JP2018058210A - Intermediate transfer medium, and method of forming printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate transfer medium having excellent transferability in transferring a transfer layer including a receiving layer, and a method of forming printed matter using the intermediate transfer medium.SOLUTION: An intermediate transfer medium has, on a base material 1, a transfer layer 5 so that it can be peeled from the base material 1. The transfer layer 5 has a peeling layer 3 nearest to the base material 1 and a receiving layer 4 farthest from the base material 1, the peeling layer containing a cellulose resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an intermediate transfer medium and a printed material forming method.

  As a medium for forming a printed material without being restricted by the transfer target, an intermediate in which a transfer layer in which a protective layer and a receiving layer are laminated in this order from the substrate side is provided on the substrate. A transfer medium or the like is used (for example, Patent Document 1). According to the intermediate transfer medium, a thermal transfer sheet having a color material layer is used to form a thermal transfer image on the receiving layer located on the outermost surface of the intermediate transfer medium, and then the receiving layer on which the thermal transfer image is formed is included. By transferring the transfer layer onto an arbitrary transfer target, a printed material having a thermal transfer image formed on the transfer target can be obtained.

  The above-mentioned intermediate transfer medium is required to have good transferability when the transfer layer including the receiving layer on which the thermal transfer image is formed is transferred onto the transfer target. As the transfer property of the transfer layer is lowered, when the transfer layer is transferred onto the transfer medium, the base material of the intermediate transfer medium and the transfer layer are thermally fused, and the transfer layer is peeled off from the base material. Transfer failure that cannot be performed, or the transfer layer that should be transferred at the interface with the base material is peeled off between any layers constituting the transfer layer and should be transferred onto the transfer target A transfer defect in which the entire transfer layer or a part of the transfer layer remains on the substrate side is likely to occur.

  In addition, recently, there is a demand to obtain a printed matter with high design using an intermediate transfer medium.

JP 2012-71545 A

  The present invention has been made in view of such circumstances, and provides an intermediate transfer medium having good transferability of a transfer layer, and a method for forming a print using the intermediate transfer medium. Let it be the main issue.

  The present invention for solving the above-mentioned problems is an intermediate transfer medium in which a transfer layer is provided on a base material so as to be peelable from the base material, and the transfer layer is a layer constituting the transfer layer. The laminate layer is located closest to the substrate and the receptor layer is located farthest from the substrate. The release layer contains a cellulosic resin. .

  Further, the cellulose resin may be one or both of a cellulose acetate butyrate resin and a cellulose acetate propionate resin.

  Moreover, this invention for solving the said subject is a formation method of the printed matter using an intermediate transfer medium, Comprising: The transfer layer was provided on the 1st base material so that peeling from the said 1st base material was possible. An intermediate transfer medium preparation step for preparing an intermediate transfer medium, a thermal transfer sheet preparation step for preparing a thermal transfer sheet in which a first color material layer and a second color material layer are provided in a surface sequence on a second substrate, and a transfer target A transfer body preparation step for preparing a body, and the transfer layer of the intermediate transfer medium prepared in the intermediate transfer medium preparation step includes a release layer positioned closest to the first substrate; The receiving layer located farthest from the first base material, and the release layer contains a cellulosic resin, and the first color material layer of the thermal transfer sheet is used for the intermediate transfer medium. A first image forming step of forming a first image on the receiving layer; After the image forming step, the peeling of the intermediate transfer medium using the transfer layer transfer step of transferring the transfer layer of the intermediate transfer medium onto the transfer member and the second color material layer of the thermal transfer sheet. And a second image forming step of forming a second image on the layer.

  In the method for forming a printed matter, the thermal transfer sheet is a thermal transfer sheet in which the first color material layer, the heat seal layer, and the second color material layer are provided in the surface order on the second base material. The method further comprises a heat seal layer transfer step for transferring the heat seal layer of the thermal transfer sheet onto the transfer layer on which the first image is formed after the first image forming step, and in the transfer layer transfer step, The transfer layer on which the first image is formed may be transferred onto the transfer target body so that the transfer target body and the heat seal layer are in direct contact with each other.

  According to the intermediate transfer medium of the present invention, the transferability when transferring a transfer layer including a receiving layer can be improved. In addition, according to the method for forming a print product of the present invention, a print product in which the transfer layer is transferred onto the transfer medium with good transferability can be obtained.

