heated and melted. It has been found that planar peeling is less likely to occur due to the foil cuttability of the transfer control layer being greatly improved.

  As mentioned above, as a result of the present inventor's examining in order to solve all the subjects, a heat-resistant lubricating layer is provided in one side of a substrate film, and a transfer control layer and an ink layer are laminated one by one on the other side. The ink layer contains at least a coloring material and a thermoplastic resin having a glass transition temperature of 50 ° C. or more and 110 ° C. or less, and the transfer control layer is formed by differential scanning calorimetry Containing 50% by mass or more of fine particles of high density polyethylene wax having a measured melting peak temperature of 110 ° C. or more and 135 ° C. or less and a temperature difference between the melting peak temperature and the extrapolation melting start temperature within 10.0 ° C. The inventors have arrived at the invention of a heat melting transfer type ink ribbon.

  When the heat melting transfer type ink ribbon of the present invention is used, problems of environmental preservation performance such as blocking phenomenon and deterioration of printing quality hardly occur even when preservation is carried out under high temperature environment, and printing is carried out even under high temperature environment Print quality problems such as surface peeling are less likely to occur on the print image.

BRIEF DESCRIPTION OF THE DRAWINGS Typical sectional drawing which shows an example of embodiment of the heat melting transfer type | mold ink ribbon of this invention. The schematic plan view of the printing image for demonstrating planar peeling. FIG. 2 is a schematic cross-sectional view of the thermal head peripheral portion of the thermal transfer printer for describing the generation principle of planar peeling. Explanatory drawing about the melting peak of the DSC curve measured by the differential scanning calorimeter.

  The heat melting transfer type ink ribbon 1 of the present invention is basically provided with a heat resistant slip layer 3 on one side of a substrate film 2 as shown in FIG. 1 and a transfer control layer 4 and an ink layer 5 on the other side. Are sequentially stacked and provided.

<< Each component of heat melting transfer ink ribbon >>
Next, details of each component of the heat-melt transfer type ink ribbon in the present invention will be shown below.

<Base film>
The base film used in the present invention is not particularly limited as long as it has a certain degree of heat resistance and strength, and conventionally known materials can be appropriately selected and used. Examples of such a heat resistant substrate film include polyethylene terephthalate film (PET), polypropylene film, polystyrene film, polyimide film, polyamide film, polycarbonate film, polyvinyl chloride film, etc. It is most preferred to use. Although the thickness of the substrate film is not particularly limited, it may be 2 μm or more and 12 μm or less depending on the material so that the strength, heat resistance and thermal conductivity may be appropriate, but the thermal conductivity is good. 3 micrometers or more and 6 micrometers or less are more preferable from the reason of being.

<Heat resistant slip layer>
In the heat melting transfer type ink ribbon of the present invention, the heat of the thermal head during printing causes the base film to break, the base film to be fused to the thermal head, and the base film to have wrinkles. In order to prevent the occurrence of the sticking phenomenon that the slipperiness between the base film and the thermal head is deteriorated, various silicon modified resins, fluorocarbon resins, nitrocellulose resins, and polyimides are formed on one surface of the base film. A heat-resistant slip layer is provided, which is mainly composed of various known heat-resistant resins such as resins, and an adhesive resin, a crosslinking agent, a lubricant, and various organic-inorganic fillers as an auxiliary material.

Coating amount after drying of the heat-resistant lubricating layer is not particularly limited, it is determined appropriately selected from 0.01 g / m ² or more 0.50 g / m ² or less in the range in accordance with the type of usage and printer good, and more preferred range for reasons of stability of cost and performance 0.05 g / ^{m 2} or more 0.40 g / ^{m 2} or less. When the coating amount after drying of the heat resistant sliding layer is less than 0.01 g / m ² , the expected heat resistance effect can not be obtained, and conversely, the coating amount after drying of the heat resistant sliding layer is 0.5 g / m ^{When it is 2} or more, the sensitivity at the time of printing is apt to deteriorate, and problems such as foil peeling tend to occur.

<Transfer control layer>
In the present invention, a transfer control layer is provided between the base film and the ink layer to control the peeling force between the base film and the ink layer and the print repelling. The transfer control layer of the present invention, in addition to the role of a normal transfer control layer, does not adversely affect the environmental preservation performance under a high temperature environment, and further suppresses the generation of surface peeling during printing under a high temperature environment. The transfer control layer needs to satisfy the performance.

  As a result of examining the heat melting material for imparting the releasability to be used for the transfer control layer in order to satisfy the performance described above by the inventor, the melting point is relatively high and the width of the melting peak is narrow. It has been found that a heat fusible substance which is very good in releasability from the base film and is difficult to mix with the ink layer at the time of melting is preferable. As a result of further examination of such a heat-melting substance, it was found that it is most preferable to add high density polyethylene wax to the transfer control layer.

  Furthermore, as a result of continuing investigations by the present inventors for high density polyethylene wax used in the transfer control layer, melting peak temperature measured by differential scanning calorimetry of high density polyethylene wax is 110 ° C. or more and 135 ° C. or less, more preferably 120 C. to 130 ° C., and the temperature difference between the melting peak temperature and the extrapolation melting start temperature is within 10.0 ° C., more preferably within 6.0, and most preferably within 4.0 ° C. By using high density polyethylene wax as the transfer control layer, the high density polyethylene wax does not melt at all even if heat of 60 ° C is added to the transfer control layer, so the transfer control layer itself is softened under high temperature environment. It has been found that it is effective in preventing deformation and at the same time preventing the occurrence of surface peeling during printing in a high temperature environment.

