Thermal transfer ink ribbon

Abstract

To provide a thermofusion transfer type ink ribbon which has good printing sensitivity to various display labels for clothing, printing transferability and printing sharpness, is excellent in cleaning resistance and dry cleaning resistance of printing formed on the display labels for clothing, and is excellent in a scumming phenomenon in printing, a blocking phenomenon in storage under high temperature and high humidity environment and an effect for suppressing a bleed phenomenon of a plasticizer.SOLUTION: There is provided a thermofusion transfer type ink ribbon 5 in which a transfer control layer 2, an ink layer 3 and an adhesive layer 4 are sequentially laminated on one surface of a film base material 1, the ink layer 3 contains a coloring agent, nitrocellulose and a toluenesulfonamide derivative, and the adhesive layer 4 contains a thermoplastic resin and polymethylsilsesquioxane resin fine particles.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a thermal melt transfer ink ribbon capable of forming durable prints with excellent resistance to washing and dry cleaning on various clothing labels such as laundry labels and quality labels for clothing. [Background technology]

[0002] Generally, printing methods for various clothing labels such as laundry labels and quality labels include printing with a letterpress printing machine using solvent-based ink or ultraviolet-curing ink, printing with a thermal printer using a thermal melt transfer ink ribbon, etc. While printing with a letterpress printing machine is suitable for mass production, the advantages of printing with a thermal printer using a thermal melt transfer ink ribbon include that it is suitable for printing on small lots of various products because it does not require the production of printing plates, the printer is small, has excellent durability and maintainability, and further, it is possible to easily form prints without the need for curing or drying after printing.

[0003] On the other hand, the disadvantages of printing with a thermal printer using a thermal transfer ink ribbon are that when a thermoplastic material with a relatively low softening point, low melting point, or low molecular weight is selectively used in the ink layer to improve print quality such as print sensitivity, print transferability, or print sharpness, the wash resistance and dry cleaning resistance of the print tend to deteriorate, and conversely, when a thermoplastic material with a relatively high softening point, high melting point, or high molecular weight is selectively used in the ink layer to improve the wash resistance and dry cleaning resistance of the print, the print sensitivity, print transferability, and print sharpness of the clothing display label deteriorate. As seen from the above, there is a tendency for print quality, such as print sensitivity, print transferability, and print sharpness, to have a trade-off relationship with the washability and dry-cleaning resistance of the print. Also, because of the printing method in which the thermal melt transfer ink ribbon is pressed against the clothing label in direct surface contact to print, the transferability of the print is significantly affected by the smoothness and surface condition of the surface of the clothing label, which is the printing medium (if the transferability of the print deteriorates, the washability and dry-cleaning resistance of the print also tend to deteriorate).

[0004] In order to solve such problems, Patent Document 1 proposes that in a thermal transfer image receiving sheet having a surface layer made mainly of nylon and having microporous surfaces on the surface of a woven substrate such as nylon or polyester, by making the surface extremely smooth, it becomes possible to form high-resolution images when printing with a thermal printer using resin-type thermal ink. It suggests that improvements to the printing medium, the clothing display label (thermal transfer image receiving sheet), can make up for deficiencies in printing quality such as printing sensitivity, print transferability, and print sharpness of the thermal melt transfer ink ribbon (resin-type thermal ink).

[0005] Patent Document 2 also proposes that a thermal transfer ink sheet having an ink layer containing at least a colorant, nitrocellulose, and a low melt viscosity substance is combined with a thermal transfer image receiving cloth having specific properties made of nylon for printing, thereby improving image density and obtaining a clothing label with excellent washing resistance and dry cleaning resistance, and suggests that by combining a specific thermal melt transfer ink ribbon (thermal transfer ink sheet) with a specific clothing display label (thermal transfer image receiving cloth), it is possible to improve the transferability of the print, the sharpness of the print, and the washing resistance and dry cleaning resistance of the print.

[0006] However, since there are other required qualities for the material of clothing display labels, such as design, dyeability, cost, and texture, it is practically difficult to always use only clothing labels with specific properties, such as excellent print quality, washability, and dry-cleaning resistance. For example, it is known that a clothing display label having an image-receiving layer (surface layer) as shown in Patent Document 1 can greatly improve print quality, such as print sensitivity, print transferability, and print sharpness, as well as washability and dry-cleaning resistance, when used in combination with an appropriate thermal melt transfer ink ribbon, but on the other hand, such clothing display labels have an aspect of not being very pleasant to the touch. Furthermore, it is shown that clothing display labels that do not have an image receiving layer, as used in the examples of Patent Document 2, have a pleasant feel to the touch and are made using various threads such as nylon, polyester, acetate, acrylic, etc. However, even for clothing display labels made using these various threads, when a specific type of thread is used or when the surface of the clothing display label is poorly smooth, the transferability of the print and the washability and dry cleaning resistance of the print tend to deteriorate, suggesting that the transferability of the print and the washability and dry cleaning resistance of the print can be improved only when a specific thermal melt transfer ink ribbon is used in combination with a specific clothing display label.

[0007] In this way, in the past, various performance improvements have been made to the printing quality, such as printing sensitivity, transferability, and sharpness of the print, as well as the washing resistance and dry cleaning resistance of the print, by using clothing display labels that have an image-receiving layer (the surface layer in Patent Document 1) to make it easier to receive the print, or by combining specific clothing display labels with specific thermal melt transfer ink ribbons. Conversely, in situations where it is not possible to select an appropriate clothing display label, it has not been possible to expect all of the above-mentioned improvements in various performance characteristics.

[0008] In addition, when various clothing display labels are printed using a thermal transfer ink ribbon having an ink layer in which a heat-resistant resin, nitrocellulose, and a plasticizer, orthotoluenesulfonamide, are combined in a weight ratio of 1:1 as a binder component as shown in the examples of Patent Document 2, the print quality such as print sensitivity, print transferability, print sharpness, and the washability and dry cleaning resistance of the print tend to be generally good, but depending on the combination of the material of the thread of the clothing display label and the smoothness of the surface, the print transferability, washability, and dry cleaning resistance of the print may not be sufficient, and there is also another problem that the phenomenon in which the non-printed parts of the clothing display label are stained during printing, so-called "scumming," tends to occur. Furthermore, when an environmental storage test is performed in a high-temperature and high-humidity environment with this thermal transfer ink ribbon wound around a ribbon core, it has been found that the blocking phenomenon of the ink layer and the bleeding phenomenon of orthotoluenesulfonamide onto the surface of the thermal transfer ink ribbon tend to occur easily. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 07-232484 [Patent Document 2] Patent No. 3594246 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in consideration of the above-mentioned circumstances, and the main object of the present invention is to provide a thermal melt transfer type ink ribbon which has good printing sensitivity, transferability and sharpness of printing on various clothing display labels, excellent washing resistance and dry cleaning resistance of the print formed on the clothing display label, and which is excellent in suppressing the background scumming phenomenon during printing, the blocking phenomenon during storage in a high temperature and high humidity environment, and the bleeding phenomenon of plasticizers. [Means for solving the problem]

[0011] In order to solve these problems, the present inventors have conducted research and found that a thermal melt transfer ink ribbon having a transfer control layer, an ink layer, and an adhesive layer laminated in sequence on one side of a film substrate, the ink layer containing a colorant, nitrocellulose, and a toluenesulfonamide derivative, and an adhesive layer containing polymethylsilsesquioxane resin fine particles and a thermoplastic resin on the ink layer, can improve the print quality such as print sensitivity, print transferability, and print sharpness on various clothing display labels, and can form prints with excellent washability and dry cleaning resistance. It has also been found that the use of the thermal melt transfer ink ribbon of the present invention can suppress background scumming during printing, blocking phenomenon during storage in a high temperature and high humidity environment, and bleeding phenomenon of plasticizer.