It is a schematic sectional drawing which shows an example of the intermediate transfer medium of one Embodiment. It is a schematic sectional drawing which shows an example of the intermediate transfer medium of one Embodiment. It is a schematic sectional drawing which shows an example of a thermal transfer sheet. It is a schematic sectional drawing which shows an example of a thermal transfer sheet. It is a schematic sectional drawing which shows an example of a thermal transfer sheet. It is process drawing for demonstrating the formation method of the printed matter of one Embodiment, (a)-(d) is a schematic sectional drawing. It is process drawing for demonstrating the formation method of the printed matter of one Embodiment, (a)-(e) is a schematic sectional drawing.

<< Intermediate transfer medium >>
Hereinafter, an intermediate transfer medium according to an embodiment of the present invention (hereinafter referred to as an intermediate transfer medium according to an embodiment) will be specifically described with reference to an example. Note that the present invention can be implemented 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 with respect to the width, thickness, shape, and the like of each part in comparison with actual aspects for the sake of clarity of explanation, but are merely examples, and the interpretation of the present invention is not limited. It is not limited. In addition, in the present specification and each drawing, the same elements as those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate.

  As shown in FIGS. 1 and 2, an intermediate transfer medium 10 according to an embodiment has a transfer layer 5 provided on a base material 1 so as to be peelable from the base material 1. It includes a release layer 3 located closest to the substrate and a receiving layer 4 located farthest from the substrate 1. In other words, the transfer layer 5 has a laminated structure in which the peeling layer 3 and the receiving layer 4 are laminated from the base material 1 side. The peeling layer 3 is located closest to the base material 1, and the receiving layer 4 is located farthest from the substrate 1. In the form shown in FIG. 1, the release layer 3 and the receiving layer 4 are in direct contact with each other. In the form shown in FIG. 2, the release layer is interposed via another layer (intermediate layer 7 in the form shown). 3 and the receiving layer 4 are in indirect contact with each other. Hereinafter, each configuration of the intermediate transfer medium 10 according to one embodiment will be described with an example.

(Base material)
The substrate 1 is an essential component in the intermediate transfer medium 10 of one embodiment, and holds the transfer layer 5. There is no limitation in particular about the base material 1, For example, stretched or unstretched films of plastics such as high heat-resistant polyester such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, polycarbonate, cellulose acetate, polyethylene derivatives, polyamide, and polymethylpentene Can be used. Moreover, the composite film which laminated | stacked 2 or more types of these materials can also be used. The thickness of the substrate 1 can be appropriately selected depending on the material so that its strength, heat resistance, etc. are appropriate, but is usually in the range of 4 μm to 30 μm, preferably 6 μm to 20 μm. Is within the range.

(Transfer layer)
As shown in FIGS. 1 and 2, a transfer layer 5 is provided on the substrate 1. The transfer layer 5 is provided so as to be peelable from the base material 1 and is a layer that is peeled off from the base material 1 by thermal transfer and transferred onto a transfer target 200 described later.

  The transfer layer 5 includes at least a release layer 3 and a receiving layer 4. The release layer 3 constituting the transfer layer 5 is located closest to the substrate 1, and the receiving layer 4 constituting the transfer layer 5 is The receiving layer 4 is located farthest from the substrate 1. Of the layers constituting the transfer layer 5, the layer farthest from the substrate 1 is the receiving layer 4. If the receiving layer 4 is not positioned farthest from the substrate 1, in other words, If the receiving layer 4 is not positioned on the outermost surface of the intermediate transfer medium 10, a thermal transfer image cannot be formed on the transfer layer 5 using a thermal transfer sheet having a color material layer.

"Peeling layer"
The transfer property of the transfer layer 5 when transferring the transfer layer 5 onto the transfer medium is the layer that is located closest to the substrate 1 among the layers that constitute the transfer layer 5, in other words, the layer that is located at the transfer interface. It is thought that it is influenced by the transferability of. Therefore, in the intermediate transfer medium 10 according to the embodiment in which the layer located closest to the substrate 1 among the layers constituting the transfer layer 5 is the release layer 3, the transferability of the release layer 3 is sufficiently increased. There is a need.