  The melting peak temperature of the high density polyethylene wax used in the transfer control layer is below the lower limit of 110 ° C. in the above range, or the temperature difference between the melting peak temperature of the high density polyethylene wax and the extrapolation melting start temperature is above 10.0 ° C. In addition, the temperature at a of the melting peak of the DSC curve in FIG. 4 tends to be smaller than 60 ° C., because the high density polyethylene wax starts to absorb heat and the softening and melting start to start slightly. As a result, high-density polyethylene wax begins to partially soften and melt even at temperatures lower than 60 ° C. As a result, the transfer control layer softens and deforms under high temperature environments, and environmental preservation performance tends to deteriorate. In addition, surface peeling is likely to occur during printing in a high temperature environment. Conversely, if the melting peak temperature of high-density polyethylene wax exceeds 135 ° C., which is the upper limit of the above range, the printing sensitivity and printing transferability are due to the heat quantity during printing and the melt viscosity near the melting point rapidly increasing. It tends to be worse, and problems such as printing blur easily occur particularly in a low temperature environment.

Furthermore, when the characteristics of the melting peak measured by differential scanning calorimetry of high density polyethylene wax suitable for use in the transfer control layer of the present invention were further examined, the melting peak is a single peak and the melting peak The narrower the width, the more effective the prevention of deterioration of environmental preservation performance under high temperature environment and the prevention of surface peeling under high temperature environment, and the width of the melting peak is at least the extrapolation melting end temperature (JIS K 7121) The temperature difference between (T _{em in} FIG. 4) and the extrapolation melting temperature (T _{im in} FIG. 4) is preferably within 15 ° C., more preferably within 10 ° C., and most preferably within 8 ° C. I understand that.

  Furthermore, when the characteristics of the melting peak measured by differential scanning calorimetry of high density polyethylene wax suitable for use in the transfer control layer of the present invention were examined, the differential scanning calorimetry of high density polyethylene wax was examined. It was found that the measured heat of fusion (JIS K 7122) is preferably 150 J / g or more and 300 J / g or less, more preferably 180 J / g or more and 280 J / g or less. If the heat of fusion of the high-density polyethylene wax is within the above range, it is difficult to cause the transfer control layer to melt by a small amount of heat, which proves effective in preventing surface peeling during printing in a high temperature environment. The

  Furthermore, when the high density polyethylene wax suitable for use in the transfer control layer of the present invention was examined, the weight average molecular weight (Mw) in terms of styrene measured by the GPC method of the high density polyethylene wax is 4,000 to 50,000. It has been found that is more preferably 10000 or more and 40000 or less. When a high density polyethylene wax having a weight average molecular weight in the above range is used in the transfer control layer of the present invention, the influence of low molecular weight components is small, and a linear high density polyethylene wax having a relatively high molecular weight is used as a main component. In addition, the melting peak temperature of high density polyethylene wax is high, the width of melting peak is narrow, and almost no endotherm is seen on the low temperature side below 60 ° C of melting peak, so the environmental preservation performance deterioration under high temperature environment is prevented or high temperature It is effective in preventing surface peeling under environmental conditions. Furthermore, since the melt viscosity at melting is relatively high compared to other low molecular weight waxes, the ink layer and transfer control layer are difficult to mix, and the penetration is also very low. Therefore, the scratch resistance of the printed image tends to be improved. When the weight average molecular weight of the high density polyethylene wax used for the transfer control layer is below the lower limit of the above range, the melting peak temperature is lowered and the width of the melting peak is broadened due to the influence of the low molecular weight component becoming large. Because heat absorption tends to occur even on the low temperature side of less than 60 ° C. of the melting peak, environmental preservation performance tends to deteriorate in high temperature environments or planar peeling tends to occur in high temperature environments. Furthermore, since the melt viscosity is lowered and the ink layer and the transfer control layer are easily mixed and the penetration degree is also increased, the scratch resistance of the printed image tends to be lowered. Conversely, if the weight-average molecular weight of the high-density polyethylene wax used in the transfer control layer exceeds the upper limit of the above range, the melt viscosity near the melting point gradually increases and the fluidity gradually disappears. Even when used in the control layer, the problem of transfer failure tends to occur easily.

Further, in consideration of high density polyethylene wax suitable for use in the transfer control layer of the present invention, the high density polyethylene wax having a density of 960 kg / m ³ or more, more preferably 970 kg / m ³ or more is used. It turns out that things are preferable. When a high density polyethylene wax having a density in the above range is used for the transfer control layer, the width of the melting peak of the DSC curve measured by differential scanning calorimetry is narrow, and the endotherm is on the low temperature side lower than 60 ° C. of the melting peak. Since it is not seen, it is effective in preventing deterioration of environmental preservation performance under high temperature environment and preventing surface peeling under high temperature environment, and further, since the penetration degree becomes high, the scratch resistance of the printed image is also improved.

  The high density polyethylene wax used for the transfer control layer of the present invention is used in the state of being processed into fine particles. By dispersing and adding high density polyethylene wax in the form of fine particles in the transfer control layer, the structural difference between the portion where the fine particles are melted and the portion where the fine particles are not melted by the heat during printing becomes large As a result, the foil-breakability of the ink layer and the transfer control layer at the time of printing became very good, and as a result, the planar peeling phenomenon became difficult to occur.

The particle diameter of the fine particles of high density polyethylene wax added to the transfer control layer is not particularly limited, but the median diameter D ₅₀ of the volume diameter of the particles measured by laser diffraction / scattering method is 3.0 μm or more and 13.0 μm or less It is more preferable that the thickness is 5.0 μm or more and 11.0 μm or less. Foil cutting property of the ink layer and the transfer control layer during the median diameter D ₅₀ of fine particles of high-density polyethylene wax printing Within the range is satisfactory, surface peeling hardly occurs.