[0012] As a result of further investigations, the inventors have found that even better results can be obtained in terms of the dry cleaning properties of the print by using at least one of vinyl chloride-vinyl acetate copolymer resin or polyurethane resin as the thermoplastic resin for the adhesive layer.

[0013] As a result of further investigation by the inventors, it was found that the content of polymethylsilsesquioxane resin particles in the adhesive layer was 0.005 g / m 2 More than 0.1g / m 2It was found that within the following range, the printing sensitivity, the transferability of the print, and the print sharpness are maintained while suppressing background scumming during printing, the blocking phenomenon during storage in a high temperature and high humidity environment, and the bleeding phenomenon of the plasticizer. For the same reason, it was also found that the average particle size of the polymethylsilsesquioxane resin fine particles is preferably in the range of 0.5 μm to 10.0 μm.

[0014] As a result of further investigations, the inventors have found that better results can be obtained in terms of print sensitivity, print transferability, print sharpness, wash resistance and dry cleaning resistance of the print by making the ink layer contain 20 parts by mass or more and 100 parts by mass or less of toluenesulfonamide derivative per 100 parts by mass of nitrocellulose.The inventors have also found that better results can be obtained in terms of wash resistance and dry cleaning resistance of the print by making the ink layer contain 10% by mass or more and 70% by mass or less of nitrocellulose as a whole.

[0015] As a result of further investigations, the inventors have found that by using at least N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide as the toluenesulfonamide derivatives contained in the ink layer, the transferability of the print is further improved, and the bleeding phenomenon of the plasticizer during storage in a high-temperature, high-humidity environment can be further suppressed. Effect of the Invention

[0016] By using the thermal melt transfer ink ribbon of the present invention, it is possible to print high quality images on various clothing display labels that are excellent in resistance to washing and dry cleaning, and further, it is possible to reduce the occurrence of background staining during printing and to suppress the blocking phenomenon and the bleeding phenomenon of plasticizers when stored in a high temperature and high humidity environment. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a thermal melt transfer ink ribbon of the present invention. [Diagram 2]FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a thermal melt transfer ink ribbon of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The thermal melt transfer ink ribbon 5 of the present invention basically has a structure in which a transfer control layer 2, an ink layer 3, and an adhesive layer 4 are laminated in this order on one side of a heat-resistant film substrate 1, as shown in Fig. 1. In addition, as shown in Fig. 2, a heat-resistant slip layer 6 made of a material having excellent heat resistance and slipperiness may be provided on the other side as necessary.

[0019] <<Components of thermal transfer ink ribbon>> Next, the components of the thermal melt transfer ink ribbon of the present invention will be described in detail below.

[0020] <Film substrate> The film substrate 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 heat-resistant film substrates include polyethylene terephthalate film (PET), polypropylene film, polystyrene film, polyimide film, polyamide film, polycarbonate film, polyvinyl chloride film, etc., and it is most preferable to use polyethylene terephthalate film. The thickness of the film substrate is not particularly limited, but should be appropriately considered depending on the material so that the strength, heat resistance, and thermal conductivity are appropriate. It is sufficient if it is 2 μm or more and 12 μm or less, but more preferably 3 μm or more and 6 μm or less because of good thermal conductivity.

[0021] <Heat-resistant slippery layer> In the thermal melt transfer ink ribbon of the present invention, in order to prevent the sticking phenomenon, in which the heat of the thermal head during printing causes the film substrate to fuse to the thermal head and break, wrinkles to form in the film substrate, or the slipperiness between the film substrate and the thermal head to deteriorate, resulting in printing problems, a heat-resistant slipping layer may be provided on one side of the film substrate as necessary, the heat-resistant slipping layer being made of various known heat-resistant resins such as various silicone modified resins, fluorine-based resins, cellulose-based resins, polyimide-based resins, etc. as main raw materials, with various adhesive resins, various crosslinking agents, various lubricants, and various organic and inorganic fillers mixed appropriately as other secondary raw materials.

[0022] The amount of the heat-resistant slip layer applied after drying is not particularly limited, and may be from 0.01 g / m2 to 0.50 g / m2 depending on the usage conditions and the type of printer. 2 The thickness may be appropriately selected from the following ranges: The adhesion weight of the heat-resistant slip layer after drying is 0.01 g / m 2 If the thickness is less than 0.5g / m2, the expected heat resistance effect cannot be obtained. Conversely, if the adhesion amount of the heat-resistant slipping layer after drying is less than 0.5g / m2, 2 If the temperature exceeds this level, the sensitivity during printing tends to deteriorate and problems such as foil peeling tend to occur.

[0023] <Transfer control layer> In the present invention, a transfer control layer is provided between the film substrate and the ink layer in order to control the peeling force between the film substrate and the ink layer, printing sharpness, etc. The raw materials constituting the transfer control layer are not particularly limited as long as they are mainly composed of various known heat-melting substances and thermoplastic resins, etc.

[0024] As various known heat-melting substances used in the transfer control layer, it is preferable to use various known waxes. Wax melts when heated and has a very low viscosity, which has the effect of improving the releasability of the ink layer from the film substrate. Examples of waxes include, but are not limited to, carnauba wax, montanic acid wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, polyolefin wax, amide-modified wax, and fluorine-modified wax. The waxes may be used alone or in combination.

[0025] As various known thermoplastic resins used in the transfer control layer, resins that are soft and flexible and have an appropriate adhesiveness between the film substrate and the ink layer to prevent the ink layer from falling off, and prevent the surface peeling phenomenon of the print to make the print clear are preferred. Examples of thermoplastic resins include, but are not limited to, EVA resin, EEA resin, polyamide resin, polyester resin, polyurethane resin, phenol resin, modified polyolefin resin, etc. The thermoplastic resins may be used alone or in combination.

[0026] The transfer control layer may further contain small amounts of various known surfactants, fillers and lubricants as additives as necessary to improve and adjust the paint viscosity, foil cutting property and melt viscosity.

[0027] The content ratio of the wax and the thermoplastic resin contained in the transfer control layer is not particularly limited, but is preferably in the range of 99:1 to 70:30 by mass ratio, and more preferably in the range of 97:3 to 80:20. If the content ratio of the thermoplastic resin in the transfer control layer is below the lower limit of the range, the adhesion between the film substrate and the ink layer is poor, and the ink layer tends to fall off or the print sharpness tends to be poor. Conversely, if the content ratio of the thermoplastic resin in the transfer control layer is above the upper limit of the range, the adhesion between the film substrate and the ink layer becomes too high, or the melt viscosity of the transfer control layer becomes too high, which causes the ink layer to not be transferred well, and the print sensitivity and print transferability tend to deteriorate.

