JP2019064033A - Combination of thermal transfer image-receiving sheet and thermal transfer sheet - Google Patents

Abstract

To provide a combination of a thermal transfer image receiving sheet and a thermal transfer sheet, capable of concurrently solving a plurality of problems which may individually occur in each of the thermal transfer image receiving sheet and the thermal transfer sheet.SOLUTION: In a combination of a thermal transfer image receiving sheet 100 and a thermal transfer sheet, the thermal transfer image receiving sheet includes at least a substrate 1 and a receiver layer 2. The Martens hardness measured from the receiver layer-side is 20 N/mmor more. When printing is performed using a heating member under a printing pressure of 38 N at an applied voltage of 26.5 V, the maximum frictional force between the surface of the thermal transfer sheet in contact with the heating member and the heating member is 30 N or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a combination of a thermal transfer image receiving sheet and a thermal transfer sheet.

  As a means for forming a print having a thermal transfer image, a thermal transfer sheet having a color material layer and a thermal transfer image receiving sheet having a receptor layer are combined, energy is applied to the thermal transfer sheet, and the color material layer of the thermal transfer sheet contains There is known a sublimation thermal transfer system in which a sublimation dye is transferred to a receiving layer of a thermal transfer image receiving sheet to obtain a print having a thermal transfer image.

  Various proposals have been made, for example, as disclosed in Patent Documents 1 to 3 for the thermal transfer image-receiving sheet and the thermal transfer sheet used for such a sublimation thermal transfer type print product forming method.

JP, 2009-071931, A Patent No. 5534134 gazette Patent No. 2911517

  Although various developments have been made for both the thermal transfer image receiving sheet and the thermal transfer sheet in order to meet the recent complicated demands, it can not be said that they are sufficient.

  For example, in the case of a thermal transfer image receiving sheet, curling may occur during storage, embossing may occur when printing, or the paper serving as a support for the thermal transfer sheet may be lifted. There may be a problem such as occurrence of so-called formation unevenness.

  On the other hand, in the case of the thermal transfer sheet, there have been cases in which the occurrence of printing wrinkles or sticking during printing has become a problem.

  Although these problems in the thermal transfer image receiving sheet and the thermal transfer sheet may be individually solved one by one, these problems are often in a so-called trade-off relationship with one another. It was very difficult to solve at the same time.

  The present invention has been made under such circumstances, and in carrying out a sublimation thermal transfer printing method, a plurality of problems which may individually occur in the thermal transfer image receiving sheet and the thermal transfer sheet to be used may be simultaneously obtained. The main object of the present invention is to provide a thermal transfer image receiving sheet and a thermal transfer sheet combination that can be solved.

The present invention for solving the above problems is a combination of a thermal transfer image receiving sheet and a thermal transfer sheet, wherein the thermal transfer image receiving sheet includes at least a support and a receiving layer, and the martens measured from the receiving layer side Hardness is 20 N / mm ² or more, and the maximum of the surface of the thermal transfer sheet in contact with the heating member with the heating member when printing is performed with a printing pressure of 38 N and an applied voltage of 26.5 V using the heating member The frictional force is 30 N or less.

  In the above invention, the back layer may be located on the surface of the thermal transfer sheet in contact with the heating member.

  In the above invention, the thermal transfer image receiving sheet may consist of only the support and the receiving layer.

  In the above invention, the thermal transfer image-receiving sheet may consist of only the support, the primer layer, and the receiving layer.

  According to the combination of the thermal transfer image receiving sheet of the present invention and the thermal transfer sheet, it is possible to simultaneously suppress the occurrence of a plurality of problems which have conventionally arisen separately for the thermal transfer image receiving sheet and the thermal transfer sheet. More specifically, the occurrence of curling during storage of the thermal transfer image receiving sheet can be suppressed, and the occurrence of embossing during printing can be suppressed, and at the same time, the occurrence of printing wrinkles and sticking on the thermal transfer sheet can be suppressed.

It is a schematic sectional drawing which shows an example of the thermal transfer image receiving sheet concerning this embodiment. It is a schematic sectional drawing which shows an example of the thermal transfer image receiving sheet concerning this embodiment. It is a schematic sectional drawing which shows an example of the thermal transfer image receiving sheet concerning this embodiment. It is a schematic sectional drawing which shows an example of the thermal transfer image receiving sheet concerning this embodiment. It is a figure for demonstrating the measuring method of Martens hardness. It is a schematic sectional drawing which shows an example of the thermal transfer sheet concerning this embodiment. It is a schematic sectional drawing which shows an example of the thermal transfer sheet concerning this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention can be carried out in many different modes, and is not construed as being limited to the description of the embodiments exemplified below. In addition, the drawings may be schematically represented as to the thickness, shape, etc. of each layer as compared to the actual embodiment in order to clarify the description, but this is merely an example and limits the interpretation of the present invention. is not. In the specification of the present application and the drawings, the same elements as those described above with reference to the drawings in the drawings may be denoted by the same reference numerals, and the detailed description may be appropriately omitted.

-Thermal transfer image receiving sheet Hereinafter, a thermal transfer image receiving sheet (hereinafter sometimes referred to as "the thermal transfer image receiving sheet according to the present embodiment") constituting a combination of the thermal transfer image receiving sheet according to the embodiment of the present invention and the thermal transfer sheet. explain.

  1 to 4 are each a schematic cross-sectional view of a thermal transfer image-receiving sheet, which constitutes a combination of the thermal transfer image-receiving sheet and the thermal transfer sheet according to the embodiment of the present invention.