  The fine particles of high density polyethylene wax used in the transfer control layer of the present invention as described above are preferably added at least 50% by mass or more of the transfer control layer, more preferably 70% by mass or more, and 80% by mass. It is most preferable to add% or more, and at most 100% by mass may be added. If the amount of fine particles made of high density polyethylene wax is within the above range, expected effects such as prevention of deterioration of environmental preservation performance under high temperature environment and prevention of surface peeling during printing under high temperature environment are exhibited become.

  The transfer control layer of the present invention may be composed only of high-density polyethylene wax which is a heat melting material, but since the adhesion of the transfer control layer to the substrate film is weak, the heat transfer transfer ink ribbon is thermally transferred There is a tendency that the so-called flaking phenomenon in which the transfer control layer or the ink layer is detached from the substrate film tends to occur easily when setting in a printer, etc. or the planar peeling phenomenon tends to occur easily in printing. . Therefore, it is preferable to add a resin having thermoplastic adhesiveness to the transfer control layer as necessary.

  The thermoplastic adhesive resin to be added to the transfer control layer of the present invention is not particularly limited, and various known thermoplastic adhesive resins can be used, but it is preferable to add an olefin copolymer resin. preferable. As such olefin type copolymer resin, for example, ethylene-methyl (meth) acrylate copolymer resin, ethylene-ethyl (meth) acrylate copolymer resin, ethylene-propyl (meth) acrylate copolymer, ethylene- Butyl (meth) acrylate copolymer · propylene-methyl (meth) acrylate copolymer · propylene-ethyl (meth) acrylate copolymer · propylene-propyl (meth) acrylate copolymer · propylene-butyl (meth) acrylate co Α-olefin-alkyl (meth) acrylate copolymer resin such as polymer, α-olefin-vinyl acetate copolymer resin such as ethylene-vinyl acetate copolymer resin / propylene-vinyl acetate copolymer resin, Ethylene-(meth) atalilamide copolymer-propylene For example, various olefin-based copolymer resins such as α-olefin- (meth) acrylamide copolymer such as (meth) acrylamide copolymer, and those copolymer resins modified with various carboxylic acids such as maleic anhydride, for example α-olefin-alkyl (meth) acrylate-maleic anhydride terpolymer · α-olefin-vinyl acetate-maleic anhydride terpolymer · α-olefin-(meth) acrylamide-maleic anhydride terpolymer etc And various olefin-based terpolymers and the like, but are not limited thereto. Among the above-mentioned olefin copolymers, the most preferable one to be added to the transfer control layer of the present invention is an ethylene copolymer resin having ethylene as a main skeleton.

  When a coating prepared by mixing fine particles of high density polyethylene wax and solvent-soluble matter of an olefin copolymer resin as described above is coated on a substrate film and dried to form a transfer control layer, In the transfer control layer, fine particles made of high-density polyethylene wax form islands of islands, and the olefin copolymer resin forms a sea-island structure of the sea. During printing, heat is applied from the thermal head to the transfer control layer to melt the transfer control layer. Then, since the olefin copolymer resin and the high density polyethylene wax are easily mixed at the time of melting, the portion to which heat is applied becomes a uniform mixture, and as a result, the base material is compared with that before heat is applied. At the same time as the transfer is performed very smoothly because the adhesion to the film is greatly reduced, the base film of the heat-melted portion and the non-melted portion Planar peeling for the difference of the adhesive force increases against even less likely to occur. Therefore, as the thermoplastic adhesive resin used in the present invention, it is preferable to select and use a resin which is compatible with the high density polyethylene wax at the time of melting.

  When the present inventor examined the thermal characteristics of the thermoplastic adhesive resin added to the transfer control layer, it is preferable that the melting peak temperature of the thermoplastic adhesive resin is at least 60 ° C. or more and 150 ° C. or less, more preferably It turned out that it is preferable that it is 65 to 130 degreeC. When the melting peak temperature of the thermoplastic adhesive resin is in the above range, the printing sensitivity is appropriate, and the environmental preservation performance under high temperature environment and the surface peeling phenomenon under high temperature environment are not adversely affected.

  Furthermore, when the present inventor examined the thermal characteristics of the thermoplastic adhesive resin added to the transfer control layer, the glass transition point (Tg) of the thermoplastic adhesive resin is not particularly limited, but is -20 ° C or lower. It turned out that it is preferable that the temperature is preferably -30.degree. C. or less. The glass transition point in the present invention means the midpoint glass transition temperature (JIS K 7121) measured by differential scanning calorimetry. If the glass transition point of the thermoplastic adhesive resin is in the above range, the flaking phenomenon does not occur because the flexibility is not lost even in a low temperature environment, and the state of the resin does not change even in low temperature printing. There is no change in print quality.

  Since thermoplastic adhesive resins having a glass transition temperature of 0 ° C. or less as described above have a low glass transition temperature, they tend to deform due to their properties when stored for a long time under pressure in a high temperature environment. For example, if it is added to the transfer control layer as it is, the transfer control layer may be deformed in an environmental preservation test under a high temperature environment, and as a result, problems such as a blocking phenomenon and deterioration of printing quality may occur. However, the transfer control layer has a sea-island structure by forming a transfer control layer using a paint prepared by mixing fine particles of high density polyethylene wax as described above with a solvent melt of a thermoplastic adhesive resin or the like. Furthermore, by making fine particles consisting of high density polyethylene wax in the island part protrude from the coating film of thermoplastic adhesive resin which is the sea part, the high density polyethylene wax particles do not soften or deform at all even when pressure is applied under high temperature environment As a result, it became possible to prevent the softening and deformation of the transfer control layer itself from occurring at all.