[0028] The melting point (DSC method) or softening point (ring and ball method) of the transfer control layer is not particularly limited, but is preferably in the range of 60° C. to 150° C., and more preferably in the range of 80° C. to 130° C. If the melting point (DSC method) or softening point (ring and ball method) of the transfer control layer is less than 60° C., the heat resistance and abrasion resistance of the printed image and the sharpness of the print tend to deteriorate, while conversely, if the melting point (DSC method) or softening point (ring and ball method) of the transfer control layer is 150° C. or higher, a large amount of heat is required to melt the transfer control layer during printing, and the print sensitivity and transferability of the print tend to deteriorate.

[0029] The amount of the transfer control layer adhered after drying is not particularly limited, but is preferably 0.1 g / m 2 More than 3.0g / m 2 The range of 0.3 g / m 2 More than 1.5g / m 2 It is more preferable to select from the following ranges: The amount of adhesion of the transfer control layer after drying is 0.1 g / m 2 If the thickness is less than 3.0 g / m, sufficient peeling cannot be obtained at the interface with the ink layer, and transfer defects tend to occur. 2 If it exceeds this range, the printing sensitivity will deteriorate, and the components of the transfer control layer in the printing will increase, resulting in deterioration of the abrasion resistance and heat resistance of the printed image.

[0030] <Ink layer> The present invention is characterized in that an ink layer containing at least a colorant such as carbon black or various known organic or inorganic pigments or dyes, nitrocellulose, and a toluenesulfonamide derivative is laminated on top of the transfer control layer.

[0031] The composition ratio of the colorant and the binder component in the ink layer of the present invention is not particularly limited, but the content of the colorant in the ink layer is preferably in the range of 10% by mass to 70% by mass of the entire ink layer, and more preferably in the range of 20% by mass to 40% by mass of the entire ink layer. The content of the colorant in the ink layer, for example, carbon black, has a relatively strong hiding power, so the content may be small, but some color pigments have a weak hiding power, and in that case, it is necessary to increase the content of the colorant in the ink layer. If the content of the colorant in the ink layer increases, the content of the binder component in the ink layer decreases accordingly, and as a result, not only the printing sensitivity and the transferability of the print deteriorate, but also the washing resistance and dry cleaning resistance of the print tend to deteriorate.

[0032] The ink layer of the present invention uses nitrocellulose as one of the binder components. By using nitrocellulose as the binder component of the ink layer, the heat resistance, abrasion resistance, and chemical resistance of the print are improved, and as a result, the wash resistance and dry cleaning resistance of the print tend to be greatly improved. The properties of the nitrocellulose used in the present invention are not particularly limited, but it is more preferable in terms of print sensitivity and print sharpness to use nitrocellulose with a nitrogen content of 11.5% to 12.2% and a viscosity (25% solids) of 3.0 seconds or less measured based on JIS K-6703.

[0033] The content of nitrocellulose in the ink layer is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 60% by mass or less, of the entire ink layer. If the content of nitrocellulose in the ink layer is within the above range, the wash resistance and dry cleaning resistance of the print are good. If the content of nitrocellulose in the ink layer is below the lower limit of the above range, the wash resistance and dry cleaning resistance of the print tend to deteriorate, and conversely, if the content of nitrocellulose in the ink layer exceeds the upper limit of the above range, the print sensitivity, the transferability of the print, and the sharpness of the print tend to deteriorate extremely, which in turn deteriorates the wash resistance and dry cleaning resistance of the print.

[0034] The ink layer of the present invention uses a toluenesulfonamide derivative as one of the binder components. The toluenesulfonamide derivative has a function of a so-called plasticizer, and has the effect of modifying various properties of the resin components such as the above-mentioned nitrocellulose. As the toluenesulfonamide derivative preferred for use in the ink layer of the present invention, it is preferable to select at least one from o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, Nn-butylbenzenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, etc., and it is more preferable to select at least one from o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, etc., and it is most preferable to use at least both N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide. As a result of the inventor's repeated investigations, it was found that the use of both N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide as toluenesulfonamide derivatives in the ink layer improves the transferability of the print of the thermal melt transfer ink ribbon, and further improves the bleeding phenomenon of the plasticizer in a high temperature and high humidity environment. The preferred content of the mixture of N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide in the toluenesulfonamide derivative used in the ink layer is preferably in the range of 50% by mass to 100% by mass, more preferably in the range of 70% by mass to 100% by mass, of the entire toluenesulfonamide derivative. The mixing ratio of N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide in the mixture is not particularly limited, but is preferably in the range of 80:20 to 20:80 by mass, more preferably in the range of 70:30 to 30:70 by mass.

[0035] On the other hand, when a thermal melt transfer ink ribbon in which a large amount of toluenesulfonamide derivative has been added to the ink layer is stored in a high temperature and high humidity environment, the adhesive layer or ink layer tends to migrate to the back side (heat-resistant slipping layer side) of the film substrate, which is known as a blocking phenomenon, and the toluenesulfonamide derivative that has bled onto the surface of the thermal melt transfer ink ribbon tends to migrate to the back side (heat-resistant slipping layer side) of the film substrate. As a result, it is known that problems such as poor printing occur when the guide roll or thermal head is contaminated by ink components or toluenesulfonamide derivative during printing.

[0036] The content of the toluenesulfonamide derivative in the ink layer is preferably in the range of 5% by mass to 40% by mass of the entire ink layer, and more preferably in the range of 10% by mass to 30% by mass. If the content of the toluenesulfonamide derivative in the ink layer is within the above range, the printing sensitivity, the transferability of the print, and the sharpness of the print are good. If the content of the toluenesulfonamide derivative in the ink layer is below the lower limit of the above range, the printing sensitivity, the transferability of the print, and the sharpness of the print tend to deteriorate, and as a result, the washing resistance and dry cleaning resistance of the print also tend to deteriorate. Conversely, if the content of the toluenesulfonamide derivative in the ink layer exceeds the upper limit of the above range, blocking phenomenon and bleeding phenomenon of the plasticizer during storage in a high temperature and high humidity environment tend to occur, and the washing resistance and dry cleaning resistance of the print also tend to deteriorate.

[0037] The mass ratio of the nitrocellulose to the toluenesulfonamide derivative in the ink layer is preferably in the range of 20 to 100 parts by mass of the toluenesulfonamide derivative per 100 parts by mass of nitrocellulose, and more preferably in the range of 25 to 66 parts by mass of the toluenesulfonamide derivative per 100 parts by mass of nitrocellulose. When the mass ratio of the nitrocellulose to the toluenesulfonamide derivative in the ink layer is within the above range, the printing sensitivity, the transferability of the print, the sharpness of the print, and the washing resistance and dry cleaning resistance of the print are good. If the mass ratio of the toluenesulfonamide derivative in the ink layer is below the lower limit of the above range, the printing sensitivity, the transferability of the print, and the sharpness of the print tend to deteriorate, and as a result, the washing resistance and dry cleaning resistance of the print also tend to deteriorate. Conversely, if the mass ratio of the toluenesulfonamide derivative in the ink layer exceeds the upper limit of the above range, the printing sensitivity, the transferability of the print, and the sharpness of the print do not deteriorate, but the blocking phenomenon and the bleeding phenomenon of the plasticizer during storage in a high temperature and high humidity environment are more likely to occur, and the washing resistance and dry cleaning resistance of the print also tend to deteriorate.