Here, as shown in FIGS. 1 to 4, the thermal transfer image receiving sheet 100 according to the present embodiment can have various laminated structures, and the structure is not limited, but any laminated structure may be used. The present invention is characterized in that the Martens hardness of the entire thermal transfer image receiving sheet 100 is 20 N / mm ² or more. As described above, by setting the Martens hardness of the thermal transfer image receiving sheet 100 to 20 N / mm ² or more, the thermal transfer image receiving sheet 100 is prevented from curling even when there is an environmental change due to long-term storage and the like. In addition to the above, even when printing is performed on the thermal transfer image receiving sheet 100, it is possible to suppress the formation of undesired emboss on the surface.

  FIG. 5 is a view for explaining a method of measuring Martens hardness of the thermal transfer image receiving sheet.

  The Martens hardness in the present specification is a value measured using a surface film physical property tester (PICODENTOR HM-500, Fisher Instruments Inc.), and a specific measuring method is as follows.

In this measurement method, using a diamond indenter (Vickers indenter) shown in FIG. 5 (a), as shown in FIG. 5 (b), a pyramidal indenter is pressed on the surface of the thermal transfer image receiving sheet to be measured. The surface area A (mm ² ) is calculated from the length of the diagonal of the indentation of the shape and the hardness is determined by dividing the test load F (N). The pushing conditions are as follows: at room temperature (laboratory environment temperature), as shown in FIG. 5 (c), a load from 0 mN to 5 mN is first applied for 10 seconds, then held for 5 seconds with a 5 mN load, and finally 5 mN To 0 mN in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F is said Martens hardness (N / mm < ² >).

  The Martens hardness of the thermal transfer image receiving sheet 100 in the present specification was measured by pressing a diamond indenter from the receiving layer side of the thermal transfer image receiving sheet.

The upper limit value of the Martens hardness of the thermal transfer image receiving sheet 100 according to this embodiment measured in this manner is not particularly limited, but is preferably, for example, about 30 N / mm ² or less. By setting the Martens hardness of the thermal transfer image receiving sheet 100 to 30 N / mm ² or less, it is possible to prevent the deterioration of the followability of the thermal transfer image receiving sheet to the heating member and to suppress the generation of printing blur.

Hereinafter, an example of a specific layer configuration of the thermal transfer image receiving sheet 100 according to the present embodiment having a Martens hardness of 20 N / mm ² or more will be described.

  As shown in FIGS. 1 to 4, the thermal transfer image receiving sheet 100 according to the present embodiment has one layer (FIG. 1) consisting of only the receptive layer 2 on one surface of the support 1 (upper surface in the illustrated embodiment). Reference) or two or more layers (refer FIGS. 2-4) including the receptive layer 2 are provided, and the receptive layer 2 exhibits the structure located in outermost surface. 1 to 4 are schematic cross-sectional views showing an example of the thermal transfer image receptor sheet of one embodiment, and the thermal transfer image receptor sheet 100 of the present invention is not limited to the illustrated embodiment. For example, in the thermal transfer image receiving sheet shown in FIGS. 1 and 2, the support 1 may have a multilayer structure, and in the thermal transfer image receiving sheet 100 shown in FIGS. 3 and 4, the primer layer 3 and the back layer 8 may be used. It is good also as composition which is not provided. In addition, the respective layers constituting the thermal transfer image-receiving sheet 100 shown in the respective drawings may be combined as appropriate to be different from the respective drawings.

(Support)
The support 1 of the thermal transfer image receiving sheet 100 is not particularly limited as long as it can support the receiving layer 2. The support 1 may have a single-layer structure as shown in FIGS. 1 and 2, or may have a multi-layer structure as shown in FIGS. 3 and 4. The support 1 of the form shown in FIG. 3 has a laminated structure in which a base 61, an adhesive layer 62, and a film 63 are laminated in this order. The support 1 shown in FIG. 4 has a laminated structure in which a film 63, an adhesive layer 62, a base 61, an adhesive layer 62, and a film 63 are laminated in this order. As the support 1 of a single layer structure, the support 1 which consists of the base material 61, the support 1 which consists of the film 63, etc. can be mentioned, for example.

  Examples of the base material 61 forming the support 1 having a multilayer structure include high-quality paper, coated paper, resin-coated paper, art paper, cast-coated paper, paperboard, synthetic paper (polyolefin-based or polystyrene-based), synthetic resin or emulsion Examples include impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internally added paper, cellulose fiber paper, etc., and films or sheets of various plastics such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate etc. it can. There is no particular limitation on the thickness of the substrate 61, and it is usually in the range of 10 μm to 300 μm. The range of 110 μm to 140 μm is particularly preferable. Moreover, a commercially available base material can also be used, For example, RC paper paper (STF-150 Mitsubishi Paper Industries, Ltd.), coated paper (Aurora coat Nippon Paper Industries, Ltd.), etc. can be used suitably.

  Examples of the film 63 forming the support 1 having a multilayer structure include polyesters with high heat resistance such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, polypropylenes, polycarbonates, cellulose acetates, polyethylene derivatives, plastics such as polyamides and polymethylpentenes. And a white opaque film formed by adding a white pigment and a filler to these synthetic resins.

  In addition, an adhesive layer 62 may be provided between the base 61 and the film 63. The adhesive layer 62 for bonding and bonding the substrate 61 and the film 63 includes an adhesive and has an adhesive function. Examples of the adhesive component include urethane resins, polyolefin resins such as α-olefin-maleic anhydride resins, polyester resins, acrylic resins, epoxy resins, urea resins, melamine resins, phenol resins, Examples include vinyl acetate resins and cyanoacrylate resins. Among them, reactive resins of acrylic resins and modified resins are preferably used. The adhesive is preferably cured using a curing agent, because the adhesive strength is improved and the heat resistance is also improved. As a curing agent, an isocyanate compound is generally used, but aliphatic amines, cyclic aliphatic amines, aromatic amines, acid anhydrides and the like can be used.