  Although the addition amount of the thermoplastic adhesive resin added to the transfer control layer of the present invention is not particularly limited, it is preferably 1% by mass to 30% by mass of the transfer control layer, more preferably 5% by mass to 20%. It is preferable that it is% or less. If the addition amount of the thermoplastic adhesive resin is in the above range, it does not adversely affect the transferability of printing, the environmental preservation performance under high temperature environment, and the surface peeling phenomenon under high temperature environment, and the base film and the transfer control layer And, by improving the adhesion between the ink layer and the transfer control layer, the flaking phenomenon can be prevented, and a certain effect can be exhibited also in the occurrence prevention of the planar peeling phenomenon. When the thermoplastic adhesive resin is added to the transfer control layer beyond the upper limit of the above range, the adhesion between the transfer control layer and the base film becomes too large, and the transferability of the print deteriorates, and further, the thermoplastic adhesive Due to the thickness of the coating film made of resin being larger than the particle diameter of the fine particles made of high density polyethylene wax, the environmental preservation performance under high temperature environment tends to deteriorate.

  In the transfer control layer of the present invention, various well-known organic / inorganic fillers, various waxes, various thermoplastic resins, surfactants and antistatic agents in addition to the fine particles made of high density polyethylene wax and thermoplastic adhesive resins mentioned above And the like may be added as appropriate.

The coating amount after drying of the transfer control layer of the present invention is not particularly limited and may be suitably selected from the range of 0.1 g / m ² or more and 2.0 g / m ² or less, but in consideration of printing sensitivity and transferability. It is more preferable to select from the range of 0.2 g / m ² or more and 1.0 g / m ² or less. If the applied amount after drying of the transfer control layer is less than 0.1 g / m ² , peeling may not be properly performed at the interface between the transfer control layer and the base film, and transfer defects tend to occur, and conversely When the coating amount after drying of the transfer control layer exceeds 2.0 g / m ² , the sensitivity may be insufficient at the time of printing, or the components of the transfer control layer transferred to the print may be increased. There is a tendency for the sex to decrease.

<Ink layer>
In the present invention, on the transfer control layer, an ink layer comprising at least a coloring agent such as various known organic / inorganic pigments such as carbon black and dyes and a binder component such as a thermoplastic resin is provided. The addition amount of the colorant is not particularly limited, but is appropriately selected from the range of 10% by mass to 50% by mass, more preferably 20% by mass to 30% by mass, of the total mass ratio of the ink layer. Things are preferred. When the addition amount is less than 10% by mass, the print density of the printed matter is not sufficient, and when it exceeds 50% by mass, the transferability of the print tends to be adversely affected.

  As a result of the present inventors examining the main component of the binder component used in the ink layer of the present invention, the glass transition point is 50 ° C. or more and 110 ° C. or less, more preferably 60 ° C. as the main component of the binder component of the ink layer. It is preferable to use a thermoplastic resin of 100 ° C. or less. If the glass transition point of the thermoplastic resin is 50 ° C. or more and 110 ° C. or less, it does not soften or deform in a high temperature environment of at least 50 ° C., and therefore the environmental preservation performance is not adversely affected. Conversely, when the glass transition temperature of the thermoplastic resin used for the ink layer is less than 50 ° C., the resin tends to start to soften and deform under the high temperature environment of 50 ° C. Therefore, the blocking phenomenon occurs and the ink layer softens and deforms. There is a tendency for a drastic drop in print quality due to When the glass transition temperature of the thermoplastic resin used for the ink layer exceeds 110 ° C., not only the heat quantity required for melting the ink layer in printing increases, but also the melt viscosity of the thermoplastic resin increases. As a result, printing quality problems such as printing defects and transfer defects tend to occur easily.

  The softening point (ring and ball method) of the thermoplastic resin used in the ink layer of the present invention is not particularly limited, but is preferably 60 ° C. or more and 190 ° C. or less, and more preferably 70 ° C. or more and 170 ° C. or less More preferable. When the softening point of the thermoplastic resin is in the above range, the environmental preservation performance under high temperature environment is excellent, and the surface peeling phenomenon hardly occurs at the time of printing under high temperature environment, and print blur and transfer failure occur at the time of printing. Proper printing can be performed without occurrence. Normally, when a thermoplastic resin with a glass transition temperature of 50 ° C or higher is selected, the softening point of the thermoplastic resin is almost all 60 ° C or higher, but conversely, a thermoplastic resin with a softening point of 60 ° C or higher is selected Also, the glass transition point of the thermoplastic resin is not all 50 ° C. or higher, and there are many resins whose temperature is lower than 50 ° C. or lower than 0 ° C. in some cases. In other words, if the glass transition point of the thermoplastic resin is higher than the environmental temperature during the environmental preservation test, the softening point of the thermoplastic resin is higher than the environmental temperature and does not soften, and the glass transition point is also higher than the environmental temperature. No accompanying deformation or property change occurs, so there is no blocking phenomenon or deterioration of printing quality due to softening or deformation of the ink layer, etc. However, even if the softening point of the thermoplastic resin is higher than the environmental temperature, the glass transition point is When the temperature is lower than the environmental temperature, the blocking phenomenon or the deterioration of the printing quality due to the softening or deformation of the ink layer may occur due to the deformation or the property change due to the volume change of the thermoplastic resin. Therefore, in the present invention, the glass transition point is used as a factor for limiting the thermal characteristics of the thermoplastic resin of the ink layer.