[0038] The binder component of the ink layer of the thermal melt transfer ink ribbon of the present invention may further contain a thermoplastic resin in addition to the above-mentioned nitrocellulose and toluenesulfonamide derivative. The "thermoplastic resin" contained in the ink layer hereinafter refers to a thermoplastic resin other than nitrocellulose, which is an essential component in the ink layer in the present invention. The thermoplastic resin contained as the binder component of the ink layer is not particularly limited, but polyester resin, urethane modified polyester resin, cellulose resin, polyamide resin, modified polyolefin resin, novolac type phenolic resin, acrylic resin, styrene resin, styrene-(meth)acrylic copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, etc. can be used, and it is preferable to use a thermoplastic resin that shows adhesiveness when thermally melted, and it is more preferable to use polyester resin, polyamide resin, modified polyolefin resin, styrene-(meth)acrylic copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, and most preferable to use vinyl chloride-vinyl acetate copolymer resin, polyurethane resin. The above-mentioned various thermoplastic resins contained as the binder component of the ink layer may be used alone or in combination of one or more thermoplastic resins. By further adding the above-mentioned thermoplastic resin to the ink layer, it is possible to further improve the transferability and adhesion of the print to the clothing display label, and to improve the adhesion to the adhesive layer provided on the ink layer, and as a result, it is possible to further improve the washing resistance and dry cleaning resistance of the print. In particular, from the viewpoint of improving the adhesion between the adhesive layer and the ink layer, it is more preferable that the ink layer further contains at least one thermoplastic resin that is the same as the thermoplastic resin contained in the adhesive layer described below, since this can further enhance the above-mentioned effects.

[0039] The various thermal properties of the thermoplastic resin contained in the ink layer are not particularly limited, but in the case of a thermoplastic resin having a melting point or softening point, the melting point or softening point is preferably in the range of 70° C. or more and 180° C. or less, and more preferably in the range of 80° C. or more and 170° C. or less. In addition, in the case of a thermoplastic resin having a glass transition point (DSC method), the glass transition point (Tg) is preferably in the range of 50° C. or more and 110° C. or less, and more preferably in the range of 70° C. or more and 100° C. or less. When the various thermal property values ​​of the thermoplastic resin contained in the ink layer are within the above ranges, the printing sensitivity, transferability of the print, sharpness of the print, washing resistance and dry cleaning resistance of the print are good. When the various thermal property values ​​of the thermoplastic resin contained in the ink layer are below the lower limit of the aforementioned range, the washing resistance and dry cleaning resistance of the print tend to deteriorate. Conversely, when the various thermal property values ​​exceed the upper limit of the aforementioned range, excessive energy is required during printing or the foil sharpness of the ink layer deteriorates, which deteriorates the printing sensitivity, transferability of the print, and sharpness of the print, and as a result, the washing resistance and dry cleaning resistance of the print also tend to deteriorate.

[0040] The number average molecular weight (Mn) of the thermoplastic resin contained in the ink layer is not particularly limited, but is preferably in the range of 8000 to 50000, and more preferably in the range of 15000 to 40000. If the number average molecular weight of the thermoplastic resin contained in the ink layer is within the above range, the printing sensitivity, the transferability of the print, and the sharpness of the print are good, and the washing resistance and cleaning resistance of the print do not deteriorate. If the number average molecular weight of the thermoplastic resin contained in the ink layer is below the lower limit of the above range, the chemical resistance of the thermoplastic resin itself becomes poor, so that the washing resistance and dry cleaning resistance of the print tend to deteriorate. Conversely, if the number average molecular weight of the thermoplastic resin exceeds the upper limit of the above range, the melt viscosity of the ink layer increases, and so on, which tends to deteriorate the printing sensitivity, the transferability of the print, and the sharpness of the print.

[0041] The content of the thermoplastic resin in the ink layer is not particularly limited, but is preferably in the range of 0.5% by mass to 20.0% by mass, and more preferably in the range of 1.0% by mass to 10.0% by mass. If the content of the thermoplastic resin in the ink layer is in the above range, the transferability and adhesion of the print to the clothing display label having an uneven surface are further improved, and the washability and cleanability of the print are also improved accordingly. If the content of the thermoplastic resin in the ink layer is below the lower limit of the above range, the effect of improving the transferability and adhesion of the print to the clothing display label having an uneven surface cannot be obtained. Conversely, if the content of the thermoplastic resin in the ink layer exceeds the upper limit of the above range, the effect of improving the washability and dry cleaning resistance of the print by nitrocellulose is canceled, and as a result, the washability and dry cleaning resistance of the print tend to decrease.

[0042] To the ink layer of the present invention, various known surfactants, lubricants, inorganic fillers, organic fillers and waxes may be added in small amounts as additives as necessary to improve and adjust the dispersibility of the colorant, the foil-cutting property of the ink, the blocking resistance of the ink layer, the melt viscosity of the ink layer, and the like.

[0043] The amount of the ink layer after drying in the present invention is not particularly limited, and is preferably 0.5 g / m 2 More than 3.0g / m 2 The range is preferably 0.7 g / m 2 More than 2.0g / m 2 If the adhesion amount of the ink layer after drying is below the lower limit of the above range, sufficient print density and print resistance to washing and dry cleaning tend not to be obtained, whereas if the adhesion amount exceeds the upper limit of the above range, print sensitivity and print sharpness tend to deteriorate.

[0044] <Adhesive layer> The present invention is characterized in that an adhesive layer containing at least a thermoplastic resin and polymethylsilsesquioxane resin fine particles is laminated on the ink layer.

[0045] In the configuration of the thermal melt transfer ink ribbon of the present invention, for example, when printing is performed on a clothing display label without providing an adhesive layer on the ink layer, excellent print quality and wash resistance and dry cleaning resistance of the print may be shown for a clothing display label made of a certain material or a clothing display label provided with an image receiving layer, but when printing is performed on a clothing display label having a relatively uneven surface, the print is difficult to transfer, and as a result, the wash resistance and dry cleaning resistance of the print tend to be insufficient. Therefore, when the amount of plasticizer such as toluenesulfonamide derivative added to the ink layer is increased to improve the transferability of the print, the transferability of the print to the clothing display label is somewhat improved but is insufficient, and further, the increase in the amount of plasticizer reduces the chemical resistance and heat resistance of the ink layer itself, which reduces the wash resistance and dry cleaning resistance of the print, and the increase in the amount of plasticizer tends to worsen the blocking phenomenon and plasticizer bleeding phenomenon during storage in a high temperature and high humidity environment, and the background scumming during printing tends to worsen.

