JP6945123B2 - Heat-melt transfer type ink ribbon - Google Patents

Description

The present invention relates to a heat-melt transfer type ink ribbon having excellent environmental storage performance and print quality in a high temperature environment.

A heat-melt transfer type ink ribbon in which an ink layer containing at least a colorant such as a pigment and a binder such as various waxes and resins is provided on a base film is loaded into a heat transfer printer and used in factories and distribution warehouses. It is widely used for printing character information and bar codes on various slips, product tags, distribution management labels, and the like.

Compared to office printers such as laser printers, thermal transfer printers are easy to carry because the size of the printer itself is compact, and because they have a simple structure, they are less likely to break down. , It is expected to be used in various environments. For example, it may actually be used in a low temperature environment such as a cold area or a place where the air conditioning is not effective in winter, or in a high temperature environment such as a tropical area or a place where the air conditioning is not effective in summer.

Even under these circumstances, especially in a high temperature environment, even if the heat-melt transfer type ink ribbon is stored for a long time in a wound state, the ink layer and heat-resistant slipperiness are affected by the heat of the outside temperature and the winding pressure. Problems with environmental preservation performance such as a blocking phenomenon in which the layers adhere to each other and a deterioration in print quality due to softening and deformation of the ink layer and the transfer control layer may occur.

In addition, when a thermal transfer type ink ribbon is loaded into a thermal transfer printer and continuous printing is performed, the heat generated during printing is stored in the thermal head, and the heat causes a problem of print quality called planar peeling. Although it sometimes occurred, this phenomenon of planar peeling tended to occur more easily in a high temperature environment.

Explaining the planar peeling, as shown in FIG. 2, the planar peeling was formed unevenly in a scaly shape on the opposite side of the printed image portion 7a to be printed in the transport direction, which was originally planned to be formed. It refers to the printed image portion 7b, and while the printed image portion 7a is firmly transferred and adhered to the printed medium 6, the surface-peeled portion 7b is normally adhered to the printed medium 6. Not done. When this surface peeling occurs, not only the appearance is bad in printing character information, but also the characters cannot be recognized when the condition is terrible, and the barcode reading failure occurs in the printing of barcodes. Not only does this cause problems with print quality, but it also causes problems such as contaminating the printed medium and the surrounding environment due to the peeled-out portion being removed and scattered.

Explaining the normal printing mechanism performed by the thermal transfer printer, as shown in FIG. 3, the printing medium 6 and the thermal melt transfer type ink ribbon 1 are sandwiched between the thermal head 8 and the platen roll 9 of the thermal transfer printer and crimped. It is set in the thermal transfer printer in the state where it is set. At the time of printing, the transfer control layer 4 and the ink layer 5 of the portion where the printed image is formed by the thermal head 8 are heated to soften and melt, and they permeate or get wet with respect to the surface layer portion of the printing medium 6. After that, the heat-melt transfer type ink ribbon 1 and the printing medium 6 are peeled off at the timing when the ink ribbon 1 and the printing medium 6 are cooled and solidified to some extent, so that a printed image composed of 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 AB in FIG. 3 are overheated by the thermal head 8 to soften and melt, and the transfer control layer 4 and the base have the weakest adhesive force. Delamination occurs near the interface with the material film 2, and only the transfer control layer 4 and the ink layer 5 between AB in FIG. 3 are transferred to the printing medium 6, that is, the original portion 7a in FIG. 3 Only the printed image portion that was planned to be formed is formed.

However, in the case of printing in which surface peeling occurs, a large amount of the thermal head 8 is accumulated in the thermal head 8 during printing even though the thermal head 8 is heated only between A and B in FIG. At least a part of the transfer control layer 4 on the side close to the base film 2 between BC and BC in FIG. 3 is softened and melted by the heat generated, but the outermost layer of the ink layer 5 is not softened and melted. This is the originally planned print image portion in which the softened / melted ink layer 5 and the transfer control layer 4 between A and B are solidified when the heat-melt transfer type ink ribbon 1 and the print medium 6 are peeled off. A part of the transfer control layer 4 and the ink layer 5 between BC and BC in FIG. 3 is transferred as a printed image 7b which is a planar peeling portion while being pulled by the printed image 7a. The portion of the printed image 7b is transferred to the portion of the printed image 7a in a form of being forcibly pulled, and the transfer control layer 4 and the ink layer 5 between BC in FIG. 3 are mechanically forcibly broken. The fracture surface is formed very non-uniformly as shown in FIG. 2, and the ink layer 5 in this portion is not softened or melted, so that the ink layer 5 is transferred to the transfer medium 6. Not glued. Since the printed image 7b that has been stripped from the surface in this way is not a portion originally intended for print formation and is not adhered to the transfer medium 6, the problems of print quality and contamination as described above can be solved. cause.

In order to improve the above-mentioned problems, for example, Patent Document 1 has a feeling that a coloring material layer containing a coloring material, a heat-meltable substance, a thermoplastic substance, and a surfactant is applied on a support. In the thermal transfer recording medium, since 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 it is possible to show good print quality even in a high temperature environment. Have been described.

Further, Patent Document 2 uses a resin in which the primer layer in the thermal transfer recording medium is composed of wax and a thermoplastic resin incompatible with the wax, and the thermoplastic resin is not melted by the residual heat of the thermal head. It is described that it is possible to prevent the surface peeling of the recorded image and impart high scratch resistance to the recorded image.

However, in 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 set to 45 ° C., the constituent material starts to melt from a temperature slightly lower than the melting point, so that the actual temperature is actually high. Even when stored in an environment of 40 ° C, it may not be possible to reliably prevent the occurrence of blocking phenomenon and deterioration of print quality, and such a heat-melt transfer type ink ribbon naturally has a temperature of 50 ° C. In the environment preservation under the environment, it was almost impossible to prevent the blocking phenomenon and the like.