  The thickness of the adhesive layer 62 is usually in the range of 2 μm to 10 μm in the dry state. The adhesive layer is prepared by preparing a coating solution for an adhesive layer in which the adhesive exemplified above and the additive added as necessary are dispersed or dissolved in an appropriate solvent, and this coating solution is prepared by It can be applied and dried on the substrate 61.

  Also, instead of bonding the substrate 61 and the film 63 using the adhesive layer 62, the substrate 61 and the film 63 may be bonded by EC sand lamination using polyethylene or the like.

(Receptive layer)
In the thermal transfer image receiving sheet 100 according to the present embodiment, the receptive layer 2 is positioned on the surface (upper surface in FIGS. 1 to 4), but the receptive layer 2 is also particularly limited. However, it can be appropriately selected from conventionally known receptive layers on the condition that the Martens hardness of the entire thermal transfer image receiving sheet 100 is 20 N / mm ² or more.

  For example, as a binder resin having a dye-receptive property constituting the receptor layer 2, vinyl chloride resins, polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride Vinyl acetate copolymers, vinyl resins such as ethylene-vinyl acetate copolymer or polyacrylate, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, olefins such as ethylene or propylene And copolymer resins with other vinyl polymers, polycarbonate and the like. The receptor layer 2 may contain one type, or two or more types as a binder resin having dye receptivity. In addition, in the receiving layer 2, various additives typified by inorganic pigments may be added in addition to the above-mentioned binder resin.

  There is no particular limitation on the method of forming such a receptor layer 2, and a binder resin having dye receptivity, an inorganic pigment, and any optional additive added as necessary may be dispersed or dissolved in a suitable solvent. A layer coating liquid can be prepared, and the coating liquid can be formed by coating and drying on the support 1 or an optional layer (for example, the primer layer 3) provided on the support 1. The coating method for the receiving layer coating solution is not particularly limited, and a conventionally known coating method can be appropriately selected and used. Examples of the coating method include a gravure printing method, a screen printing method, a reverse coating method using a gravure plate, and the like. Moreover, the application method other than this can also be used. The same applies to the coating methods of various coating liquids described later.

(Primer layer)
In the thermal transfer image receiving sheet 100 according to the present embodiment, as shown in FIGS. 2 to 4, the primer layer 3 may be provided between the support 1 and the receiving layer 2. The primer layer 3 is also not particularly limited, and can be appropriately selected from conventionally known primer layers provided that the Martens hardness of the entire thermal transfer image-receiving sheet 100 is 20 N / mm ² or more.

  The binder resin constituting the primer layer 3 is also not particularly limited, and examples thereof include polyurethane resin, acrylic resin, polyethylene resin, polypropylene resin, epoxy resin, polyester resin and the like. Moreover, the binder resin which has adhesiveness other than this can also be selected suitably, and can be used. The primer layer 3 may contain 1 type individually as binder resin, and may contain 2 or more types. The primer layer 3 may be a water-dispersed primer layer or a solvent-dispersed primer layer.

  The thickness of the primer layer 3 is also not particularly limited, but is preferably in the range of 0.1 μm to 20 μm.

(Back layer)
In the thermal transfer image receiving sheet 100 according to the present embodiment, as shown in FIG. 3 and FIG. 4, the back surface layer 8 is provided on the surface of the support 1 opposite to the side on which the receiving layer 2 is provided. It may be

  As the back surface layer 8, one having a desired function can be appropriately selected and used according to the application and the like of the thermal transfer image receiving sheet 100 of one embodiment. Among them, it is preferable to use the back surface layer 8 having the transportability improvement function of the thermal transfer image receiving sheet 100, the curl prevention function, and the writing property. As the back layer 8 having such a function, among resins such as acrylic resins, cellulose resins, polycarbonate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyamide resins, polystyrene resins, polyester resins, halogenated polymers, etc. Used as additives, as well as organic fillers such as nylon filler, acrylic filler, polyamide filler, fluorine filler, polyethylene wax, amino acid powder, and inorganic fillers such as silicon dioxide and metal oxides it can. Moreover, what hardened these resin by hardening | curing agents, such as an isocyanate compound and a chelate compound, can be used as a back surface layer. The thickness of the back surface layer 8 is usually in the range of 0.1 μm to 20 μm, preferably in the range of 0.5 μm to 10 μm. A back surface primer layer (not shown) may be provided between the support 1 and the back surface layer 8.

In the thermal transfer image receiving sheet 100 according to the present embodiment, as described above, the layer configuration is not particularly limited, but as shown in FIGS. 1 to 4, a heat insulating layer having a so-called void structure is provided. Preferably, as shown in FIG. 1, the thermal transfer image receiving sheet 100 is composed of only the support 1 and the receptive layer 2, or as shown in FIG. It is preferred that the layer 3 and the receptive layer 2 only be constituted. When a heat insulating layer having a void structure is provided, it may be difficult to make the Martens hardness of the entire thermal transfer image receiving sheet 100 20 N / mm ² or more. When a heat insulation layer having a void structure is provided, it is necessary to provide a film on both sides of the support or to thicken the resin layer of the resin coated paper on the opposite side to which the film is provided, in order to maintain curl balance. It is because it becomes disadvantageous in manufacturing cost.