  The transferability referred to in this specification means that the transfer layer does not remain on the substrate side when the transfer layer is transferred to the transfer target side, or the transfer target and the intermediate transfer medium are integrated. It is an index that indicates whether or not the transfer layer can be accurately transferred (transferred) to the transfer target without being transferred. High transferability means that energy is applied to the intermediate transfer medium and the transfer target is transferred. When transferring the transfer layer onto the body, the transfer layer corresponding to the area where energy is applied does not remain on the substrate side, and the transfer target and the intermediate transfer medium are not integrated with each other. It means that it can be accurately transferred onto the transfer object. On the other hand, low transferability means that when energy is applied to the intermediate transfer medium and the transfer layer is transferred to the transfer target side, part or all of the transfer layer corresponding to the region to which energy is applied. In the region, the base material, or a layer that is optionally provided on the base material, and the transfer layer cause heat fusion, in other words, the base material, or a layer that is optionally provided on the base material, and a release layer. Causes heat fusion, the transfer layer cannot be peeled off from the base material, and the transfer target and the intermediate transfer medium are integrated, or the base material or a layer arbitrarily provided on the base material The release layer included in the transfer layer causes thermal fusion, and the transfer layer that should be peeled off at the interface with the base material or any layer provided on the base material constitutes the transfer layer. All of the transfer layer to be transferred onto the transfer target Partly meant that remained to the substrate side of the intermediate transfer medium.

  Therefore, in the intermediate transfer medium 10 of one embodiment, the release layer 3 located closest to the base material 1 among the layers constituting the transfer layer 5 is, in other words, the transfer interface when the transfer layer 5 is transferred. The release layer 3 positioned is characterized by containing a cellulosic resin. According to the transfer layer 5 including the release layer 3 having this feature, the transferability of the release layer 3 located at the transfer interface can be sufficiently satisfied. That is, the transferability of the transfer layer 5 can be sufficiently satisfied. Further, even when the energy applied to the intermediate transfer medium 10 during transfer of the transfer layer 5 is increased, the transferability of the transfer layer 5 including the release layer 3 and the receiving layer 4 can be sufficiently satisfied. it can. That is, in a wide energy range, the transferability of the transfer layer 5 including the release layer 3 and the receiving layer 4 on the transfer target can be sufficiently satisfied. Moreover, dyeing | staining property can be provided to the peeling layer 3 by setting it as the peeling layer 3 containing a cellulose resin.

  In the intermediate transfer medium 10 of the embodiment in which the layer located closest to the substrate 1 among the layers constituting the transfer layer 5 is the release layer 3, when the transfer layer 5 is transferred onto the transfer medium. The release layer 3 is located on the outermost surface. As described above, the release layer 3 containing a cellulose-based resin has dye-dyeing properties. Therefore, according to the intermediate transfer medium 10 of one embodiment, even after the transfer layer 5 is transferred onto the transfer target. A thermal transfer image can be formed on the surface of the transfer layer 5 transferred onto the transfer target, in other words, on the release layer 3 using a sublimation thermal transfer system.

  There is no limitation in particular about a cellulose resin, For example, a cellulose acetate resin, a cellulose acetate butyrate resin, a cellulose acetate propionate resin, a nitrocellulose resin, a cellulose acetate etc. can be used. The release layer 3 in a preferred form contains one or both of cellulose acetate butyrate resin and cellulose acetate propionate resin. According to the release layer 3 containing cellulose acetate butyrate resin or cellulose acetate propionate resin, the transferability of the transfer layer 5 including the release layer 3 can be further improved.

  The peeling layer 3 may contain 1 type independently as a cellulose resin, and may contain 2 or more types. Moreover, other resin may be contained with the cellulose resin.

  The release layer 3 in a preferred form contains a cellulose resin having a number average molecular weight (Mn) of less than 70,000, preferably 55000 or less, particularly preferably 40000 or less. According to the transfer layer 5 including the release layer 3 in a preferable form, the transfer layer 5 is transferred onto the transfer object as compared with the transfer layer including the release layer 3 containing only a cellulose resin having a number average molecular weight (Mn) of 70000 or more. The foil breakability when transferring the layer 5 can be improved.