  The thermoplastic resin used for the ink layer of the present invention includes polyester resins, polyamide resins, polystyrene resins, styrene acrylic resins, acrylic resins and their modified products and their copolymers, etc. Relatively high molecular weight thermoplastic resin with a molecular weight (Mn) of 3000 or more, coumarone resin, rosin resin, ketone resin, styrene hydrocarbon resin, terpene resin, terpene phenol resin, petroleum resin, aliphatic Relatively low molecular weight thermoplastic resins with a number average molecular weight (Mn) of less than 3000, which are called tackifying resins, such as hydrocarbon resins, aromatic hydrocarbon resins and their modified products, etc. may be mentioned, but are limited thereto It does not mean that The thermoplastic resin may be used singly or in combination of two or more, but more preferably a thermoplastic resin having a relatively high molecular weight of 3,000 or more and a heat of a relatively low molecular weight less than 3,000. It is preferable to mix and use a plastic resin, more preferably, a relatively high molecular weight thermoplastic resin having a number average molecular weight of 5,000 or more and a relatively low molecular weight thermoplastic resin having a number average molecular weight of less than 3,000.

  When a relatively high molecular weight thermoplastic resin having a number average molecular weight of 3000 or more is added to the composition of the ink layer, the coating film strength of the ink layer is improved, and the scratch resistance and chemical resistance of the printed image can be improved. However, the higher the number average molecular weight of these thermoplastic resins, the higher the coating film strength of the ink layer and the higher the melt viscosity of the ink layer. There is a tendency for the adhesiveness and the foil-cutting property of the ink layer to be deteriorated, and as a result, the transferability of the printed image and the definition of the printed image tend to be lowered. The upper limit of the number average molecular weight of such a relatively high molecular weight thermoplastic resin is 100000 or less from the relationship between the adhesiveness of the ink layer to the medium to be printed and the transferability of the printing medium, and the removability of the printed image. Is preferable, 50000 or less is more preferable, and 30000 or less is most preferable.

  When a thermoplastic resin having a number average molecular weight of less than 3000 is added to the ink layer, the melt viscosity of the ink layer is lowered, and the adhesion to a medium to be printed and the foil breakage of the ink phase tend to be greatly improved. Therefore, the transferability of the printed image and the definition of the printed image are greatly improved, but on the other hand, the abrasion resistance and the chemical resistance of the printed image tend to be greatly reduced. The lower limit of the number average molecular weight of such a relatively low molecular weight thermoplastic resin is not particularly limited, but the number average molecular weight of such a thermoplastic resin is at least 300 or more, and usually 500 or more.

  As a result of examining the thermoplastic resin used in the ink layer by the present inventor, it is found that a thermoplastic polyester resin having a number average molecular weight of 5,000 to 30,000 and a thermoplastic resin having a number average molecular weight of 300 to less than 3,000 are mixed. It turned out that it is most preferable to use. The thermoplastic resin having a number average molecular weight in the range of 300 to less than 3000 is not particularly limited, but it is preferable to use a ketone resin, a styrene hydrocarbon resin, a terpene phenol resin, or the like. The mixing ratio of the thermoplastic polyester resin having a number average molecular weight of 5,000 to 30,000 and the thermoplastic resin having a number average molecular weight of 300 to less than 3,000 is not particularly limited, but a thermoplastic polyester resin having a number average molecular weight of 5,000 to 30,000 or less The mixing ratio of the thermoplastic resin having a number average molecular weight of 300 or more and less than 3000 is preferably in the range of 7/3 to 3/7 in mass ratio. By using the mixture of the thermoplastic resins for the ink layer, the adhesion and transferability of the ink layer to the printing medium at the time of printing is good, the foil cutting property of the ink layer is good, and the definition of the printed image It has been found that an ink layer having a good balance of properties is obtained, which is excellent in the properties and further in the performance such as the scratch resistance of the printed image.

  Although the addition amount of the thermoplastic resin used in the ink layer of the present invention is not particularly limited, it may be 30% by mass to 90% by mass of the ink layer, and more preferably 60% by mass to 80% by mass. It is preferable that If the addition amount of the thermoplastic resin in the ink layer is within the above range, the adhesion and transferability of the ink layer to the printing medium at the time of printing, the definition of the printed image, the scratch resistance and the like are appropriate. Furthermore, since the influence of the thermoplastic resin on the environmental preservation performance under the high temperature environment of the ink layer is sufficient, it is possible to reflect the properties of the thermoplastic resin to the ink layer almost as it is.

  In the ink layer of the present invention, a small amount of wax may be added to the ink layer as an auxiliary material in order to improve the foil-cutting property of the ink layer, the printing sensitivity and the blocking resistance. Examples of the wax include, but are not limited to, carnauba wax, montanic acid wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax and the like. In addition, small amounts of various known surfactants and inorganic and organic fillers may be added as appropriate to the ink layer as necessary as other auxiliary materials, and the colorant dispersibility, ink foil breakage, ink layer melt viscosity, etc. Modifications and adjustments may be made.

The application amount after drying of the ink layer of the present invention is not particularly limited, and may be appropriately selected from the range of 0.3 g / m ² or more and 3.0 g / m ² or less according to the required quality. it is more preferably selected appropriately from 0.5 g / ^{m 2} or more 2.0 g / ^{m 2} or less in the range in terms of performance stability. If the coating amount after drying of the ink layer is less than 0.3 g / m ² , sufficient print density and scratch resistance tend not to be obtained, and conversely, if the coating amount exceeds 3.0 g / m ² , printing There is a tendency for the sensitivity and the foil breakage to deteriorate.