Further, if a heat-melt transfer type ink ribbon as shown in Patent Document 2 is used, it is effective in preventing surface peeling of the printed image due to heat storage of the thermal head during printing in a normal temperature environment of about 25 ° C. However, due to the higher heat storage temperature of the thermal head in a high temperature environment of 40 ° C, the surface peeling of the printed image is effective depending on the amount of wax added to the primer layer and the melting point conditions. There were some things that could not be prevented. Further, when the primer layer is composed of raw materials that are incompatible with each other and the melting point or softening point of the thermoplastic resin as an adhesive is very high, the primer layer and the base film are used during printing. Since the adhesive strength does not decrease so much and remains relatively strong, planar peeling is unlikely to occur, but there are other problems such as transferability problems such as blurring of the printed image that was originally intended to be formed and difficulty in transferring fine lines. Print quality problems tended to occur.

Japanese Unexamined Patent Publication No. 63-3995 Japanese Unexamined Patent Publication No. 2003-182254

The present invention has been made in view of such a situation, and has excellent environmental storage performance in a high temperature environment, and further, when printing is performed in a high temperature environment, the printed image is less likely to have surface peeling. The main task is to provide an excellent heat-melt transfer type ink ribbon.

The first problem to be solved by the present invention is to provide a heat-melt transfer type ink ribbon having excellent environmental preservation performance in a high temperature environment. As a result of studies by the present inventor in order to solve this problem, by incorporating at least a coloring material and a thermoplastic resin having a glass transition point of 50 ° C. or higher and 110 ° C. or lower in the ink layer, the ink can be stored in an environment at least at a temperature of 50 ° C. It was found that the layer itself hardly softened or deformed. 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, melting is started 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 between the extrapolated initial melting temperature (JIS K7121 _{(T im} in FIG. 4)) within 10.0 ° C., occur softening and deformation of the transfer control layer itself in the environment storage test at the temperature 50 ° C. at all I found that there wasn't. By using the ink layer and the transfer control layer in combination as described above, the present inventor causes a blocking phenomenon and softening / deformation of the ink layer and the transfer control layer even if the ink layer and the transfer control layer are stored in a high temperature environment of at least 50 ° C. It has been found that it is possible to obtain a heat-melt transfer type ink ribbon having excellent environmental preservation performance in a high temperature environment in which the print quality is hardly deteriorated due to the above.

A second problem to be solved by the present invention is to provide a heat-melt transfer type ink ribbon having excellent print 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 examination by the present inventor in order to solve this problem, the melting peak temperature measured by the differential scanning calorific value measurement method on the transfer control layer is 110 ° C. or higher and 135 ° C. or lower, and the melting peak temperature and the external melting start temperature. By containing 50% by 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 BC in FIG. 3 when continuous printing was performed in a high temperature environment of 40 ° C. Even if the temperature of the thermal head rises to 60 ° C, the fine particles made of high-density polyethylene wax contained in the transfer control layer do not soften or melt at all, so the adhesive force between the transfer control layer and the base film is completely strong. It was found that the temperature did not decrease, and as a result, the occurrence of planar peeling was prevented. Further, the present inventor used fine particles made of high-density polyethylene wax, and as a result, the state change of the transfer control layer became very large between the portion normally heated and melted 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 fact that the foil breakability of the transfer control layer is greatly improved.

As a result of studies by the present inventor to solve all the problems as described above, a heat-resistant slippery layer is provided on one surface of the base film, and a transfer control layer and an ink layer are sequentially laminated on the other surface. The heat-melt transfer type ink ribbon provided in the above, wherein the ink layer contains at least a coloring material and a thermoplastic resin having a glass transition point of 50 ° C. or higher and 110 ° C. or lower, and the transfer control layer is formed by a differential scanning calorific value measurement method. It contains 50% by mass or more of fine particles made of high-density polyethylene wax whose measured melting peak temperature is 110 ° C. or higher and 135 ° C. or lower, and the temperature difference between the melting peak temperature and the external melting start temperature is 10.0 ° C. or lower. He has invented the heat-melt transfer type ink ribbon.

If the heat-melt transfer type ink ribbon of the present invention is used, problems of environmental storage performance such as blocking phenomenon and deterioration of print quality are unlikely to occur even if the ink ribbon is stored in a high temperature environment, and even if printing is performed in a high temperature environment. Print quality problems such as surface peeling are unlikely to occur in the printed image.

FIG. 6 is a schematic cross-sectional view showing an example of an embodiment of the heat-melt transfer type ink ribbon of the present invention. A schematic plan view of a printed image for explaining surface peeling. A schematic cross-sectional view of the peripheral portion of the thermal head of a thermal transfer printer for explaining the principle of occurrence of planar peeling. Explanatory drawing about the melting peak of a DSC curve measured by a differential scanning calorimeter.

The heat-melt transfer type ink ribbon 1 of the present invention basically has a heat-resistant slippery layer 3 provided on one surface of the base film 2 as shown in FIG. 1, and a transfer control layer 4 and an ink layer 5 on the other surface. Has a structure in which the above are sequentially laminated.

<< Each component of the heat-melt transfer type ink ribbon >>
Next, details of each component of the heat-melt transfer type ink ribbon in the present invention are 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 the base film having such heat resistance include polyethylene terephthalate film (PET), polypropylene film, polystyrene film, polyimide film, polyamide film, polycarbonate film, polyvinyl chloride film and the like. It is most preferable to use it. The thickness of the base film is not particularly limited, but it may be 2 μm or more and 12 μm or less, considering appropriate consideration according to the material so that the strength, heat resistance, and thermal conductivity are appropriate, but the thermal conductivity is good. It is more preferably 3 μm or more and 6 μm or less for the reason that there is.