  The release layer 3 may contain one kind of cellulose resin alone, or may contain two or more kinds of cellulose resins having different number average molecular weights (Mn). When the release layer 3 containing two or more types of cellulose resins is used, at least one type of cellulose resin of two or more types of cellulose resins is used as the cellulose resin having the above preferred number average molecular weight (Mn). It is preferable. In addition, the number average molecular weight (Mn) said in this specification means the molecular weight by polystyrene conversion measured by gel permeation chromatography (GPC) based on JISK7252-1: 2008.

  The content of the cellulose resin is not particularly limited. For example, when the content of the cellulose resin is about 0.5% by mass with respect to the total mass of the release layer 3 by adding a very small amount to the release layer 3. However, the transferability of the transfer layer 5 including the release layer 3 can be improved. In other words, regardless of the content, according to the release layer 3 containing the cellulosic resin, the release layer 3 can be formed in a wider energy range than the release layer 3 not containing the cellulose resin. The transferability of the transfer layer 5 that is included can be made extremely good. This is also clear from the results of Examples and Comparative Examples. There is no limitation in particular also about the upper limit of content of a cellulose resin, and it is 100 mass%.

  As described above, the content of the cellulose-based resin is not limited in any way, but the content of the cellulose-based resin is determined by transferring the transfer layer 5 onto the transfer target, and the release layer 3 positioned on the outermost surface. The separation of the release layer 3 and the color material layer when the color material contained in the color material layer (second color material layer (53)) of the thermal transfer sheet 100 to be described later is transferred to form a thermal transfer image. It is desirable to determine in consideration of moldability (hereinafter, simply referred to as releasability). In the case where measures for improving the releasability are taken on the color material layer side of the thermal transfer sheet, for example, when the color material layer contains a release agent, the cellulose resin What is necessary is just to set it as arbitrary content, without considering the content. On the other hand, if no measures are taken to improve releasability on the color material layer side of the thermal transfer sheet, depending on the type of resin contained in the color material layer of the thermal transfer sheet, the cellulose resin It is preferable to determine the content. In this case, the releasability varies depending on the type of resin contained in the color material layer of the thermal transfer sheet, for example, the resin contained in the color material layer of the thermal transfer sheet is a polyvinyl acetal resin, When it is a polyvinyl butyral resin and the color material layer does not contain a release agent, the content of the cellulose resin with respect to the total mass of the release layer 3 is preferably less than 25% by mass. In addition, even when both the release layer 3 and the color material layer of the thermal transfer sheet do not contain a release agent or the like, thermal transfer including a resin having a good releasability with the release layer 3 containing a cellulose resin. By setting it as the color material layer of a sheet | seat, mold release property can be made favorable irrespective of content of a cellulose resin. That is, the content of the cellulose resin with respect to the total mass of the release layer 3 can be 100% by mass. Moreover, the release layer 3 can contain a release agent to improve the release property.

  The release layer 3 may contain a resin other than the cellulose resin, a release agent, and the like. Examples of resins other than cellulose resins include polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, and ethylene-acetic acid. Examples thereof include vinyl resins such as vinyl copolymers or polyacrylic acid esters, polyester resins, polystyrene resins, acrylic resins, and the like.

  Examples of the release agent include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorine-based and phosphate-based surfactants, silicone resins, silicone oils, and the like. As the silicone oil, reactive silicone oil, curable silicone oil, or the like can be used. Other conventionally known release agents other than these can be appropriately selected and used. The peeling layer 3 may contain 1 type independently as a mold release agent, and may contain 2 or more types.

  The release layer 3 is a release layer coating solution obtained by dispersing or dissolving an additive such as a release agent or the like in addition to the above cellulose-based resin, a cellulose-based resin added as necessary. Is applied to the substrate 1 or any layer provided on the substrate 1 by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate, and dried. Can be formed. Although there is no limitation in particular about the thickness of the peeling layer 3, when aiming at the further improvement of transferability, or when aiming at the improvement of the density | concentration of the thermal transfer image formed on the peeling layer 3, etc., a peeling layer The thickness of 3 is preferably in the range of 0.3 μm to 10 μm.