  Next, the present invention will be specifically described by way of examples.

<Method of forming base film and heat resistant slip layer>
In a gravure coating machine, the coating for a heat-resistant slip layer shown below is applied on one side of a 4.5 μm thick polyethylene terephthalate film (PET film) using a gravure coating machine, and the coating is dried to a coating weight of 0.2 g / m ² Heat resistant slip layer of The following examples and comparative examples of the present invention all use the heat resistant substrate film and the heat resistant slip layer.
(Composition of coating for heat resistant slip layer)
Raw material component mass%
-Methyl ethyl ketone / toluene = 1/1 solvent solution (solid content 15%) of silicone modified polyester polyurethane resin 25.0
・ Methyl ethyl ketone 60.0
・ Toluene 15.0
The above-mentioned paint for a heat-resistant slip layer is prepared by adding a solution obtained by dissolving a mixed solvent of methyl ethyl ketone and toluene and a silicon-modified polyester polyurethane resin in a solvent having a methyl ethyl ketone and toluene mass ratio of 1: 1 in each container according to the above composition. It is prepared by stirring and mixing with a dissolver or the like. The preparation method of the coating material for a heat resistant sliding layer mentioned above and the application method of a heat resistant sliding layer are an example, it is not limited to this, and various known methods can be used.

<Method of forming transfer control layer>
Details of the properties of each of the heat-melting materials used in the transfer control layer of the examples and comparative examples of the present invention are shown in Table 1.

The coating for a transfer control layer shown below is applied by a gravure coating machine to the surface on the opposite side of the PET film on which the heat resistant slip layer is applied and formed, dried and a transfer control layer having a coating amount of 0.5 g / m ² It formed. Using the respective heat fusible materials in Table 1 as heat fusible materials in the formulation of the following transfer control layer, the paints for respective transfer control layers used in the respective examples and comparative examples of the present invention were prepared. The details of the blending ratio by each raw material in the blending of the transfer control layer paint are shown in Table 3 below.

(Composition of paint for transfer control layer)
Component Parts by mass · Toluene dispersion of heat fusible substance (solid content 10%) 85.0
· Ethylene vinyl acetate resin "Tg: -30 ° C, melting peak temperature: 60 ° C,
VA: 33% "in toluene solution (solid content 10%) 15.0
As a method of preparing the transfer control layer paint, first, toluene and a thermally fusible substance are metered into a container which can be sealed and capable of stirring and heating, and the container is sealed and then heated with stirring while heating. After completely dissolving the fusible substance in toluene, the particles of the thermally fusible substance are dispersed in toluene by gradually cooling them to 30 ° C. or less while stirring. A toluene dispersion of the volatile substance. Next, after measuring the toluene and ethylene vinyl acetate resin in a container which can be sealed and capable of stirring and heating, they are heated with stirring to completely dissolve the ethylene vinyl acetate resin in toluene, and after 30 ° C. or less The solution is cooled to form a toluene solution of ethylene vinyl acetate resin having a solid content of 10%. Finally, the toluene dispersion of the heat fusible substance and the toluene solution of ethylene vinyl acetate resin are metered into the container according to the above composition, stirred and mixed with the dissolver, and dispersed by the bead mill, the median diameter of fine particles of heat fusible substance By adjusting D ₅₀ to be in the range of 5.0 to 11.0 μm, a paint for transfer control layer is completed. When two or more types of heat fusible substances are used in the paint composition for the transfer control layer described above, toluene dispersions of the heat fusible substance are separately prepared for each heat fusible substance. Before the dispersion of the bead mill, they may be mixed and used. The method of preparing the transfer control layer coating material and the method of applying the transfer control layer described above are an example, and the present invention is not limited thereto, and various known methods can be used.

<Method of forming ink layer>
(Ink layer)
The details of the properties of the thermoplastic resin used in the ink layer of the examples and comparative examples of the present invention are shown in Table 2.

The coating material for ink layer shown below was apply | coated with the gravure coating machine on the said transfer control layer, it dried, and formed the ink layer of 1.2 g / m < ² > of application amounts. Using each thermoplastic resin of the above-mentioned Table 2 as thermoplastic resin in the paint composition for the following ink layers, paints for each ink layer used for each example and comparative example of the present invention were created. The details of the compounding ratio for each raw material in the ink layer paint composition are shown in Table 3 below.

(Composition of paint for ink layer)
Component parts by weight · Thermoplastic resin 14.0
・ Carbon black 6.0
・ Toluene 40.0
・ Methyl ethyl ketone 40.0
As a method of preparing the above-mentioned coating composition for ink application, after the toluene, methyl ethyl ketone and the thermoplastic resin are metered into a container which can be sealed, stirred and heated, they are heated with stirring to completely convert the thermoplastic resin into a solvent. After the solution is cooled to 30 ° C. or less, carbon black is further metered in and well stirred and mixed, and then dispersed by a bead mill to complete the color formation of carbon black. In addition, two or more types of thermoplastic resins may be mixed and used in the above-mentioned paint composition for the ink layer. The method for producing the ink layer coating material and the method for applying the ink layer described above are an example, and the present invention is not limited thereto, and various known methods can be used.