<Heat-resistant slippery layer>
In the heat-melt transfer type ink ribbon of the present invention, the base film may be broken, the base film may be fused to the thermal head, or the base film may be wrinkled due to the heat of the thermal head during printing. In order to prevent the sticking phenomenon that the slipperiness between the base film and the thermal head deteriorates, various silicon-modified resins, fluorine-based resins, nitrocellulose-based resins, and polyimide-based resins are used on one surface of the base film. A heat-resistant slippery layer is provided in which various known heat-resistant resins such as resins are used as a main raw material, and an adhesive resin, a cross-linking agent, a lubricant, and various organic-inorganic fillers are appropriately mixed as other auxiliary raw materials.

The amount of the heat-resistant slippery layer applied after drying is not particularly limited, and can be appropriately selected and determined from the range of ^{0.01 g / m 2} or more and 0.50 g / m ^{2 or less according to the usage conditions and the type of 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. If the amount of the heat-resistant slippery layer applied after drying is ^{less than 0.01 g / m 2} , the expected effect of heat resistance cannot be obtained, and conversely, the amount of the heat-resistant slippery layer applied after drying is 0.5 g / m. ^{If it is 2} or more, the sensitivity at the time of printing tends to deteriorate, and problems such as foil dropping 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, the sharpness of printing, and the like. In addition to the role of a normal transfer control layer, the transfer control layer of the present invention does not adversely affect the environmental storage performance in a high temperature environment, and further suppresses the occurrence of planar peeling during printing in a high temperature environment. It needs to be a transfer control layer that satisfies the performance.

As a result of examining a heat-meltable substance used for the transfer control layer to impart peelability in order to satisfy the above-mentioned performance, the present inventor has a relatively high melting point and a narrow melting peak width, and at the time of melting. It was found that a heat-meltable substance having very good releasability from the base film and which is difficult to mix with the ink layer at the time of melting is preferable. As a result of further scrutiny of such a heat-meltable substance, it was found that it is most preferable to add a high-density polyethylene wax to the transfer control layer.

Further, as a result of the present invention continuing to study the high-density polyethylene wax used for the transfer control layer, the melting peak temperature measured by the differential scanning calorimetry of the high-density polyethylene wax is 110 ° C. or higher and 135 ° C. or lower, more preferably 120 ° C. High temperature of ° C. or higher and 130 ° C. or lower, and the temperature difference between the melting peak temperature and the external melting start temperature is within 10.0 ° C., more preferably within 6.0 ° C., and most preferably within 4.0 ° C. By selecting the density polyethylene wax and using it for the transfer control layer, the transfer control layer itself softens in a high temperature environment because the high density polyethylene wax does not melt at all even if heat of 60 ° C. is applied to the transfer control layer. It has been found that it has the effect of 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 for the transfer control layer is below the lower limit of 110 ° C., or the temperature difference between the melting peak temperature of the high-density polyethylene wax and the external melting start temperature exceeds 10.0 ° C. Then, the temperature at the melting peak a of the DSC curve in FIG. 4, which is considered to start absorbing heat and softening / melting slightly, tends to be lower than 60 ° C. As a result, the high-density polyethylene wax begins to partially soften and melt even at temperatures lower than 60 ° C, and as a result, the transfer control layer softens and deforms in a high-temperature environment, and the environmental preservation performance tends to deteriorate. In addition, surface peeling is likely to occur during printing in a high temperature environment. On the contrary, when the melting peak temperature of the high-density polyethylene wax exceeds 135 ° C., which is the upper limit of the above range, the heat quantity at the time of printing and the melting viscosity near the melting point suddenly increase, so that the printing sensitivity and the transferability of printing become high. It tends to be worse, and problems such as print blurring are likely to occur especially in a low temperature environment.

Further studies were conducted on the characteristics of the melting peaks measured by the differential scanning calorimetry of high-density polyethylene wax suitable for use in the transfer control layer of the present invention. As a result, the melting peaks were single peaks and the melting peaks were found. The narrower the width, the more effective it is to prevent deterioration of environmental storage performance in a high temperature environment and to prevent planar peeling in a high temperature environment, and the width of the melting peak is at least the supplementary melting end temperature (JIS K7121). it is preferable temperature difference (Fig. 4 T _em)) and extrapolated initial melting temperature (T _im in FIG. ₄₎ is within 15 ° C., more preferably within 10 ° C., it is most preferably within 8 ° C. I found out.

Furthermore, when the characteristics of the melting peak measured by the differential scanning calorimetry method of the high-density polyethylene wax suitable for use in the transfer control layer of the present invention were examined, the differential scanning calorimetry method of the high-density polyethylene wax was used. It was found that the measured heat of fusion (JIS K7122) 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. It was found that if the amount of heat of fusion of the high-density polyethylene wax is within the above range, the transfer control layer is unlikely to be melted by a small amount of heat, so that it is effective in preventing surface peeling during printing in a high temperature environment. rice field.

Further, as a result of examining a high-density polyethylene wax suitable for use in the transfer control layer of the present invention, the styrene-equivalent weight average molecular weight (Mw) measured by the GPC method of the high-density polyethylene wax is 4000 or more and 50,000 or less. Is preferable, and more preferably 10,000 or more and 40,000 or less. If a high-density polyethylene wax having a weight average molecular weight in the above range is used for the transfer control layer of the present invention, it is less affected by low molecular weight components and is composed mainly of a relatively high-molecular-weight linear high-density polyethylene wax. In addition, the melting peak temperature of the high-density polyethylene wax is high, the width of the melting peak is narrow, and almost no heat absorption is observed on the low temperature side of the melting peak below 60 ° C. It is effective in preventing planar peeling in the environment, and since the melt viscosity at the time of melting is relatively high compared to other low molecular weight waxes, it is difficult for the ink layer and transfer control layer to mix, and the degree of needle insertion 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 lower than the lower limit of the above range, the melting peak temperature becomes low and the melting peak width becomes wide due to the large influence of the low molecular weight component. Since heat absorption tends to occur even on the low temperature side of the melting peak of less than 60 ° C, the environmental preservation performance tends to deteriorate in a high temperature environment and planar peeling tends to occur in a high temperature environment. Further, the melt viscosity is lowered, the ink layer and the transfer control layer are easily mixed, and the degree of needle insertion is also increased, so that the scratch resistance of the printed image tends to be lowered. On the contrary, when the weight average molecular weight of the high-density polyethylene wax used for 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 if it is used as a control layer, the problem of transfer failure tends to occur easily.