Thermal Transfer Sheet Next, a thermal transfer sheet (hereinafter, sometimes referred to as “a thermal transfer sheet according to the present embodiment”) constituting a combination of the thermal transfer image receiving sheet according to the embodiment of the present invention and the thermal transfer sheet will be described. Do.

  6 to 7 are each a schematic cross-sectional view of a thermal transfer sheet constituting a combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to the embodiment of the present invention.

  Here, the thermal transfer sheet 200 according to the present embodiment can take various laminated structures as in the thermal transfer image receiving sheet 100 described above, and the structure is not limited, but any of the laminated structures. Even when using a heating member, when printing is performed with a printing pressure of 38 N and an applied voltage of 26.5 V, the maximum friction force with the heating member on the surface of the thermal transfer sheet 200 in contact with the heating member is 30 N or less It has a feature. As described above, by setting the maximum frictional force between the surface of the thermal transfer sheet 200 in contact with the heating member and the heating member to 30 N or less, the occurrence of printing wrinkles and sticking can be effectively suppressed at the time of print formation.

The maximum frictional force in the present specification is the maximum frictional force when an image is printed under the following printing conditions using a thermal transfer printer with a frictional force measuring function described in JP-A 2003-300338.
<Print conditions>
-Thermal head: Toshiba Hokuto Electronics Co., Ltd. thermal head-Heating element average resistance value: 5020 Ω
・ Printing density in the main scanning direction: 300 dpi (dots per inch)
・ Printing density in the sub scanning direction: 300 dpi (dots per inch)
Line period: 1 msec. / Line
・ Pulse duty ratio: 90%
・ Press pressure: 38 N
・ Applied voltage: 26.5 V
Print image: A STEP image having 16 gradations in a size of 1388 pixels in width × 945 pixels in length.

  The maximum frictional force with the heating member on the surface of the thermal transfer sheet 200 according to the embodiment measured in this manner and in contact with the heating member is 24 N or less from the viewpoint of more exerting the above-mentioned effects. Particularly preferred.

  An example of a specific layer configuration of the thermal transfer sheet 200 according to the present embodiment will be described below.

  The thermal transfer sheet 200 according to the present embodiment shown in FIG. 6 has a configuration in which the base material 21 and the coloring material layer 22 are laminated in this order, and the thermal transfer sheet 200 shown in FIG. 21 has a configuration in which the peeling layer 23, the protective layer 24, and the coloring material layer 22 are laminated in this order. The thermal transfer sheet 200 shown in FIGS. 6 and 7 is an example, and the present invention is not limited to these configurations. For example, although the thermal transfer sheet 200 shown in FIG. 7 is an example of a thermal transfer type thermal transfer sheet, in the case of a sublimation type thermal transfer sheet, the back layer 25, the substrate 21, the peeling layer 23, and the protective layer 24 are A portion having a configuration in which the layers are stacked in this order and a portion having a configuration in which the back layer 25, the base 21, and the color material layer 22 are stacked in this order may be arranged (not shown) .

  Further, in the thermal transfer sheet 200 according to the present embodiment, the surface in contact with the heating member is the surface of the base 21 on which the color material layer 22 is not provided in the thermal transfer sheet 200 shown in FIG. 6 is the lower surface), and in the case of the thermal transfer sheet 200 shown in FIG. 7, it is the surface of the back layer 25 not in contact with the substrate 21 (the lower surface in FIG. 7).

(Base material)
There is no particular limitation on the substrate 21 constituting the thermal transfer sheet 200 according to the present embodiment, and any conventionally known substrate may be appropriately selected as long as it has heat resistance and mechanical properties without any problem in handling. Can be used. Examples of such a substrate 21 include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyarylates, polycarbonates, polyurethanes, polyimides, polyetherimides, cellulose derivatives, polyethylenes, ethylene-vinyl acetate copolymers, polypropylenes, polystyrenes, etc. Acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene- Ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene It can include various plastic films or sheets such as polyvinylidene fluoride. Each of these materials can be used alone, but may be used as a laminate in combination with other materials. The thickness of the substrate 21 can be appropriately set according to the material so that the strength and heat resistance thereof become appropriate, and is generally about 2.5 μm to 100 μm.

  Moreover, as for the base material 21, the adhesion | attachment process may be performed to the surface in which the peeling layer 23 mentioned later is formed. By performing the adhesion process, the adhesion between the base 21 and the release layer 23 can be improved. As the adhesion treatment, for example, known resin surfaces such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet light treatment, surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, grafting treatment, etc. The modification technology can be applied as it is. Also, two or more of these treatments can be used in combination.

  In the case where the surface of the base 21 on which the color material layer 22 is not provided is the surface in contact with the heating member as shown in FIG. 6, the surface of the base 21 and the heating member It is necessary to select a material or to apply some treatment so that the maximum friction force with this is 30 N or less.

  Specifically, the base material 21 may be made of a resin having a melting point of 100 ° C. or more and 250 ° C. or less, or the lubricant may be uniformly dispersed in the resin forming the base material 21.

(Peeling layer)
The thermal transfer sheet 200 according to the present embodiment may have a peeling layer 23. The release layer 23 is an optional layer and is not necessarily a necessary layer. Therefore, although not shown, the release layer 23 may be replaced with a release layer.

  The material for forming the peeling layer 23 is not particularly limited, and can be appropriately selected from those used in conventionally known thermal transfer sheets. For example, waxes, silicone waxes, silicone resins, silicone modified resins, fluorine resins, fluorine modified resins, polyvinyl alcohols, acrylic resins, thermally crosslinkable epoxy-amino resins, and thermally crosslinkable alkyd-amino resins can be mentioned. One of these resins may be used alone, or two or more thereof may be used in combination.