[0046] In order to solve the above problems, the present inventors have attempted to improve the transferability of the print to the clothing display label while improving the washing resistance and dry cleaning resistance of the print and to suppress the blocking phenomenon and the bleeding phenomenon of plasticizers during storage in a high temperature and high humidity environment and the scumming during printing by further providing an adhesive layer on top of the ink layer. However, simply providing a general adhesive layer mainly composed of a heat-fusible substance such as wax or a thermoplastic resin on top of the ink layer improves the transferability of the print, but the washing resistance and dry cleaning resistance of the print may decrease depending on the composition of the adhesive layer, etc. Even if the washing resistance and dry cleaning resistance of the print are improved, the blocking phenomenon and the bleeding phenomenon of plasticizers during storage in a high temperature and high humidity environment and the scumming during printing cannot be suppressed, and therefore a fundamental problem could not be solved.

[0047] As a result of extensive research into solving the above-mentioned problems, the inventors have found that by sequentially laminating a transfer control layer, an ink layer containing a colorant, nitrocellulose, and a toluenesulfonamide derivative, and an adhesive layer containing at least a thermoplastic resin and polymethylsilsesquioxane resin microparticles on one side of a film substrate, it is possible to obtain a hot-melt transfer ink ribbon that has excellent printing sensitivity, print transferability, print sharpness, washability, and dry-cleaning resistance for various clothing display labels, is less likely to cause background scumming during printing, and has excellent environmental storage performance such as being less susceptible to blocking and plasticizer bleeding during storage in high temperature and high humidity environments.

[0048] The adhesive layer of the present invention contains at least fine particles made of polymethylsilsesquioxane resin. Polymethylsilsesquioxane resin is a resin having the structural formula (CH 3 SiO 1.5 It is a type of organopolysiloxane resin having a three-dimensional network-like crosslinked structure represented by the formula (1) and has excellent heat resistance, chemical resistance and lubricity. As a result of the inventor's investigation of the raw materials for the adhesive layer, it was found that when polymethylsilsesquioxane resin fine particles are used in the adhesive layer, the transferability of the print to various clothing display labels is hardly inhibited, so the print sensitivity and the transferability of the print are hardly deteriorated, there is no adverse effect on the washability and dry cleaning resistance of the print, and further, there is a large effect of suppressing background scumming during printing, blocking phenomenon during storage in a high temperature and high humidity environment, and bleeding phenomenon of plasticizers.

[0049] The average particle diameter of the polymethylsilsesquioxane resin fine particles used in the adhesive layer is preferably in the range of 0.5 μm to 10.0 μm, more preferably in the range of 1.0 μm to 8.0 μm. If the average particle diameter of the polymethylsilsesquioxane resin fine particles is within the above range, the printing sensitivity, the transferability of the printing, the sharpness of the printing, the washing resistance and the dry cleaning resistance of the printing are not reduced, the background staining during printing is unlikely to occur, and it is also effective in suppressing the blocking phenomenon and the bleeding phenomenon of the plasticizer during storage under a high temperature and humidity environment. Note that when the average particle diameter of the polymethylsilsesquioxane resin fine particles is equal to or greater than the calculated thickness of the adhesive layer calculated from the adhesion amount of the adhesive layer and the specific gravity of the constituent raw materials, that is, when a part of the polymethylsilsesquioxane resin fine particles protrudes from the surface of the adhesive layer, the effect of adding the above-mentioned polymethylsilsesquioxane resin fine particles is most clearly manifested. If the average particle size of the polymethylsilsesquioxane resin fine particles is below the lower limit of the above range, the effect of suppressing background scumming during printing and blocking and bleeding phenomena during storage in a high temperature and humidity environment tends to deteriorate, and conversely, if it exceeds the upper limit of the above range, the print quality such as print sensitivity, print transferability, and print sharpness deteriorates, and as a result, the wash resistance and dry cleaning resistance of the print also tend to deteriorate. The shape of the polymethylsilsesquioxane resin fine particles used in the present invention is not particularly limited, and may be spherical or amorphous, but it is more preferable that they are spherical in terms of the stability of performance affected by the average particle size.

[0050] The content of the polymethylsilsesquioxane resin fine particles in the adhesive layer is not particularly limited, but is preferably in the range of 1.0% by mass to 80.0% by mass of the entire adhesive layer, and more preferably in the range of 20.0% by mass to 60.0% by mass. If the content of the polymethylsilsesquioxane resin fine particles in the adhesive layer is within the above range, the print quality, wash resistance and dry cleaning resistance of the print are not deteriorated, background staining during printing is unlikely to occur, and blocking phenomenon and plasticizer bleeding phenomenon during storage in a high temperature and high humidity environment are effectively suppressed. The content and effect of the polymethylsilsesquioxane resin microparticles in the adhesive layer do not necessarily show a unique trend, as they vary depending on the average particle size of the polymethylsilsesquioxane resin microparticles, the thickness of the adhesive layer, and the balance with other constituent materials. However, as the content of polymethylsilsesquioxane resin microparticles in the adhesive layer decreases, the effect of suppressing background scumming during printing and blocking and bleeding phenomena during storage in high temperature and humidity environments tends to decrease. Conversely, as the content increases, printing quality such as printing sensitivity, print transferability, and print sharpness gradually decreases, and as a result, the washing resistance and dry cleaning resistance of the print also tend to decrease.

[0051] The present inventors further investigated the optimum amount of polymethylsilsesquioxane resin fine particles to be added to the adhesive layer from a different perspective, and found that the content of polymethylsilsesquioxane resin fine particles in the adhesive layer was 0.005 g / m 2 More than 0.100g / m 2 The range is preferably 0.01 g / m 2 More than 0.05g / m 2It has been found that the following range is more preferable. If the content of the polymethylsilsesquioxane resin fine particles in the adhesive layer per unit area is within the above range, the print quality such as print sensitivity, print transferability, and print sharpness, and the wash resistance and dry cleaning resistance of the print will not decrease, and it is also effective in suppressing background scumming during printing, blocking phenomenon during storage in a high temperature and high humidity environment, and bleeding phenomenon of the plasticizer. If the content of the polymethylsilsesquioxane resin fine particles in the adhesive layer per unit area is below the lower limit of the above range, the effect of suppressing background scumming during printing, blocking phenomenon during storage in a high temperature and high humidity environment, and bleeding phenomenon tends to deteriorate, and conversely, if it exceeds the upper limit of the above range, the print quality such as print sensitivity, print transferability, and print sharpness will deteriorate, and as a result, the wash resistance and dry cleaning resistance of the print will also tend to deteriorate.

[0052] The adhesive layer of the present invention is characterized by containing at least a thermoplastic resin in addition to polymethylsilsesquioxane resin fine particles. The thermoplastic resin used in the adhesive layer is added mainly to improve the transferability and adhesion of the print to a print-receiving medium such as a clothing display label, and as a result, has the effect of improving the print quality and the washability and dry-cleaning resistance of the print.