"Receptive layer"
As shown in FIGS. 1 and 2, the receiving layer 4 is provided on the release layer 3 directly or indirectly via another layer. The receiving layer 4 is a layer that constitutes the transfer layer 5 and is a layer that is transferred to the transfer target side together with the release layer 3 when the transfer layer 5 is transferred onto the transfer target. The receiving layer 4 is located farthest from the substrate 1 among the layers constituting the transfer layer 5, in other words, the layer located on the outermost surface of the intermediate transfer medium 10, and the color material layer of the thermal transfer sheet By transferring the color material contained in (for example, the first color material layer (51) of the thermal transfer sheet described later) onto the receiving layer 4, a thermal transfer image can be formed on the receiving layer 4. .

  The component contained in the receiving layer 4 is not particularly limited, and a conventionally known resin capable of receiving a coloring material such as a sublimation dye contained in the coloring material layer of the thermal transfer sheet can be appropriately selected and used. . Such resins include vinyl chloride resins, polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate. Copolymers or vinyl resins such as polyacrylates, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene or propylene and other vinyl polymers And polycarbonate. Moreover, it can also be set as the receiving layer 4 containing a cellulose resin.

  The receiving layer 4 is located farthest from the substrate 1 among the layers constituting the transfer layer 5, and when the transfer layer 5 is transferred onto the transfer target, the receiving layer 4 is directly connected to the transfer target. Will come into contact. Therefore, when no measures are taken on the transfer target side to improve the adhesion (sometimes referred to as adhesion) with the transfer layer 5, the receiving layer 4 contains a resin having adhesiveness. It is preferable.

  The preferred form of the receiving layer 4 contains a binder resin having a number average molecular weight (Mn) of 8000 to 32000, more preferably a vinyl chloride resin having a number average molecular weight (Mn) of 8000 to 32000. doing. According to the preferable form of the receiving layer 4, it is possible to form a thermal transfer image having a higher density on the receiving layer 4 while imparting adhesiveness to the receiving layer 4.

  The vinyl chloride resin referred to in the present specification includes a polymer obtained by homopolymerizing vinyl chloride, a copolymer of vinyl chloride and other monomers capable of copolymerizing with vinyl chloride, and the polymer and the copolymer. It means a mixture of coalescence. Examples of other monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, and vinyl acetate. These vinyl chloride resins may be produced by any of the conventionally known production methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. Moreover, it may be manufactured by a method other than this.

  Among these vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins and vinyl chloride homopolymers are preferred chlorides because they enable the formation of higher density thermal transfer images under high thermal energy conditions. Vinyl resin.

  Moreover, the receiving layer 4 may contain a release agent together with a resin capable of receiving a color material such as the sublimable dye. The release agent is an optional component in the receiving layer 4. As the release agent, the release agent described in the release layer 3 can be appropriately selected and used, and detailed description thereof is omitted here. Although there is no limitation in particular about content of a mold release agent, it is preferable that it is 6 mass% or more with respect to the total mass of the receiving layer 4, and it is more preferable that it is 8 mass% or more. Although there is no particular limitation on the upper limit value, it is preferably 15% by mass or less in consideration of the adhesiveness between the transfer layer 5 and the transfer target when the transfer layer 5 is transferred onto the transfer target. In addition, when the countermeasure for improving the adhesiveness with the transfer layer 5 is taken on the transfer target side, the upper limit value of the preferable content of the release agent is not limited to this. In addition, after forming a thermal transfer image on the receiving layer 4, an adhesive layer (for example, a heat seal layer 52 described later) is transferred onto the receiving layer 4 on which the thermal transfer image is formed. By transferring the transfer layer 5 onto the transfer body so that the layer having the transfer medium and the transfer body are in direct contact with each other, the adhesion between the transfer body and the transfer layer 5 can be improved.

  The receiving layer 4 in a more preferable form contains a resin having a number average molecular weight (Mn) of 8000 or more and 32000 or less and a release agent having a content in the above preferable range. The particularly preferred form of the receiving layer 4 contains a vinyl chloride resin having a number average molecular weight (Mn) of 8000 or more and 32000 or less and a release agent having a content within the above preferred range. According to the receiving layer 4 in a more preferable form, it is possible to form a thermal transfer image having a high density on the receiving layer 4 while suppressing the occurrence of uneven printing. In particular, even when the energy applied during the formation of the thermal transfer image is increased in order to cope with the speeding up of the printer, the thermal transfer image having a high density can be displayed on the receiving layer 4 while suppressing the occurrence of uneven printing. Can be formed. Furthermore, it is possible to improve the foil breakability when the transfer layer 5 including the receiving layer 4 on which the thermal transfer image is formed is transferred onto the transfer target.