  Further, the thickness of the peeling layer 13 is not particularly limited, but generally in the range of 0.5 μm to 5 μm.

(Protective layer)
The thermal transfer sheet 200 according to the present embodiment may have a protective layer 24. This protective layer 24 is also an optional layer as in the case of the release layer 23, and is not necessarily a necessary layer.

  The material for forming the protective layer 24 is not particularly limited, and can be selected appropriately from those used in conventionally known thermal transfer sheets. For example, ultraviolet absorber copolymer resin, acrylic resin, polyester resin, polycarbonate resin, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, polyvinyl chloride resin, polyvinyl acetate -Based resin, vinyl chloride-vinyl acetate copolymer, acid-modified polyolefin resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin Resins, polybutadiene resins, rubber compounds and the like can be mentioned. One of these resins may be used alone, or two or more thereof may be used in combination. In addition, fillers such as micro silica and polyethylene wax may be used in combination.

  The thickness of the protective layer 24 is not particularly limited, but is generally in the range of 0.5 μm to 5 μm.

(Color material layer)
The thermal transfer sheet 200 according to the present embodiment has a color material layer 22. The color material layer 22 is an essential layer in the thermal transfer sheet 200.

  The color material layer 22 may be a so-called heat melting type color material layer, or may be a sublimation type color material layer, and as components constituting the color material layer 22, various kinds such as pigments and dyes may be used. Various additives such as coloring materials, binders and mold release agents can be mentioned.

  The coloring material can be appropriately selected from known organic or inorganic pigments or dyes. For example, those having a sufficient coloring material concentration and not discoloring or fading due to light, heat or the like are preferable. Further, it may be a substance that develops a color upon heating, or a substance that develops a color upon contact with a component applied to the surface of a transferee. Furthermore, the color of the colorant is not limited to cyan, magenta, yellow and black, and colorants of various colors can be used.

  Examples of the wax component used as a binder include microcrystalline wax, carnauba wax and paraffin wax. Furthermore, various kinds of Fischer-Tropsch wax, various low molecular weight polyethylenes, wood wax, beeswax, bees wax, ivory wax, wool wax, shellac wax, candelilla wax, petrolactam, polyester wax, partially modified wax, fatty acid ester, fatty acid amide, etc. Can be mentioned.

  Moreover, as a resin component used as a binder, For example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, polyethylene resin, polystyrene resin, polypropylene resin, polybuden resin, petroleum resin, vinyl chloride resin, chloride Vinyl-vinyl acetate copolymer, polyvinyl alcohol resin, vinylidene chloride resin, acrylic resin, methacrylic resin, polyamide resin, polycarbonate resin, fluorine resin, polyvinyl formal resin, polyvinyl butyral resin, acetyl cellulose resin, nitrocellulose resin, poly acetic acid Vinyl resin, polyisobutylene resin, ethyl cellulose resin or polyacetal resin may be mentioned, but in particular, the relatively low softening point conventionally used as a heat sensitive adhesive, for example, 50 ° C. or more 8 ℃ preferably those having a softening point below.

  As various additives, for example, in order to impart good thermal conductivity to the color material layer 22, a thermally conductive substance may be blended as an additive of the binder. Examples of such additives include carbonaceous materials such as carbon black, metals such as aluminum, copper, tin oxide and molybdenum disulfide, and metal compounds.

  The method for forming the color material layer 22 is not particularly limited. For example, a color material coating liquid is prepared by dissolving or dispersing the color material, the binder, and various additives added as necessary in a solvent such as water, an organic solvent, etc. It can form by apply | coating and drying on one side of the base material 21, or on the peeling layer 23 and the protective layer 24 using a coating means.

  The thickness of the color material layer can be appropriately set within the range in which the necessary printing density and thermal sensitivity can be achieved, and the thickness is not particularly limited, but is preferably in the range of 0.1 μm to 30 μm. About 3 micrometers or more and 20 micrometers or less are more preferable.

(Back layer)
In the thermal transfer sheet 200 according to the present embodiment, as shown in FIG. 7, the back layer 25 is provided on the surface of the base 21 on which the coloring material layer 22 is not provided, that is, the surface in contact with the heating member. You may provide. In this case, the condition is that the maximum frictional force between the back layer 25 and the heating member is 30 N or less. By providing such a back layer 25, there is no need to consider the maximum frictional force with the heating member in selecting the base 21, so the degree of freedom in selecting the base 21 can be enhanced.

  Such a back layer 25 can be formed preferably using, for example, a binder resin to which a lubricant, a surfactant, inorganic particles, organic particles, a pigment, and the like are added. The binder resin used for the back layer 25 is, for example, ethyl cellulose resin, hydroxyethyl cellulose resin, hydroxypropyl cellulose resin, methyl cellulose resin, methyl cellulose resin, cellulose acetate resin, cellulose acetate butyrate resin, cellulose resin such as cotton nitrate, polyvinyl alcohol resin, poly Vinyl acetate resin, polyvinyl butyral resin, polyvinyl acetal resin, polyvinyl pyrrolidone resin, acrylic resin, polyacrylamide resin, vinyl resin such as acrylonitrile-styrene copolymer, polyester resin, polyurethane resin, silicone modified or fluorine modified urethane resin, etc. It can be mentioned.