Further, as a result of examining a high-density polyethylene wax suitable for use in the transfer control layer of the present invention, a 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. If 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 the differential scanning calorimetry method is narrow, and heat absorption is absorbed on the low temperature side of the melting peak lower than 60 ° C. Since it is not seen, it is effective in preventing deterioration of environmental storage performance in a high temperature environment and preventing planar peeling in a high temperature environment, and further, since the degree of needle insertion is increased, 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 a state of being processed into fine particles. By adding high-density polyethylene wax in the form of fine particles dispersed in the transfer control layer, the structural difference between the portion where the fine particles are melted by the heat during printing and the portion where the fine particles are not melted becomes large. As a result, the foil breakability of the ink layer and the transfer control layer during printing has become very good, and as a result, the surface peeling phenomenon has become less likely to occur.

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 This is more preferable, and more preferably 5.0 μm or more and 11.0 μm or less. If the volume-based median diameter D ₅₀ measured by the laser diffraction / scattering method of fine particles made of high-density polyethylene wax is within the above range, the foil breakability of the ink layer and transfer control layer during printing is good, and the surface shape Peeling phenomenon is unlikely to occur.

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

The transfer control layer of the present invention may be composed of only high-density polyethylene wax which is a heat-meltable substance, but since the adhesion of the transfer control layer to the base film is weak, the heat-melt transfer type ink ribbon is thermally transferred. The so-called flaking phenomenon in which the transfer control layer and the ink layer are removed from the base film when setting in a printer tends to occur, and the planar peeling phenomenon also tends to occur during printing. .. Therefore, it is preferable to add a resin having thermoplastic adhesiveness to the transfer control layer as needed.

The thermoplastic adhesive resin 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. Examples of such an olefin-type copolymer resin include ethylene-methyl (meth) acrylate copolymer resin, ethylene-ethyl (meth) acrylate copolymer resin, ethylene-propyl (meth) acrylate copolymer resin, and ethylene-. Butyl (meth) acrylate copolymer, propylene-methyl (meth) acrylate copolymer, propylene-ethyl (meth) acrylate copolymer, propylene-propyl (meth) acrylate copolymer, propylene-butyl (meth) acrylate 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, Various olefin-based copolymer resins such as ethylene- (meth) atarylamide copolymer and α-olefin- (meth) acrylamide copolymer such as propylene (meth) acrylamide copolymer and their copolymer resins are anhydrous. For example, α-olefin-alkyl (meth) acrylate-maleic anhydride ternary copolymer, α-olefin-vinyl acetate-maleic anhydride ternary copolymer, α-olefin- (meth) modified with various carboxylic acids such as maleic acid. Examples thereof include, but are not limited to, various olefin-based ternary copolymers such as acrylamide-maleic anhydride ternary copolymer. Among the above-mentioned olefin-based copolymers, the most preferable one to be added to the transfer control layer of the present invention is an ethylene-based copolymer resin having ethylene as a main skeleton.

When a paint prepared by mixing fine particles made of high-density polyethylene wax and a solvent solution of an olefin-based copolymer resin as described above is applied and dried on a base film to prepare a transfer control layer, In the transfer control layer, fine particles made of high-density polyethylene wax are islands, and the olefin-based copolymer resin has a sea-island structure in 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-based copolymer resin and the high-density polyethylene wax are easily mixed at the time of melting, the portion to which the heat is applied becomes a uniform mixture, and as a result, the base material is compared with that before the heat is applied. The transfer is very smooth because the adhesiveness to the film is significantly reduced, and at the same time, the difference in adhesive strength between the heat-melted part and the unmelted part to the base film becomes large. State peeling is less likely to occur. Therefore, as the thermoplastic adhesive resin used in the present invention, it is preferable to select and use a resin that is compatible with the high-density polyethylene wax at the time of melting.

When the present inventor examined the thermal properties of the thermoplastic adhesive resin added to the transfer control layer, the melting peak temperature of the thermoplastic adhesive resin is preferably at least 60 ° C. or higher and 150 ° C. or lower, more preferably. It was found that it is preferable that the temperature is 65 ° C. or higher and 130 ° C. or lower. When the melting peak temperature of the thermoplastic adhesive resin is within the above range, the printing sensitivity is appropriate and does not adversely affect the environmental storage performance in a high temperature environment and the planar peeling phenomenon in a high temperature environment.

Furthermore, when the present inventor examined the thermal properties of the thermoplastic adhesive resin added to the transfer control layer, the glass transition point (Tg) of the thermoplastic adhesive resin was not particularly limited, but was -20 ° C or lower. It was found that the temperature is preferably −30 ° C. or lower, more preferably −30 ° C. or lower. The glass transition point in the present invention means the intermediate point glass transition temperature (JIS K7121) measured by the differential scanning calorimetry method. If the glass transition point of the thermoplastic adhesive resin is within 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 during low temperature printing. There is no change in print quality.

Since the above-mentioned thermoplastic adhesive resin having a glass transition point of 0 ° C. or less has a low glass transition point, if it is stored for a long time under pressure in a high temperature environment, it will inevitably be deformed due to its nature. For example, if it is added to the transfer control layer as it is, the transfer control layer will be deformed in the environmental preservation test in a high temperature environment, and as a result, problems such as blocking phenomenon and deterioration of print quality may occur. However, by creating a transfer control layer using a paint prepared by mixing fine particles made of high-density polyethylene wax as described above with a solvent solution of a thermoplastic adhesive resin or the like, the transfer control layer becomes a sea-island structure. Furthermore, by projecting fine particles of high-density polyethylene wax on the islands from the coating of the thermoplastic adhesive resin on the sea, the high-density polyethylene wax particles do not soften or deform at all even when pressure is applied in a high-temperature environment. Therefore, as a result, it has become possible to prevent the transfer control layer itself from being softened or deformed at all.