[0053] The thermoplastic resin used in the adhesive layer is not particularly limited, and for example, polyester resin, urethane-modified polyester resin, polyamide resin, cellulose resin, modified polyolefin resin, novolac-type phenol resin, styrene resin, styrene-(meth)acrylic copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, etc. can be used. Furthermore, it is preferable to use a thermoplastic resin that shows adhesiveness when heat-melted, and it is more preferable to use polyester resin, modified polyolefin resin, styrene-(meth)acrylic copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, and most preferable to use vinyl chloride-vinyl acetate copolymer resin, polyurethane resin. The various thermoplastic resins used in the adhesive layer described above may be used alone or may be used in combination of one or more thermoplastic resins. In particular, when at least one of vinyl chloride-vinyl acetate copolymer resin or polyurethane resin is used as the thermoplastic resin used in the adhesive layer, not only is the transferability of the print to clothing display labels, etc., the sharpness and adhesion of the print particularly excellent, but also the chemical resistance is excellent, so that the dry cleaning resistance of the print tends to be improved.

[0054] In order to improve the performance of the washing resistance and dry cleaning resistance of the print in the formulation design of the ink layer, the content of nitrocellulose contained in the ink layer must be increased to a certain extent, but if an adhesive layer is not provided on the upper layer of the ink layer, the printing sensitivity, the transferability of the print, and the adhesion between the print and the clothing display label will be significantly deteriorated, and as a result, the printing quality, the washing resistance and dry cleaning resistance of the print will also be significantly deteriorated. In order to compensate for the printing sensitivity, the transferability of the print, and the adhesion between the print and the clothing display label that are impaired by such a formulation design of the ink layer, an adhesive layer is provided on the upper layer of the ink layer, and a thermoplastic resin that exhibits adhesiveness when heat-melted is further added to the adhesive layer, thereby improving the printing sensitivity, the transferability of the print, and the adhesion between the print and the clothing display label, and as a result, it is possible to improve the washing resistance and dry cleaning resistance of the print. Furthermore, as described above, from the viewpoint of improving the adhesion between the ink layer and the adhesive layer, it is more preferable that the ink layer further contains at least one thermoplastic resin that is the same as the thermoplastic resin contained in the adhesive layer, which makes it possible to further enhance the effects described above, and in particular tends to further improve washing resistance.

[0055] The various thermal properties of the thermoplastic resin contained in the adhesive layer are not particularly limited, but in the case of a thermoplastic resin having a melting point or softening point, the melting point or softening point is preferably in the range of 70°C to 180°C, and more preferably in the range of 80°C to 170°C. In addition, in the case of a thermoplastic resin having a glass transition point (DSC method), the glass transition point (Tg) is preferably in the range of 50°C to 110°C, and more preferably in the range of 70°C to 100°C. If the various thermal property values ​​of the thermoplastic resin contained in the adhesive layer are within the above ranges, the printing sensitivity, transferability of the print, adhesion of the print to the clothing display label, etc. are improved, and as a result, the print quality, washing resistance, and dry cleaning resistance of the print are also improved. If the glass transition temperature of the thermoplastic resin contained in the adhesive layer is below the lower limit of the above range, blocking phenomenon during storage in a high temperature and high humidity environment and the washing resistance and dry cleaning resistance of the print tend to deteriorate. Conversely, if it exceeds the upper limit of the above range, excessive energy is required during printing and the foil sharpness of the adhesive layer coating film deteriorates, resulting in deterioration of the printing sensitivity, transferability of the print, and sharpness of the print, and as a result, the washing resistance and dry cleaning resistance of the print also tend to deteriorate.

[0056] The number average molecular weight (Mn) of the thermoplastic resin contained in the adhesive layer is preferably in the range of 8000 to 50000, more preferably in the range of 15000 to 40000. If the number average molecular weight of the thermoplastic resin is within the above range, the printing sensitivity, the transferability of the print, the sharpness of the print, the washing resistance and the dry cleaning resistance of the print are good. If the number average molecular weight of the thermoplastic resin is below the lower limit of the above range, the chemical resistance of the thermoplastic resin itself becomes poor, so that the washing resistance and the dry cleaning resistance of the print tend to deteriorate. Conversely, if the number average molecular weight of the thermoplastic resin exceeds the upper limit of the above range, the foil sharpness of the adhesive layer tends to deteriorate or the melt viscosity of the adhesive layer tends to increase, and as a result, the printing sensitivity, the transferability of the print, and the sharpness of the print deteriorate, and as a result, the washing resistance and the dry cleaning resistance of the print also tend to deteriorate.

[0057] The content of the thermoplastic resin in the adhesive layer is not particularly limited, but is preferably in the range of 20% by mass to 99% by mass of the entire adhesive layer, more preferably in the range of 30% by mass to 90% by mass, and most preferably in the range of 40% by mass to 80% by mass. If the content of the thermoplastic resin in the adhesive layer is within the above range, the transferability of the print and the adhesion of the print to the clothing display label are improved, resulting in good print quality and good washability and dry cleaning resistance of the print.

[0058] In addition, various known surfactants, lubricants, inorganic fillers, organic fillers, and waxes may be added to the adhesive layer of the present invention as additives, as needed, to the extent that the beneficial performance of the adhesive layer described above is not impaired.

[0059] The amount of adhesion of the adhesive layer after drying of the present invention is not particularly limited, but is preferably 0.01 g / m 2 More than 1.0g / m 2 The range is preferably 0.03 g / m 2 More than 0.70g / m 2 If the adhesion amount after drying of the adhesive layer is below the lower limit of the above range, there is a tendency that the improvement of the transferability of the print and the adhesion of the print to the clothing display label, the suppression of background staining during printing, and the suppression of the blocking phenomenon and the bleeding phenomenon of the plasticizer during storage in a high temperature and high humidity environment are not obtained, whereas if it exceeds the upper limit of the above range, there is a tendency that the performance such as the print sensitivity and the wash resistance and dry cleaning resistance of the print are deteriorated. EXAMPLES

[0060] Next, the present invention will be specifically described with reference to examples.

[0061] <<Method of forming each layer of thermal transfer ink ribbon>> The method of forming each layer of the thermal transfer ink ribbon used in the examples and comparative examples of the present invention will be described below. The method of preparing and applying the various paints used in each layer shown below is merely an example, and is not limited thereto, and various known methods can be used. The various paint formulations used in each layer shown below and the values ​​of the paint formulations shown in Tables 1 to 3 are based on mass ratios unless otherwise specified.