  The printing unevenness referred to in this specification is formed on the receiving layer 4 due to releasability between the receiving layer 4 and the color material layer of the thermal transfer sheet for forming a thermal transfer image on the receiving layer 4. It means a phenomenon in which a thermal transfer image is burnt or dull. Further, the foil breakability of the transfer layer 5 referred to in the specification of the present application indicates the degree of suppression of tailing when the transfer layer 5 is transferred onto the transfer target, and when the foil breakability is good, It means that the occurrence of tailing can be sufficiently suppressed. Further, the tailing referred to in the present specification means that, when the transfer layer 5 is transferred onto a transfer target, the boundary between the transfer region and the non-transfer region of the transfer layer 5 is a starting point, and the boundary from the boundary to the non-transfer region side. It means a phenomenon in which the transfer layer 5 is transferred so as to protrude.

  Moreover, the receiving layer 4 may contain other arbitrary additives together with a resin capable of receiving a color material such as a sublimation dye and an arbitrary release agent.

  The method for forming the receiving layer 4 is not particularly limited, but a resin capable of receiving a coloring material such as a sublimation dye, a release agent added as necessary, and an additive are dissolved or dispersed in an appropriate solvent. Preparing a coating solution for the receiving layer, and using a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate, the release layer 3 or any layer provided on the release layer 3, For example, it can be formed by applying and drying on an intermediate layer 7 described later. The thickness of the receiving layer 4 is usually in the range of 0.5 μm to 10 μm.

  As described above, the receiving layer 4 has been described by taking a preferable form as an example in consideration of adhesiveness and the density of a thermal transfer image to be formed. However, when the receiving layer 4 itself does not require adhesiveness, When a high density is not required for the thermal transfer image to be formed, a conventionally known receiving layer can be used as it is in the field of a thermal transfer image receiving sheet or an intermediate transfer medium.

  In the above description, the receiving layer 4 containing a resin capable of receiving a coloring material such as a sublimable dye has been mainly described. In other words, a thermal transfer image is formed on the receiving layer 4 using a sublimation thermal transfer system. However, when the thermal transfer image formed on the receiving layer 4 is not a sublimation type thermal transfer method but an image formed using a thermal melting type thermal transfer method, the receiving layer is formed. 4 does not need to contain a resin capable of receiving a color material such as a sublimation dye. In other words, in place of the receiving layer 4 containing a resin capable of receiving a color material such as a sublimation dye described above, a resin which cannot or cannot easily receive a color material such as a sublimation dye is contained. The receiving layer 4 can also be used. As an example, the receiving layer 4 described above may be changed to a protective layer described later, a heat seal layer, or the like. In the sublimation type thermal transfer method, energy corresponding to image information is applied from a heating device such as a thermal head, and color material components such as sublimation dye contained in the color material layer of the thermal transfer sheet are diffused on the receiving layer 4. It is a system that forms a thermal transfer image by transferring, and the thermal melting type thermal transfer system is a receiving layer for a color material layer that has been melted and softened by applying energy according to image information from a heating device such as a thermal head. 4 is a method of forming a thermal transfer image by transferring the toner image onto image 4.

(Any layer)
Further, as shown in FIG. 2, specifically, when transferring the transfer layer 5 between the release layer 3 and the receiving layer 4 in order to further improve the foil breakability of the transfer layer 5. It is also possible to provide an intermediate layer 7 for suppressing tailing, crushing of characters, etc., or for improving the adhesion between the release layer 3 and the receiving layer 4. Character collapse in this specification means that a transfer area surrounded or sandwiched between transfer areas represented as characters is transferred by a phenomenon similar to tailing, and the original character can be reproduced. Means no phenomenon.