The amount of the thermoplastic adhesive resin added to the transfer control layer of the present invention is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass of the transfer control layer. It is preferably% or less. When the amount of the thermoplastic adhesive resin added is within the above range, the transferability of printing, the environmental storage performance in a high temperature environment, and the planar peeling phenomenon in a high temperature environment are not adversely affected, and the substrate film and the transfer control layer are not adversely affected. In addition, by improving the adhesion between the ink layer and the transfer control layer, the flaking phenomenon is prevented, and a certain effect is exhibited in preventing the occurrence of the planar peeling phenomenon. When the thermoplastic adhesive resin is added to the transfer control layer in excess of the upper limit of the above range, the adhesive force between the transfer control layer and the base film becomes too large, the transferability of printing deteriorates, and further, thermoplastic adhesion occurs. Since the thickness of the coating film made of resin is larger than the particle size of the fine particles made of high-density polyethylene wax, the environmental preservation performance in a high-temperature environment tends to deteriorate.

In the transfer control layer of the present invention, in addition to the above-mentioned fine particles made of high-density polyethylene wax and the thermoplastic adhesive resin, various known organic / inorganic fillers, various waxes, various thermoplastic resins, surfactants and antistatic agents Various functional additives such as the above may be appropriately added as needed.

The amount of the transfer control layer of the present invention applied after drying is not particularly limited and ^{may be appropriately selected from the range of 0.1 g / m 2} or more and 2.0 g / m ² or less, but in consideration of print 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 coating amount of the transfer control layer after drying is ^{less than 0.1 g / m 2} , the transfer control layer and the base film cannot be properly peeled off at the interface, and transfer defects tend to occur. If the coating amount of the transfer control layer after drying ^{exceeds 2.0 g / m 2} , the sensitivity becomes insufficient during printing, and the components of the transfer control layer transferred to the printed matter increase, resulting in scratch resistance of the printed image. It tends to be less sexual.

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

As a result of the present invention examining the main constituent of the binder component used in the ink layer of the present invention, the glass transition point is 50 ° C. or higher and 110 ° C. or lower, more preferably 60 ° C. as the main constituent of the binder component of the ink layer. It is preferable to use a thermoplastic resin having a temperature of 100 ° C. or lower. When the glass transition point of the thermoplastic resin is 50 ° C. or higher and 110 ° C. or lower, it does not soften or deform in a high temperature environment of at least 50 ° C., so that the environmental storage performance is not adversely affected. On the contrary, when the glass transition point of the thermoplastic resin used for the ink layer is less than 50 ° C, it tends to soften and deform in a high temperature environment of 50 ° C, so that a blocking phenomenon occurs and the ink layer softens and deforms. There is a tendency for a significant decrease in print quality due to this. When the glass transition point of the thermoplastic resin used for the ink layer exceeds 110 ° C., not only the amount of heat required for the ink layer to melt during printing increases, but also the melt viscosity of the thermoplastic resin increases. As a result, problems with print quality such as print blurring and transfer defects tend to occur easily.

The softening point (ring ball method) of the thermoplastic resin used for the ink layer of the present invention is not particularly limited, but is preferably 60 ° C. or higher and 190 ° C. or lower, and further 70 ° C. or higher and 170 ° C. or lower. More preferred. When the softening point of the thermoplastic resin is within the above range, the environmental storage performance in a high temperature environment is excellent, the planar peeling phenomenon is unlikely to occur during printing in a high temperature environment, and printing blurring and transfer defects occur during printing. Appropriate printing can be performed without occurring. Normally, when a thermoplastic resin having a glass transition point of 50 ° C. or higher is selected, almost all the softening points of the thermoplastic resin are 60 ° C. or higher, but conversely, a thermoplastic resin having a softening point of 60 ° C. or higher is selected. However, not all the glass transition points of the thermoplastic resin are 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 at the time of 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, so the volume changes. Since the accompanying deformation and property change do not occur, the blocking phenomenon and deterioration of print quality due to softening and deformation of the ink layer do not occur, but conversely, even if the softening point of the thermoplastic resin is higher than the environmental temperature, the glass transition point will occur. When the temperature becomes lower than the ambient temperature, the thermoplastic resin may be deformed due to volume change or property change, resulting in a blocking phenomenon or deterioration of print quality due to softening / deformation of the ink layer. Therefore, in the present invention, the glass transition point is used as an element 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 resin, polyamide resin, polystyrene resin, styrene acrylic resin, acrylic resin, modified products thereof, and copolymers thereof. Relatively high molecular weight thermoplastic resin with a molecular weight (Mn) of 3000 or more, kumaron resin, rosin resin, ketone resin, styrene hydrocarbon resin, terpene resin, terpene phenol resin, petroleum resin, aliphatic Examples thereof include so-called tackifier resins having a number average molecular weight (Mn) of less than 3000, such as based hydrocarbon resins, aromatic hydrocarbon resins, and modified products thereof, but are limited to these. Not that. The thermoplastic resin may be used alone or in combination of two or more, but more preferably, a relatively high molecular weight thermoplastic resin having a number average molecular weight of 3000 or more and a relatively low molecular weight heat having a number average molecular weight of less than 3000 are used. It is preferable to use a plastic resin, more preferably a relatively high molecular weight thermoplastic resin having a number average molecular weight of 5000 or more and a relatively low molecular weight thermoplastic resin having a number average molecular weight of less than 3000.