<Print test conditions>
Various printing tests were conducted under the following conditions using the heat melting transfer ink ribbons shown in the examples and comparative examples of Table 3. Printing was performed using the thermal melting transfer ink ribbons of Examples and Comparative Examples under the following printing test conditions in a room temperature environment of a temperature of 25 ° C. Printing energy was appropriate, and transfer defects such as printing fades and thin lines were generated. Almost no problems such as surface peeling of printing occurred.
Printer: ZEBRA110XiIV (made by Sebura)
Printing resolution: 300 dpi
Printing speed: 2 inch / sec
Print density: 14/20
Print medium: PET label

<Evaluation of surface peeling of printed image in printing under high temperature environment>
The printer used for the printing test, the medium to be printed, and the heat melting transfer ink ribbon used for printing are allowed to stand for 1 hour in a constant temperature bath set at an air temperature of 40 ° C., and printing is then performed under the printing test conditions described above. Was continuously performed for 1 minute, and the printed images from the last printed image to 10 sheets before were visually confirmed and evaluated under the conditions shown below.
A: There is no surface separation at all in the printed image.
B: Partial peeling occurred slightly on part of the printed image.
Surface peeling was clear occurred in a part of the C · · · printed image.
D · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · almost the entire surface of the printed image had been peeled off badly

<Evaluation of printing sensitivity in printing under low temperature environment>
The printer used for the printing test, the medium to be printed, and the heat-melt transfer ink ribbon used for printing are allowed to stand for 1 hour in a constant temperature bath set at a temperature of 5 ° C., and printing is then performed under the printing test conditions described above. Was carried out ten times on the label, and the printed images of the ten sheets were visually confirmed and evaluated under the conditions shown below.
A: No print fade occurs at all.
B · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Print streaks occur slightly in part.
C ··· printing blur occurs clearly in almost the entire surface.
D ··· printing blur is badly printing is hardly transferred.

<Evaluation of scratch resistance>
After applying an ABS resin ball of 1 cm in diameter with a point load of 500 g to the printed image printed under the printing test conditions described above in a room temperature environment of a temperature of 25 ° C. after 30 cycles of 1 reciprocation per second. The condition of the printed image was visually observed and evaluated under the conditions shown below.
A: There is no chipping of the printed image and no deformation of the printed image.
B: There is no loss of the printed image, but a slight deformation is seen in the printed image.
C: A slight omission of the printed image is seen, and deformation of the printed image is also clearly seen.
D: Both missing and deformed printed images can be clearly seen.

<Blocking resistance (environmental preservation performance)>
For evaluation of blocking resistance, a ribbon sample (width 60 mm, length 300 m, in-ink surface) processed into a roll by winding a material obtained by slitting a raw material of a heat melting transfer ink ribbon into a predetermined size and winding it around a paper core And storing the ribbon sample in an atmosphere of temperature 50 ° C. and humidity 80% RH for 96 hours and then cooling in a room temperature environment of temperature 25 ° C. for 24 hours and blocking the winding of the ribbon sample The condition of was visually observed and evaluated under the conditions shown below.
A: No blocking is seen at all.
B: Slight blocking is observed near the paper core of the ribbon sample.
C: Blocking is partially observed from the middle of winding of the ribbon sample to near the paper core.
D: Blocking is observed on the entire surface of the ribbon sample.

<Change in print quality before and after environmental preservation test (environmental preservation performance)>
A ribbon sample (width 60 mm, length) processed into a roll shape by winding a material obtained by slitting a raw material of a heat melting transfer ink ribbon into a predetermined size and wrapping it around a paper core to evaluate the change in printing quality before and after the environmental preservation test. (300 m, ink in-plane winding), and after storing the ribbon sample in an atmosphere of air temperature 50.degree. C. humidity 80% RH for 96 hours and further standing still for 24 hours in a room temperature environment of air temperature 25.degree. The state of printing when printing was performed under the above-described printing test conditions in a room temperature environment of a temperature of 25 ° C. was visually observed and evaluated under the conditions shown below.
A: There is no change in the print quality before and after the environmental preservation test.
B · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · After the environmental preservation test, the printing quality such as printing blur, transfer failure, and surface peeling phenomenon is slightly worse than before the environmental preservation test.
C · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · After the environmental preservation test, the print quality such as printing blur, transfer failure, and surface peeling phenomenon is clearly deteriorated compared to before the environmental preservation test.
D · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · After the environmental preservation test, the print quality such as printing blur, transfer failure, and surface peeling phenomenon is much worse than before the environmental preservation test.

  The heat melting transfer type ink ribbons of various Examples and Comparative Examples were prepared, and the details of each paint composition of the Examples and Comparative Examples and the results of the various evaluations described above are shown in Table 3 below.

  From the results shown in Table 3, the ink layer contains at least a coloring material and a thermoplastic resin having a glass transition temperature of 50 ° C. or more and 110 ° C. or less, as in the heat melting transfer ink ribbons of Examples 1 to 7. The transfer control layer is made of high density polyethylene wax having a melting peak temperature of 110 ° C. to 135 ° C. measured by differential scanning calorimetry and a temperature difference between the melting peak temperature and the extrapolation melting start temperature within 10.0 ° C. When a heat melting transfer type ink ribbon containing 50% by mass or more of fine particles is used, occurrence of blocking phenomenon and deterioration of printing quality are hardly seen even if environmental preservation test is conducted under high temperature environment, and further high temperature environment Even if printing is performed under the surface, almost no surface peeling phenomenon occurs. On the other hand, as in Comparative Example 1 to Comparative Example 5, a thermal melting material having a melting peak temperature of 110 ° C. or less or a temperature difference between the melting peak temperature and the extrapolation melting start temperature exceeding 10.0 ° C. In addition to having a tendency to cause a slight blocking phenomenon when used for printing, the print control layer is softened and deformed especially after the environmental preservation test is conducted under high temperature environment. Deterioration of printing quality such as transfer failure occurs remarkably, and occurrence of planar peeling phenomenon is also clearly seen in printing under high temperature environment. Further, fine particles of high density polyethylene wax having a melting peak temperature of 110 ° C. or more and 135 ° C. or less and a temperature difference between the melting peak temperature and the extrapolation melting start temperature within 10.0 ° C. in the transfer control layer as in Comparative Example 6 Even if it is added, if the addition amount is less than 50% by mass of the transfer control layer, the environmental preservation performance under high temperature environment may deteriorate, or surface peeling may occur during printing under high temperature environment. became. Furthermore, when a thermoplastic resin having a glass transition temperature of less than 50 ° C. was used as the main component of the binder component of the ink layer as in Comparative Example 7, the environmental preservation performance under a high temperature environment deteriorated sharply.