[0062] <Method of forming heat-resistant slip layer> Based on the heat-resistant slipping layer paint formulation shown below, each raw material was weighed and placed in a container, and the mixture was thoroughly stirred and mixed with a mixer until uniform, to prepare a heat-resistant slipping layer paint. Using a gravure coater, the paint was applied to one side of a 4.5 μm-thick polyethylene terephthalate film (PET film) with a dry adhesion of 0.2 g / m2. 2 The heat-resistant slipping layer was formed by coating and drying the heat-resistant slipping layer. This PET film and heat-resistant slipping layer were used in all of the following examples and comparative examples of the present invention. (Contains paint for heat-resistant slipping layer) Raw material component mass% Silicone modified polyester polyurethane resin Methyl ethyl ketone:toluene = 1:1 mixed solvent solution (solid content 15% by mass) 25.0 Methyl ethyl ketone 60.0 Toluene 15.0

[0063] <Method of forming transfer control layer> Based on the paint formulation for the transfer control layer shown below, each raw material was weighed and placed in a container, and the mixture was thoroughly stirred and mixed with a mixer until uniform, to prepare a paint for the transfer control layer. Using a gravure coater, the paint was applied to the surface of the film substrate opposite to the surface on which the heat-resistant active layer was provided, with a coating weight of 0.8 g / m2 after drying. 2 The transfer control layer was formed by applying and drying the transfer control layer paint prepared so as to obtain the following transfer control layer. This transfer control layer was used in all of the following examples and comparative examples of the present invention. (Paint formulation for transfer control layer) Raw material component mass% ·Polyethylene wax (melting point 105℃) Dispersion in toluene (solid content 15% by mass) 63.3 EVA resin (VA 28%, melting point 70℃) Toluene solution (solid content 10% by mass) 5.0 Toluene 31.7

[0064] <Method of forming ink layer> Based on the ink layer paint formulation shown below, each raw material is weighed and placed in a container, and then thoroughly mixed with a mixer until homogeneous. Carbon is then dispersed using a bead mill or similar to prepare an ink layer paint, which is then applied to the top layer of the transfer control layer using a gravure coater until the amount of adhesion after drying is 1.0 g / m 2 The ink layer was formed by applying and drying the ink layer paint prepared so as to obtain the following: The ink layers in the other examples and comparative examples of the present invention were formed in the same manner and under the same conditions as the ink layer used in Example 1, except for the paint formulation, and the details of the paint formulation etc. are shown in Tables 1 to 3 below. (Ink layer paint formulation (used in Example 1)) Raw material component mass% Industrial nitrocellulose (70% solids, isopropanol as wetting agent) (IPA) 30% (nitrocellulose:IPA = 70:30 (mass ratio)), Nitrogen content 11.5~12.2% by mass) 10.7 N-ethyl-o-toluenesulfonamide Mixture with N-ethyl-p-toluenesulfonamide (Mix ratio is 7:3 by mass) 3.0 Carbon 4.5 Toluene 27.0 Methyl ethyl ketone (MEK) 54.8

[0065] <Method of forming adhesive layer> Based on the adhesive layer paint formulation shown below, each raw material is weighed and put into a container, and then thoroughly stirred and mixed with a mixer until homogeneous to prepare an adhesive layer paint. Using a gravure coater, apply the paint to the top layer of the ink layer so that the amount of adhesion after drying is 0.10 g / m. 2The adhesive layer was formed by applying and drying the adhesive layer paint prepared so as to obtain the following: The adhesive layers in the other examples and comparative examples of the present invention were formed in the same manner and under the same conditions as the adhesive layer used in Example 1, except for the paint formulation, and the details of the paint formulation, etc. are shown in Tables 1 to 3 below. (Adhesive layer paint formulation (used in Example 1)) Raw material component mass% Polymethylsilsesquioxane resin particles (Average particle size: 2.0μm) 3.5 Vinyl chloride / vinyl acetate copolymer resin (Tg: 77℃, Mn: 36000) 6.5 Toluene 35.0 Methyl ethyl ketone (MEK) 55.0

[0066] <<Various evaluation methods>> Various evaluation methods using the various thermal melt transfer ink ribbons prepared in the Examples and Comparative Examples are described below.

[0067] <Printing test conditions> Printing tests were carried out under the following conditions using each of the thermal melt transfer ink ribbons of the Examples and Comparative Examples, the details of which are shown in Tables 1 to 3. For the clothing display labels, which are non-printing media, a plain weave fabric made of nylon yarn with an image receiving layer (Ny plain weave fabric with image receiving layer) was used, which has a smooth surface and an image receiving layer mainly composed of polyamide resin, making it relatively easy to transfer prints using a thermal melt transfer ink ribbon, and a satin fabric made of polyester yarn (PES satin fabric) was used, which has a somewhat uneven surface and no image receiving layer, making it difficult to transfer prints using a thermal melt transfer ink ribbon. Printer: CL4NX (manufactured by Sato Corporation) Print resolution: 12dot / mm Printing speed: 4inch / sec Print energy: 8 / 10 Printing medium 1: Nylon plain weave fabric with a polyamide resin image-receiving layer Printing medium 2: Polyester satin fabric (no image receiving layer, etc.)

[0068] <Evaluation of printing sensitivity> Printing was performed 10 times on each print-receiving medium under the above-mentioned printing test conditions, and the 10 printed images were visually inspected and evaluated under the conditions shown below. A: There is absolutely no smearing of the print. B: Slight smudges in the print occur in some areas. C: Light printing smudges occur over the entire surface. D: Severe print smearing occurs all over the surface.

[0069] <Evaluation of print transferability> Printing was performed 10 times on each print-receiving medium under the above-mentioned printing test conditions, and the 10 printed images were visually inspected and evaluated under the conditions shown below. A: The printing is transferred completely over the entire surface, with absolutely no voids or uneven printing. B: Slight voids or uneven printing are observed in some parts of the print. C: Voids and uneven printing are clearly visible over the entire surface of the print. D: Severe voids or uneven printing are observed over the entire surface of the print, or the print has barely been transferred.

[0070] <Evaluation of print sharpness> Printing was performed 10 times on each print-receiving medium under the above-mentioned printing test conditions, and the 10 printed images were visually inspected and evaluated under the conditions shown below. A: No peeling or crushing of the print is observed. B: Peeling of the print or crushing of the print is observed in a very small area. C: Peeling of the print or crushing of the print is clearly observed in some areas. D: Peeling or crushing of the print is observed over almost the entire surface. Here, the planar peeling phenomenon refers to the phenomenon in which not only the coating film such as the ink layer in the part where heat is applied from the thermal head, but also the coating film to which heat is not applied is transferred to the print medium, resulting in poor print sharpness. Also, print collapse refers to the phenomenon in which the outline of the transferred print becomes thicker than the original print data, or the outline of the print becomes blurred, resulting in a loss of fine print.

[0071] <Evaluation of background scumming during printing> Printing was performed 10 times on each print-receiving medium under the above-mentioned printing test conditions, and the unprinted portions of the 10 sheets were visually inspected and evaluated under the conditions shown below. A: No scumming is observed in the non-printed areas. B: Slight background staining is observed intermittently in a very small area in the non-printed areas. C: Slight background smearing in the non-printed areas is clearly visible over the entire surface. D: Severe smudging in non-printed areas is visible over almost the entire surface.

[0072] <Evaluation of washing resistance of print> Each of the print-receiving media printed under the above-mentioned printing test conditions was used as a test piece, and a color fastness test (JIS L-0844 (A-4 method)) was performed three times to evaluate the degree of discoloration of the test pieces after the test and the degree of staining of various attached white cloths. Based on the evaluation results, evaluation was performed under the conditions shown below. A: There is almost no discoloration of the test specimen or contamination of the attached white cloth. B: There is some discoloration of the test piece and some staining of the attached white cloth, but this does not affect its use. C: Discoloration of the test specimen and contamination of the attached white cloth are clearly visible. D: The test specimen was discolored and the attached white cloth was badly stained.