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 strength of the ink layer is improved, and it is possible to improve the scratch resistance and chemical resistance of the printed image. However, as the number average molecular weight of these thermoplastic resins increases, the coating strength of the ink layer tends to increase and at the same time the melt viscosity of the ink layer tends to increase. The adhesiveness and the foil breakability of the ink layer tend to deteriorate, and as a result, the transferability of the printed image and the fineness of the printed image tend to deteriorate. The upper limit of the number average molecular weight of such a relatively high molecular weight thermoplastic resin is 100,000 or less due to the adhesiveness and transferability of the ink layer to the printing medium at the time of printing and the sharpness of the printed image. Is preferable, and it is more preferably 50,000 or less, and most preferably 30,000 or less.

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 decreases, and the adhesiveness to the printing medium during printing and the foil breakability of the ink phase tend to be greatly improved. Therefore, the transferability of the printed image and the fineness of the printed image are greatly improved, but on the other hand, the scratch 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 further study on the thermoplastic resin used for the ink layer by the present inventor, a thermoplastic polyester resin having a number average molecular weight of 5000 or more and 30,000 or less and a thermoplastic resin having a number average molecular weight of 300 or more and less than 3000 are mixed. It turned out to be the most preferable to use. The thermoplastic resin having a number average molecular weight in the range of 300 or more and less than 3000 is not particularly limited, but more preferably a ketone resin, a styrene hydrocarbon resin, a terpene phenol resin, or the like is used. The mixing ratio of the thermoplastic polyester resin having a number average molecular weight of 5000 or more and 30,000 or less and the thermoplastic resin having a number average molecular weight of 300 or more and less than 3000 is not particularly limited, but the thermoplastic polyester resin having a number average molecular weight of 5000 or more and 30,000 or less is used. 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 terms of mass ratio. By using a mixture of the thermoplastic resins in the ink layer, the adhesiveness and transferability of the ink layer to the printing medium at the time of printing are good, the foil breakability of the ink layer is good, and the fineness of the printed image is improved. It was found that an ink layer with excellent performance balance, which is excellent in performance and also excellent in performance such as scratch resistance of printed images, can be obtained.

The amount of the thermoplastic resin added to the ink layer of the present invention is not particularly limited, but may be 30% by mass or more and 90% by mass or less of the ink layer, and more preferably 60% by mass or more and 80% by mass or less. It is preferable that there is. When the amount of the thermoplastic resin added to the ink layer is within the above range, the adhesiveness and transferability of the ink layer to the printing medium at the time of printing, the fineness of the printed image, and the scratch resistance are appropriate. Furthermore, since the thermoplastic resin has a sufficient influence on the environmental preservation performance of the ink layer in a high temperature environment, it is possible to reflect the properties of the thermoplastic resin in 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 raw material in order to improve the foil breakability, printing sensitivity and blocking resistance of the ink layer. Examples of the wax include, but are not limited to, carnauba wax, montanic acid wax, paraffin wax, microcrystalline wax, Fishertropus wax, polyethylene wax and the like. Further, as other auxiliary raw materials, various known surfactants, inorganic and organic fillers are appropriately added to the ink layer as necessary to adjust the dispersibility of the colorant, the foil breakability of the ink, the melt viscosity of the ink layer, and the like. Improvements and adjustments may be made.

The coating amount of the ink layer of the present invention after drying 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, but in terms of cost and From the viewpoint of performance stability, it is more preferable to appropriately select from the range of ^{0.5 g / m 2} or more and 2.0 g / m ^{2 or less.} If the coating amount of the ink layer after drying ^{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 is performed. Sensitivity and foil breakability tend to deteriorate.

Next, the present invention will be specifically described with reference to examples.

<Method of forming base film and heat-resistant slippery layer>
Using a gravure coating machine, apply the following heat-resistant slip layer paint to one side of a polyethylene terephthalate film (PET film) with a thickness of 4.5 μm using a gravure coating machine, dry it, and apply 0.2 g / m ² A heat-resistant slippery layer was formed. Subsequent examples and comparative examples of the present invention all use the heat-resistant base film and the heat-resistant slippery layer.
(Contains paint for heat-resistant slippery layer)
Raw material component mass%
-Silicone-modified polyester polyurethane resin methyl ethyl ketone / toluene = 1/1 solvent solution (solid content 15%) 25.0
・ Methyl ethyl ketone 60.0
・ Toluene 15.0
For the above heat-resistant slip layer coating material, a solution prepared by dissolving a mixed solvent of methyl ethyl ketone and toluene and a silicon-modified polyester polyurethane resin in a solvent having a mass ratio of methyl ethyl ketone and toluene of 1: 1 is weighed and charged according to the above formulation. , Is created by stirring and mixing with a dissolver or the like. The above-mentioned method for producing the heat-resistant slip layer paint and the method for applying the heat-resistant slip layer are examples, and the present invention is not limited to this, and various known methods can be used.

<Method of forming the transfer control layer>
Table 1 shows the details of the properties of each heat-meltable substance used for the transfer control layer of Examples and Comparative Examples of the present invention.

The following coating material for transfer control layer is applied to the opposite surface of the PET film coated with the heat-resistant slippery layer with a gravure coating machine, and dried to obtain a transfer control layer having ^{a coating amount of 0.5 g / m 2.} Formed. Using each of the heat-meltable substances in Table 1 above as the heat-meltable substance in the following transfer control layer paint formulation, each transfer control layer paint used in each of the Examples and Comparative Examples of the present invention was prepared. The details of the mixing ratio of each raw material in the coating for the transfer control layer are shown in Table 3 below.