  Among these, it is preferable to use a cross-linked resin by using several reactive groups, for example, those having a hydroxyl group, in combination with a polyisocyanate as a cross-linking agent. The means for forming the back layer is not particularly limited. For example, a material obtained by adding a lubricant, surfactant, inorganic particles, organic particles, pigments and the like to a binder resin is dissolved or dispersed in an appropriate solvent. The coating liquid is prepared, and this is applied and dried on the surface of the base 21 opposite to the surface on which the color material layer 22 is provided, using a conventionally known coating method. it can.

  The thickness of the back layer 25 is not particularly limited, but is usually about 0.01 μm to 10 μm in the dry state.

  In order to set the maximum frictional force between the back layer 25 and the heating member to 30 N or less, for example, one having a melting point of 100 ° C. or more and 250 ° C. or less is selected from the above mentioned resins, or The lubricant may be dispersed uniformly.

Method for Producing a Printed Article The method for producing a printed article using a combination of the thermal transfer image receiving sheet 100 according to the present embodiment described above and the thermal transfer sheet 200 is not particularly limited. Therefore, printed products can be manufactured using various conventionally known printers. In the thermal transfer image receiving sheet 100 according to the present embodiment, since the Martens hardness is 20 N / mm ² or more, the printing pressure can be designed to be high, thereby suppressing the occurrence of so-called formation unevenness and embossing.

  Hereinafter, the thermal transfer image receiving sheet according to the embodiment of the present invention will be described by citing examples and comparative examples. In addition, "part" in a sentence is a mass reference | standard unless there is particular notice. In addition, the compounding quantity of the component which has a solid content ratio has shown the mass before converting into solid content.

Preparation of Thermal Transfer Image-Receiving Sheet A A coated paper (thickness 175 μm, icoat 180 (Daio Paper Co., Ltd.) was prepared as a support, and the coating liquid 1 for the receptor layer shown below was dried on one side thereof. By forming a receiving layer by coating and drying so as to have a thickness of 2.5 μm, a thermal transfer image-receiving sheet A in which the support and the receiving layer are laminated in this order was obtained.

<Coating fluid for receptive layer 1>
・ Vinyl chloride-vinyl acetate copolymer 20 parts (Solvaine (registered trademark) CNL Nisshin Chemical Industry Co., Ltd.)
・ Epoxyaralkyl modified silicone oil 0.4 parts (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
-Methyl ethyl ketone 70 parts-Toluene 70 parts

The Martens hardness of the thermal transfer image receiving sheet A was measured and found to be 22.2 N / mm ² .

Preparation of Thermal Transfer Image-Receiving Sheet B In the same manner as the thermal transfer image-receiving sheet A except for using a resin-coated paper (thickness 190 μm, R-STF-NB-155B (Kitakami Tech Paper Co., Ltd.)) as a support,
A thermal transfer image receiving sheet B was obtained.

The Martens hardness of the thermal transfer image receiving sheet B was measured and found to be 23.4 N / mm ² .

Preparation of Thermal Transfer Image-Receiving Sheet C A thermal transfer image-receiving sheet C was obtained in the same manner as the thermal transfer image-receiving sheet A except that a resin-coated paper (208 μm in thickness) was used as a support.

The Martens hardness of the thermal transfer image receiving sheet C was measured and found to be 23.5 N / mm ² .

Preparation of thermal transfer image-receiving sheet D A resin-coated paper (thickness 208 μm) is prepared as a support, and coated on one side with a primer layer coating solution 1 of the following composition so that the thickness after drying is 1 μm. By drying to form a primer layer, the receiving layer coating liquid 1 having the above composition is applied and dried on the primer layer so that the thickness after drying is 2.5 μm, thereby forming a receiving layer. A thermal transfer image-receiving sheet D was obtained, in which the support, the primer layer and the receiving layer were laminated in this order.

<Coating fluid for primer layer 1>
-Urethane resin 12.6 parts (Nipporan (registered trademark) Tosoh Corporation)
-6.3 parts of titanium dioxide (TCA 888 Corporation Tochem Products)
・ Fluorescent whitening agent 0.1 part (Ubitex (registered trademark) OB BASF Japan Ltd.)
-Isocyanate 1.0 part (CORONATE (registered trademark) HX Tosoh Corporation)
-80 parts of methyl ethyl ketone

The Martens hardness of the thermal transfer image receiving sheet D was measured and found to be 23.3 N / mm ² .

Preparation of Thermal Transfer Image-Receiving Sheet E A porous polyolefin film (SP-U Mitsui Chemicals Tosoh Co., Ltd.) having a thickness of 35.8 μm is used as the surface-side polyolefin resin layer, and the coating liquid 1 for the receptor layer shown above is formed thereon. Then, a receptor layer was formed by coating and drying so that the thickness after drying was 2.5 μm, to obtain a laminate in which the porous surface side polyolefin resin layer and the receptor layer were laminated in this order. Subsequently, the laminate obtained above is bonded on one side of a core paper (Utorillo 157 Nippon Paper Industries Co., Ltd.) having a thickness of 130 μm using an adhesive layer coating liquid of the following composition, and A receptive layer is formed by bonding an 18 Pm thick OPP film (HO 402 sum solvent industry) as the back side polyolefin resin layer to the other surface of the above-mentioned core material paper using an adhesive layer coating liquid of the following composition. A thermal transfer image-receiving sheet E was obtained in which the porous surface side polyolefin resin layer, the adhesive layer, the core paper, the adhesive layer, and the back side polyolefin resin layer were laminated in this order. The thickness of each adhesive layer was 2.4 μm.