  The heat melting transfer ink ribbon of the present invention can be used not only in general applications for printing character information and barcodes on various types of slips, product tags, labels for physical distribution management, etc., but also in particular under high temperature environments It can be used as a thermal melting transfer ink ribbon for a thermal printer, which is highly likely to

1; heat melting transfer type ink ribbon 2; base film 3; heat resistant slip layer 4; transfer control layer 5; ink layer 6; print medium 7a; printed image (printed image portion originally intended to be formed)
7b; Printed image (area peeled off)
8; thermal head 9; platen roll 10; melting peak (DSC curve)
Tpm; melting peak temperature Tim; extrapolation melting start temperature Tem; extrapolation melting end temperature

Particle size volume-based median diameter D ₅₀ of the particles as measured by is not particularly limited is a laser diffraction scattering method of fine particles is 3.0μm or more 13.0μm or less made of high density polyethylene wax is added to the transfer control layer It is more preferable that the thickness is 5.0 μm or more and 11.0 μm or less. If the volume-based median diameter D _{50 of the} fine particles of high density polyethylene wax measured by the laser diffraction / scattering method is within the above range, the foil-cutting properties of the ink layer and the transfer control layer at the time of printing are good. Peeling phenomenon hardly occurs.

(Composition of paint for transfer control layer)
Component Parts by mass · Toluene dispersion of heat fusible substance (solid content 10%) 85.0
· Ethylene vinyl acetate resin "Tg: -30 ° C, melting peak temperature: 60 ° C,
VA: 33% "in toluene solution (solid content 10%) 15.0
As a method of preparing the transfer control layer paint, first, toluene and a thermally fusible substance are metered into a container which can be sealed and capable of stirring and heating, and the container is sealed and then heated with stirring while heating. After completely dissolving the fusible substance in toluene, the particles of the thermally fusible substance are dispersed in toluene by gradually cooling them to 30 ° C. or less while stirring. A toluene dispersion of the volatile substance. Next, after measuring the toluene and ethylene vinyl acetate resin in a container which can be sealed and capable of stirring and heating, they are heated with stirring to completely dissolve the ethylene vinyl acetate resin in toluene, and after 30 ° C. or less The solution is cooled to form a toluene solution of ethylene vinyl acetate resin having a solid content of 10%. Finally, the toluene dispersion of the heat-fusible substance and the toluene solution of ethylene vinyl acetate resin are metered into the container according to the above formulation, stirred and mixed with the dissolver, and dispersed by the bead mill while laser diffraction of fine particles of the heat-meltable substance A coating for transfer control layer is completed by adjusting the volume-based median diameter D ₅₀ measured by the scattering method to be in the range of 5.0 to 11.0 μm. When two or more types of heat fusible substances are used in the paint composition for the transfer control layer described above, toluene dispersions of the heat fusible substance are separately prepared for each heat fusible substance. Before the dispersion of the bead mill, they may be mixed and used. The method of preparing the transfer control layer coating material and the method of applying the transfer control layer described above are an example, and the present invention is not limited thereto, and various known methods can be used.

Claims (6)

  A heat-melt transfer ink ribbon comprising a heat-resistant slip layer provided on one side of a substrate film and a transfer control layer and an ink layer sequentially laminated on the other side, the ink layer comprising at least a coloring material and glass A thermoplastic resin having a transition point of 50 ° C. to 110 ° C. is contained, and the transfer control layer has a melting peak temperature of 110 ° C. to 135 ° C. measured by differential scanning calorimetry, and a melting peak temperature and extrapolation melting start A heat-melt transfer-type ink ribbon comprising fine particles of high density polyethylene wax having a temperature difference of 10.0 ° C. or less at 50% by mass or more.   The heat-melt transfer type ink ribbon according to claim 1, wherein the weight average molecular weight in terms of styrene measured by the GPC method of high density polyethylene wax is 4000 or more and 50000 or less. Thermal melt transfer ink ribbon according to claim 1 or claim 2 median diameter D ₅₀ of fine particles of high density polyethylene wax is 3.0μm or more 13.0μm or less.   The heat melting transfer ink ribbon according to any one of claims 1 to 3, wherein the thermoplastic resin is a mixture of a thermoplastic polyester resin having a number average molecular weight of 5,000 to 30,000 and a thermoplastic resin having a number average molecular weight of 300 to less than 3,000. .   The heat-melt transfer type ink ribbon according to any one of claims 1 to 4, wherein the heat of fusion measured by differential scanning calorimetry of high density polyethylene wax is 150 J / g or more and 300 J / g or less. Thermal melt transfer ink ribbon according to any one of claims 1 to 5 density of high density polyethylene wax is 960 kg / m ³ or more.

Images