(Mixed paint for transfer control layer)
Ingredients Toluene dispersion of heat-meltable substance by mass (solid content 10%) 85.0
-Ethylene vinyl acetate resin "Tg: -30 ° C, melting peak temperature: 60 ° C,
VA: 33% "toluene solution (solid content 10%) 15.0
As a method for producing a coating material for a transfer control layer, first, toluene and a heat-meltable substance are put into a container that can be sealed and can be stirred and heated, and the container is sealed and then heated while stirring. After the meltable substance is completely dissolved in toluene, the fine particles of the heat-meltable substance are dispersed in toluene by gradually cooling to 30 ° C. or lower while stirring them, thereby thermally melting the solid content of 10%. Prepare a toluene dispersion of the sex substance. Next, after weighing toluene and ethylene vinyl acetate resin into a container that can be sealed and can be stirred and heated, heat them while stirring to completely dissolve the ethylene vinyl acetate resin in toluene, and then 30 ° C or lower. To prepare a toluene solution of ethylene vinyl acetate resin having a solid content of 10%. Finally, the toluene dispersion of the heat-meltable substance and the toluene solution of the ethylene vinyl acetate resin are weighed and mixed in a container according to the above formulation, and after stirring and mixing with a dissolver, laser diffraction of fine particles of the heat-meltable substance while dispersing with a bead mill. -The coating for the transfer control layer is completed by adjusting the volume-based median diameter D ₅₀ measured by the scattering method so as to be in the range of 5.0 to 11.0 μm. When two or more types of heat-meltable substances are used in the paint formulation for the transfer control layer described above, a toluene dispersion liquid of the heat-meltable substances is separately prepared for each heat-meltable substance. , They may be mixed and used before the bead mill is dispersed. The method for producing the coating material for the transfer control layer and the method for applying the transfer control layer described above are examples, and the present invention is not limited to this, and various known methods can be used.

<Method of forming ink layer>
(Ink layer)
Table 2 shows the details of the properties of the thermoplastic resin used for the ink layers of Examples and Comparative Examples of the present invention.

The following ink layer paint was applied onto the transfer control layer with a gravure coating machine and dried to form an ink layer having ^{a coating amount of 1.2 g / m 2.} Using each of the thermoplastic resins in Table 2 above as the thermoplastic resin in the following ink layer paint formulation, the paint for each ink layer used in each of the Examples and Comparative Examples of the present invention was prepared. The details of the blending ratio of each raw material in the blending of the ink layer paint are shown in Table 3 below.

(Mixed paint for ink layer)
Ingredients by mass, thermoplastic resin 14.0
・ Carbon black 6.0
・ Toluene 40.0
・ Methyl ethyl ketone 40.0
As a method for producing the above ink mounting paint, after weighing toluene, methyl ethyl ketone and thermoplastic resin into a container that can be sealed and can be stirred and heated, the thermoplastic resin is completely dissolved in the solvent by heating while stirring them. After dissolving in, the solution is cooled to 30 ° C. or lower, carbon black is further weighed and mixed well, and then dispersed by a bead mill to develop the color of carbon black. Two or more types of thermoplastic resins may be mixed and used in the ink layer paint formulation. The method for producing the ink layer paint and the method for applying the ink layer described above are examples, and the method is not limited to this, and various known methods can be used.

<Printing test conditions>
Various printing tests were performed under the following conditions using the heat-melt transfer type ink ribbons shown in Examples and Comparative Examples in Table 3. When printing was performed using the heat-melt transfer type ink ribbons of Examples and Comparative Examples under the following printing test conditions in a room temperature environment of 25 ° C., the printing energy was appropriate, and transfer defects such as print blurring and fine lines were defective. , Problems such as surface peeling of printing hardly occurred.
Printer: ZEBRA110XiIV (manufactured by Sebra)
Print resolution: 300 dpi
Printing speed: 2 inch / sec
Print density: 14/20
Printable medium: PET label

<Evaluation of surface peeling of printed images in printing in a high temperature environment>
The printer used for the printing test, the printing medium, and the heat-melt transfer type ink ribbon used for printing are allowed to stand for 1 hour in a constant temperature bath in which the temperature is set to 40 ° C., and then printing is performed under the above-mentioned printing test conditions. 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 ... No surface peeling has occurred in the printed image.
B ... Slightly planar peeling occurs in a part of the printed image.
C ... Surface peeling was clearly generated in a part of the printed image.
D ... Severe planar peeling occurred on almost the entire surface of the printed image.

<Evaluation of printing sensitivity in printing in a low temperature environment>
The printer used for the printing test, the printing medium, and the heat-melt transfer type ink ribbon used for printing are allowed to stand for 1 hour in a constant temperature bath in which the temperature is set to 5 ° C., and then printing is performed under the above-mentioned printing test conditions. Was performed 10 times on the label, and the printed images of the 10 sheets were visually confirmed and evaluated under the conditions shown below.
A ... No print blurring occurs.
B ... A slight amount of print blurring occurs.
C ... Printing blur is clearly generated on almost the entire surface.
D ... The print blurring is severe and the print is hardly transferred.

<Evaluation of scratch resistance>
After applying an ABS resin ball with a diameter of 1 cm to a printed image printed under the above-mentioned printing test conditions in a room temperature environment of 25 ° C. with a point load of 500 g, and reciprocating 30 times at a speed of 1 reciprocation per second. The state of the printed image was visually evaluated and evaluated under the conditions shown below.
A ... There is no chipping of the printed image, and there is no deformation of the printed image.
B ... The printed image is not chipped, but the printed image is slightly deformed.
C ... The printed image is slightly chipped, and the printed image is clearly deformed.
D ... Both chipping and deformation of the printed image are clearly seen.

<Blocking resistance (environmental storage performance)>
To evaluate the blocking resistance, a ribbon sample (width 60 mm, length 300 m, in-plane) obtained by wrapping a paper core with the original fabric of a heat-melt transfer type ink ribbon slit to a predetermined size and processing it into a roll shape. The ribbon sample is stored in an atmosphere of 50 ° C. and 80% humidity for 96 hours, then cooled in a room temperature environment of 25 ° C. for 24 hours, and the ribbon sample is unwound and blocked. The condition of the above was visually evaluated and evaluated under the conditions shown below.
A ... No blocking is seen.
B ... Slight blocking is seen near the paper core of the ribbon sample.
C ... Blocking is partially observed from the middle of winding the ribbon sample to the vicinity of the paper core.
D ... Blocking is seen on the entire surface of the ribbon sample.