[0073] <Evaluation of dry cleaning resistance of print> Each of the print-receiving media printed under the above-mentioned printing test conditions was used as a test piece, and a dye fastness test (JIS L-0860 (A-1 method)) against dry cleaning was performed three times. After the test, the test pieces were evaluated for discoloration and the degree of staining of various attached white cloths. Based on the evaluation results, evaluation was performed under the conditions shown below. A: There is almost no discoloration of the test specimen or contamination of the attached white cloth. B: There is some discoloration of the test piece and some staining of the attached white cloth, but this does not affect its use. C: Discoloration of the test specimen and contamination of the attached white cloth are clearly visible. D: The test specimen was discolored and the attached white cloth was badly stained.

[0074] <Evaluation of blocking resistance (environmental preservation performance)> To evaluate blocking resistance, a raw thermal melt transfer ink ribbon was slit to a specified size and wound around a paper core to create a rolled ribbon sample (width 60 mm, length 300 m, ink surface inward). The ribbon sample was then stored in an atmosphere with a temperature of 40°C and a humidity of 80% for 48 hours, after which it was cooled in a room temperature environment with a temperature of 23°C for 24 hours. The ribbon sample was then unwound and the state of blocking was visually inspected and evaluated under the conditions shown below. A: No blocking was observed. B: Slight blocking is observed near the paper core of the ribbon sample. C: Partial blocking is observed between the middle of winding the ribbon sample and near the paper core. D: Blocking is observed over the entire surface of the ribbon sample.

[0075] <Evaluation of plasticizer bleeding resistance (environmental preservation performance)> To evaluate plasticizer blocking resistance, a raw thermal melt transfer ink ribbon was slit to a specified size and wrapped around a paper core to create a rolled ribbon sample (width 60 mm, length 300 m, ink surface inward). The ribbon sample was then stored in an atmosphere with a temperature of 40°C and a humidity of 80% for 48 hours, after which it was left to cool for 24 hours in a room temperature environment with a temperature of 23°C. After that, printing was performed in a room temperature environment with a temperature of 23°C, and the print and the condition of each part of the printer were visually inspected and evaluated under the conditions shown below. A: No abnormalities were found in the printing or any part of the printer. B: Although there is a small amount of plasticizer attached to the thermal head and guide roll of the printer where the heat-resistant slip layer comes into contact, there is no abnormality in the printing and no problem in use. C: Plasticizer adhesion was clearly observed on the printer's thermal head and guide roll with which the heat-resistant slip layer came into contact, and this was believed to be the cause of poor printing. D: A large amount of plasticizer adheres to the printer's thermal head and guide roll with which the heat-resistant slipping layer comes into contact.

[0076] The details of the paint composition of the ink layer and adhesive layer of each Example and Comparative Example, and the results of the various performance evaluations described above performed on the thermal melt transfer ink ribbons prepared for each Example and Comparative Example, are shown in Tables 1 to 3 below.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3] *In Comparative Example 4 in Table 3 above, since the print was hardly transferred to the print-receiving medium, evaluation of print quality and washability and dry-cleanability of the print were not performed.

[0080] From the results of Tables 1 to 3, it is found that, as in the thermal melt transfer ink ribbons of Examples 1 to 17, a transfer control layer, an ink layer, and an adhesive layer are sequentially laminated on one side of a film substrate, the ink layer contains a colorant, nitrocellulose, and a toluenesulfonamide derivative, and an adhesive layer containing polymethylsilsesquioxane resin fine particles and a thermoplastic resin is further provided on the upper layer, and the ink ribbon has excellent print quality such as print sensitivity, transferability, and print sharpness on various clothing display labels, and is also excellent in wash resistance and dry cleaning resistance of the formed print, and furthermore, it is possible to suppress background scumming during printing, blocking phenomenon during storage under high temperature and humidity environment, and bleeding phenomenon of plasticizer. On the other hand, as in Comparative Example 1, if an adhesive layer is not provided on the upper layer of the ink layer, background scumming during printing is poor, washing resistance and dry cleaning resistance on polyester satin fabric are poor, and blocking phenomenon and bleeding phenomenon of plasticizer during storage under high temperature and humidity environment are worse. In the case of Comparative Example 2, when silica was added as a matting agent to the adhesive layer instead of the polymethylsilsesquioxane resin fine particles, there was a slight improvement effect on the background stain during printing and the blocking phenomenon during storage in a high temperature and high humidity environment compared to Comparative Example 1, but there was not much improvement in the bleeding phenomenon, and conversely, the transferability of the print was worsened. In addition, in the case of Comparative Example 3, when no polymethylsilsesquioxane resin fine particles were added to the adhesive layer, there was a slight improvement effect on the transferability of the print and the background stain during printing compared to Comparative Example 1, and there was a large improvement effect on the washing resistance and the dry cleaning resistance, but there was not much improvement in the blocking phenomenon during storage in a high temperature and high humidity environment and the bleeding phenomenon of the plasticizer. In addition, in Comparative Example 4, when no toluenesulfonamide derivative was contained in the ink layer, the print was hardly transferred to the non-printing medium. [Industrial Applicability]

[0081] The thermal melt transfer ink ribbon of the present invention can be used not only for clothing display labels such as washing instructions labels and quality instructions labels, but also for applications requiring the formation of robust prints that are particularly excellent in water resistance, abrasion resistance, washing resistance, and dry cleaning resistance on various synthetic resin labels, various synthetic paper labels, various waterproof paper labels, and various woven fabric labels. [Explanation of symbols]

[0082] 1. Film substrate 2. Transcriptional control layer 3. Ink layer 4; Adhesive layer 5. Thermal transfer ink ribbon 6; Heat-resistant slippery layer

Claims

1. A thermal melt transfer ink ribbon having a transfer control layer, an ink layer, and an adhesive layer laminated in that order on one side of a film substrate, the ink layer containing a colorant, nitrocellulose, and a toluenesulfonamide derivative, and the adhesive layer containing a thermoplastic resin and polymethylsilsesquioxane resin fine particles.

2. 2. The thermal melt transfer ink ribbon according to claim 1, wherein the thermoplastic resin contained in the adhesive layer is at least one of a vinyl chloride-vinyl acetate copolymer resin and a polyurethane resin.

3. The content of polymethylsilsesquioxane resin fine particles in the adhesive layer is 0.005 g / m ２ 0.100g / m or more ２ 3. The thermal melt transfer ink ribbon according to claim 1, wherein the range is as follows:

4. 4. The thermal melt transfer ink ribbon according to claim 1, wherein the ink layer contains 20 parts by weight or more and 100 parts by weight or less of the toluenesulfonamide derivative per 100 parts by weight of nitrocellulose.

5. 5. The thermal melt transfer ink ribbon according to claim 1, wherein the ink layer contains nitrocellulose in an amount of from 10% by mass to 70% by mass of the entire ink layer.

6. 6. The thermal melt transfer ink ribbon according to claim 1, wherein the ink layer further contains at least one thermoplastic resin that is the same as the thermoplastic resin contained in the adhesive layer.

7. 7. The thermal melt transfer ink ribbon according to claim 1, wherein the toluenesulfonamide derivative contained in the ink layer is at least N-ethyl-o-toluenesulfonamide and N-ethyl-p-toluenesulfonamide.

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