<Coating fluid for adhesive layer>
-30 parts of polyol resin (Takelac (registered trademark) A-969V Mitsui Chemical Co., Ltd.)
-Isocyanate 10 parts (Takenate (registered trademark) A-5 Mitsui Chemical Co., Ltd.)
-60 parts of ethyl acetate

The Martens hardness of the thermal transfer image receiving sheet E was measured and found to be 18.8 N / mm ² .

Preparation of Thermal Transfer Image-Receiving Sheet F A porous polyolefin film (SP-U Mitsui Chemicals Tosoh Co., Ltd.) having a thickness of 35.8 μm is used as the surface-side polyolefin resin layer, and the coating liquid 1 for the receptor layer shown above is formed thereon. Then, a receptor layer was formed by coating and drying so that the thickness after drying was 2.5 μm, to obtain a laminate in which the porous surface side polyolefin resin layer and the receptor layer were laminated in this order. Next, on one side of a 156 μm thick core paper (non-coated K4-156 Kitakami High-Tech Paper Co., Ltd.), a first polyethylene resin with a density of 0.956 g / cm ³ (Novatec HD HS471 Nippon Polyethylene Co., Ltd.) And a second polyethylene resin (Novatec HD LC600A Japan Polyethylene Co., Ltd.) whose density is 0.93 g / cm ³ or less, and the total mass of the first polyethylene resin and the second polyethylene resin. It mixed so that the mass ratio of the said 1st polyethylene resin with respect to 80% may become, and it extrusion-molds (EC) process, and forms the polyethylene resin layer with a thickness of 24 micrometers. Further, a support was formed on the other surface of the EC processed surface of the core paper so that the second polyethylene resin had a thickness of 14 μm. The porous polyolefin resin layer of the laminate obtained above and the polyethylene resin layer having a thickness of 14 μm of the support were pasted using the adhesive layer coating liquid shown above to obtain a thermal transfer image receiving sheet E . The thickness of the adhesive layer was 2.4 μm.

The Martens hardness of the thermal transfer image receiving sheet F was measured and found to be 14.6 N / mm ² .

Preparation of Thermal Transfer Image-Receiving Sheet G A porous polyolefin film (SP-U Mitsui Chemicals Tosoh Co., Ltd.) with a thickness of 23.8 μm is used as the surface-side polyolefin resin layer, and the coating fluid 1 for the receptor layer shown above is formed thereon. It applied and dried so that the thickness after drying might be 2.5 micrometers, and formed the receiving layer, and obtained the layered product by which the porous surface side polyolefin resin layer and the receiving layer were laminated in this order. Using the adhesive layer coating liquid shown above, the resin coated paper (thickness 205 μm, RC4 (Kitakami High-Tech Paper Co., Ltd.) as a support and the porous polyolefin resin layer side of the laminate obtained above) The thermal transfer image-receiving sheet G was obtained, and the thickness of the adhesive layer was 2.4 μm.

The Martens hardness of the thermal transfer image receiving sheet G was measured to be 15.5 N / mm ² .

Preparation of Thermal Transfer Sheet a As a substrate, a PET film of 4.5 μm in thickness was used, and on this, a coating solution 1 for the back layer having the following composition was coated to a dry thickness of 0.5 μm. It dried and formed the back layer. Next, on the side opposite to the side provided with the back layer of the substrate, the coating solution for dye primer layer of the following composition is applied and dried so that the thickness after drying becomes 0.10 μm, and the dye primer layer Formed. Subsequently, a colorant material layer was formed on the dye primer layer by coating and drying a coating material for a colorant material layer having the following composition so that the thickness after drying was 0.55 μm, to obtain a thermal transfer image receiving sheet a. .

<Coating fluid for back layer 1>
-Polyvinyl acetal resin 90.3 parts (S-LEC (registered trademark) KS-1 Sekisui Chemical Co., Ltd.)
Polyisocyanate (solid content 45%) 3.1 parts (Burnock (registered trademark) D-750 DIC Corporation)
· Stearyl phosphate zinc 10 parts (LBT-1830 refined, Fuso Chemical Industry Co., Ltd.)
-10 parts of zinc stearate (SZ-PF Sakai Chemical Industry Co., Ltd.)
-Linear polyethylene WAX 3 parts (Poly wax 3000 T-10 TOYO ADDRESS Co., Ltd.)
・ Ethoxylated alcohol-modified WAX 7 parts (UNITOX 750 Toyo Address Co., Ltd.)
-Talc 3 parts (Micro Ace (registered trademark) P-3 Nippon Talc Industry Co., Ltd.)
・ Methyl ethyl ketone 400 parts ・ Toluene 100 parts

<Coating fluid for dye primer layer>
・ Alumina sol (solid content 10%) 50 parts (alumina sol 200 (feather-like form) Nissan Chemical Industries, Ltd.)
Polyvinyl pyrrolidone resin (K-90 ASP Japan Co., Ltd.) 5 parts Water 25 parts Isopropyl alcohol 20 parts

<Coating fluid for color material layer>
C. I. Solvent Blue 63 6 parts · Polyvinyl acetal resin 4 parts (S-LEC (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
Toluene 45 parts Methyl ethyl ketone 45 parts

· Thermal transfer sheet b
A thermal transfer image receiving sheet b was obtained in the same manner as the thermal transfer sheet a except that the rear layer was formed using the rear layer coating solution 2 having the following composition instead of the rear layer coating solution 1. .