<Changes in print quality before and after the environmental preservation test (environmental preservation performance)>
To evaluate the change in print quality before and after the environmental preservation test, a ribbon sample (width 60 mm, length 60 mm, length) made by wrapping a paper core with the original fabric of a heat-melt transfer type ink ribbon slit to a predetermined size and processing it into a roll shape. After preparing a 300 m ink in-plane winding) and storing the ribbon sample in an atmosphere of a temperature of 50 ° C. and a humidity of 80% RH for 96 hours, and then allowing it to stand and cool for 24 hours in a room temperature environment of a temperature of 25 ° C. The printing state when printing was performed under the above-mentioned printing test conditions in a room temperature environment of 25 ° C. was visually evaluated under the following conditions.
A ... There is no change in print quality before and after the environmental preservation test.
B ... After the environmental preservation test, the print quality such as print blurring, transfer failure, and surface peeling phenomenon is slightly worse than that before the environmental preservation test.
C ... After the environmental preservation test, the print quality such as print blurring, transfer failure, and surface peeling phenomenon is clearly deteriorated as compared with that before the environmental preservation test.
D ... After the environmental preservation test, the print quality such as print blurring, transfer failure, and surface peeling phenomenon is significantly deteriorated as compared with that before the environmental preservation test.

The heat-melt transfer type ink ribbons of various examples and comparative examples were prepared, and the details of each paint formulation of the comparative examples and the results of the above-mentioned various evaluations are shown in Table 3 below.

From the results in Table 3, the ink layer contains at least a coloring material and a thermoplastic resin having a glass transition point of 50 ° C. or higher and 110 ° C. or lower, as in the heat-melt transfer type ink ribbons of Examples 1 to 7. The transfer control layer is made of high-density polyethylene wax in which the melting peak temperature measured by the differential scanning calorimetry method is 110 ° C. or higher and 135 ° C. or lower, and the temperature difference between the melting peak temperature and the external melting start temperature is within 10.0 ° C. When a heat-melt transfer type ink ribbon containing 50% by mass or more of fine particles is used, no blocking phenomenon or deterioration of print quality is observed even when an environmental preservation test is performed in a high temperature environment, and further, a high temperature environment is observed. Even if printing is performed below, the surface peeling phenomenon hardly occurs. On the other hand, as in Comparative Examples 1 to 5, a heat-meltable substance having a melting peak temperature of 110 ° C. or lower or a temperature difference between the melting peak temperature and the external melting start temperature exceeding 10.0 ° C. is transferred to the transfer control layer. When used in Deterioration of print quality such as transfer failure has occurred remarkably, and further, the occurrence of planar peeling phenomenon has been clearly observed when printing in a high temperature environment. Further, as in Comparative Example 6, fine particles made of high-density polyethylene wax having a melting peak temperature of 110 ° C. or higher and 135 ° C. or lower and a temperature difference between the melting peak temperature and the external melting start temperature of 10.0 ° C. or lower are formed in the transfer control layer. Even if is added, if the amount added is less than 50% by mass of the transfer control layer, the environmental storage performance in a high temperature environment deteriorates, and surface peeling occurs during printing in a high temperature environment. became. Further, when a thermoplastic resin having a glass transition point of less than 50 ° C. was used as the main constituent of the binder component of the ink layer as in Comparative Example 7, the environmental storage performance in a high temperature environment was sharply deteriorated.

The heat-melt transfer type ink ribbon of the present invention can be used not only for general purposes such as printing character information and barcodes on various slips, product tags, distribution management labels, etc., but also especially in a high temperature environment. It can be used as a heat-melt transfer type ink ribbon for thermal printers, which is highly likely to be used.

1; Heat-melt transfer type ink ribbon 2; Base film 3; Heat-resistant slippery layer 4; Transfer control layer 5; Ink layer 6; Printed medium 7a; Printed image (printed image portion originally planned to be formed)
7b; Printed image (part where the surface is 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

Claims (6)

A heat-melt transfer type ink ribbon in which a heat-resistant slippery layer is provided on one surface of a base film and a transfer control layer and an ink layer are sequentially laminated on the other surface. The ink layer is at least a coloring material and glass. It contains a thermoplastic resin with a transition point of 50 ° C. or higher and 110 ° C. or lower, and the melting peak temperature measured by the transfer control layer by differential scanning calorimetry is 110 ° C. or higher and 135 ° C. or lower, and the melting peak temperature and external melting start. A heat-melt transfer type ink ribbon containing 50% by mass or more of fine particles made of high-density polyethylene wax having a temperature difference of 10.0 ° C. or less. The heat-melt transfer type ink ribbon according to claim 1, wherein the styrene-equivalent weight average molecular weight measured by the GPC method of the high-density polyethylene wax is 4000 or more and 50,000 or less. The heat-melt transfer type ink ribbon according to claim 1 or 2, wherein the volume-based median diameter D ₅₀ measured by a laser diffraction / scattering method of fine particles made of high-density polyethylene wax is 3.0 μm or more and 13.0 μm or less. .. The heat-melt transfer type 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 5000 or more and 30,000 or less and a thermoplastic resin having a number average molecular weight of 300 or more and less than 3000. .. The heat-melt transfer type ink ribbon according to any one of claims 1 to 4, wherein the heat of fusion measured by the differential scanning calorimetry of the high-density polyethylene wax is 150 J / g or more and 300 J / g or less. The heat-melt transfer type ink ribbon according to any one of claims 1 to 5, wherein the density of the high-density polyethylene wax is 960 kg / m ^{3 or more.}

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