<Coating fluid 2 for back layer>
-Polyvinyl acetal resin 90.3 parts (S-LEC (registered trademark) KS-1 Sekisui Chemical Co., Ltd.)
Polyisocyanate (NCO = 17.3 mass%) 3.1 parts (Burnock® D750 DIC Corporation)
・ Silicone resin fine particles (particle diameter: 4 μm, polygonal shape) 0.62 parts (Tospearl 240 Momentive Performance Materials Japan GK)
-10 parts of zinc stearyl phosphate (LBT 1830 refined Fuso Chemical Industry Co., Ltd.)
-10 parts of zinc stearate (SZ-PF Sakai Chemical Industry Co., Ltd.)
・ Polyethylene wax 3 parts (Poly wax 3000 TOYO ADDRESS Co., Ltd.)
・ Ethoxylated alcohol-modified wax 7 parts (UNITOX 750 TOYO ADR CO., LTD.)
・ Methyl ethyl ketone 400 parts ・ Toluene 100 parts

· Thermal transfer sheet c
A thermal transfer image receiving sheet c was obtained in the same manner as the thermal transfer sheet a except that the rear layer was formed using the rear layer coating solution 3 having the following composition instead of the rear layer coating solution 1. .

<Coating fluid 3 for back layer>
-Polyvinyl butyral resin 6.0 parts (S-LEC (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
-Polyisocyanate curing agent 22.0 parts (Barnock D (registered trademark) 750-45 Solid content 45% DIC Corporation)
-Phosphoric ester 3.0 parts (Plysurf (registered trademark) A-208N Dai-ichi Kogyo Seiyaku Co., Ltd.)
-Talc 1.0 part (Micro Ace (registered trademark) P-3 Nippon Talc Industry Co., Ltd.)
・ Methyl ethyl ketone 60.0 parts ・ Toluene 60.0 parts

(Examples 1 to 5 and Comparative Examples 1 to 4)
By combining the above thermal transfer image receiving sheets A to F and the thermal transfer sheets a to b as shown in Table 1 below, a combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to Examples 1 to 5 and Comparative Examples 1 to 4 is obtained. The

(Maximum frictional force)
In the combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to Examples 1 to 5 and Comparative Examples 1 to 4, the maximum frictional force of the back layer of the thermal transfer sheet was measured. The results are shown in Table 1 below.

(Evaluation of curl environmental change)
A semi-black pattern was formed using a sublimation thermal transfer printer (DS-RX1 Dai Nippon Printing Co., Ltd.) using each of the thermal transfer image receiving sheet and the thermal transfer sheet according to Examples 1 to 5 and Comparative Examples 1 to 4 in combination. I printed it. The print was stored in an environment of 40 ° C. and 90% for 100 hours, and the difference in the average distance of the four corners of the print before and after storage was calculated from the table, and curl evaluation was performed according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: 0 mm or more and less than 10 mm B: 10 mm or more and less than 20 mm NG: 20 mm or more

(Emboss evaluation)
With respect to the printed matter formed by the evaluation of the change in the curl environment, the unevenness at the boundary between the black solid and the white solid was visually evaluated. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: Unevenness is not confirmed.
NG: unevenness is confirmed.

(Print wrinkle evaluation)
The print wrinkles evaluation was performed with the following evaluation criteria with respect to the printed matter formed by evaluation of the said curl environmental change. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: No wrinkles have occurred at all.
B: Mild wrinkles have occurred on part of the print.
Although wrinkles in the part of the C ··· printed matter has occurred, it is the extent there is no problem in practical use.
NG: wrinkles have occurred on the entire print.

(Sticking evaluation)
The sticking evaluation was performed to the printed matter formed by evaluation of the said curl environmental change on the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: No sticking has occurred at all.
B: Mild sticking occurred on part of the print.
C · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · printing on part of the print is sticking, but there is no problem in practical use.
NG: sticking has occurred on the whole of the print.

(Unified ground evaluation)
Using each of the thermal transfer image-receiving sheet and the thermal transfer sheet according to Examples 1 to 5 and Comparative Examples 1 to 4 and using a sublimation thermal transfer printer (DS-RX1 Dai Nippon Printing Co., Ltd.), 16 steps A STEP image having a tone was printed, and this printed matter was evaluated for uneven coverage under the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: There is no occurrence of unevenness in the printed matter.
B · · · A slight unevenness in the appearance of the print has occurred.
C: Moderate formation unevenness occurs in the printed matter, but there is no problem in practical use.
NG · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · printing unevenness is occurring in severe print.

DESCRIPTION OF SYMBOLS 100 ... Thermal transfer image receiving sheet 1 ... Support body 2 ... Receiving layer 3 ... Primer layer 8 ... Back surface layer 61 ... Base material 62 ... Adhesive layer 63 ... Film 200 ... Thermal transfer sheet 21 ... Base material 22 ... Color material layer 23 ... Peeling layer 24 ... Protective layer 25 ... Back layer

Claims (4)

A combination of a thermal transfer image receiving sheet and a thermal transfer sheet,
The thermal transfer image receiving sheet includes at least a support and a receiving layer, and the Martens hardness measured from the receiving layer side is 20 N / mm ² or more.
The maximum friction of the surface of the thermal transfer sheet in contact with the heating member with the heating member is 30 N or less when printing is performed at a printing pressure of 38 N and a voltage of 26.5 V using the heating member.
A combination of a thermal transfer image-receiving sheet and a thermal transfer sheet characterized in that A back layer is positioned on a surface of the thermal transfer sheet in contact with the heating member.
A combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to claim 1. The thermal transfer image receiving sheet comprises only a support and a receptive layer,
A combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to claim 1 or 2. The thermal transfer image receiving sheet comprises only a support, a primer layer, and a receiving layer,
A combination of the thermal transfer image receiving sheet and the thermal transfer sheet according to claim 1 or 2.

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