  The intermediate layer 7 as an example includes, for example, a urethane resin, a polyester resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl pyrrolidone resin, a binder resin such as a polyvinyl alcohol resin, and, if necessary, alumina, It contains inorganic particles such as silica, titanium oxide and carbon black. According to the intermediate layer containing inorganic particles together with the binder resin, the foil breakability of the transfer layer 5 including the intermediate layer 7 can be further improved. The intermediate layer 7 in a preferred form contains alumina fine particles and silica fine particles together with the binder resin. The intermediate layer in a particularly preferred form contains alumina fine particles derived from alumina sol and silica fine particles derived from colloidal silica together with a binder resin. Further, the intermediate layer 7 can be formed from inorganic fine particles without using a binder resin.

  When the main purpose is to improve releasability, it is preferable to provide an intermediate layer 7 containing an aqueous resin on the release layer 3. In other words, it is preferable to provide the intermediate layer 7 on the release layer 3 using an intermediate layer coating liquid obtained by dispersing or dissolving the aqueous resin in an aqueous solvent. By disposing the intermediate layer 7 containing the water-based resin between the release layer 3 and the receiving layer 4, it is possible to further improve the releasability. As used herein, “aqueous resin” refers to a water-soluble resin or a resin that is insoluble in an aqueous solvent but can be dispersed in an aqueous solvent, such as an emulsion or a dispersion. Examples of the aqueous solvent include water and a mixed solvent of water and alcohol.

  Examples of the water-soluble resin include polyvinyl pyrrolidone resin, polyvinyl alcohol resin, polyacrylic acid, polyhydroxyethyl acrylate, water-soluble (or water-dispersed) polyester resin, water-soluble (or water-dispersed) polyurethane resin, and water-dispersible vinyl chloride. Examples thereof include resins, water-dispersible acrylic chloride resins, water-dispersible epoxy resins, gelatin, hydroxyethyl cellulose resins, hydroxypropyl cellulose resins, and carboxymethyl cellulose.

  The method for forming the intermediate layer 7 is not particularly limited, and an intermediate layer coating solution is prepared by dissolving or dispersing a binder resin and, if necessary, an additive in an appropriate solvent. Further, it can be formed by coating and drying by a conventionally known forming means such as a gravure coating method, a roll coating method, a screen printing method, or a reverse roll coating method using a gravure plate.

  The thickness of the intermediate layer 7 is not particularly limited, but is preferably 0.01 μm or more and 5 μm or less, and particularly preferably 0.02 μm or more and 3 μm or less.

  A primer layer may be provided between the layers constituting the transfer layer 5 in place of or in addition to the intermediate layer 7. Examples of primer layers include UV absorber copolymer resins, polyester resins, polycarbonate resins, butyral resins, polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenol resins, and polyvinyl chloride resins. Resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acid-modified polyolefin resin, copolymer of ethylene and vinyl acetate or acrylic acid, (meth) acrylic resin, polyvinyl alcohol resin, polyvinyl Acetal resins, polybutadiene resins, rubber compounds, and the like can be given. Moreover, you may use together fillers, such as micro silica and polyethylene wax.

  There is no particular limitation on the method for forming the primer layer, and the binder resin exemplified above, an ultraviolet absorber, an antioxidant, a fluorescent whitening agent, an inorganic or organic filler component, an interface added as necessary. A primer layer coating solution in which an activator, a release agent, etc. are dispersed or dissolved in a suitable solvent is prepared, and this is formed on the receiving layer 4 by applying and drying by a method such as gravure coating or gravure reverse coating. can do. Although there is no limitation in particular about the thickness of a primer layer, the range of 0.5 micrometer or more and 10 micrometers or less is preferable, and the range of 0.8 micrometer or more and 2.0 micrometers or less is more preferable.

  Further, a concealing layer (not shown) may be provided between the peeling layer 3 and the receiving layer 4 in place of or together with the intermediate layer 7 and the primer layer which are arbitrary layers described above. By providing a concealing layer between the release layer 3 and the receiving layer 4, a print product finally obtained using the intermediate transfer medium 10 of one embodiment can be obtained from the one surface side of the print product. The thermal transfer image formed on the receiving layer 4 is made visible while concealing the thermal transfer image formed thereon, while the thermal transfer image formed on the receiving layer 4 from the other surface side of the printed material While being concealed, the thermal transfer image formed on the release layer 3 can be made visible. That is, it is possible to obtain a printed material with improved design properties. In this case, in order to make it possible to visually recognize the thermal transfer image formed on the receiving layer 4 from the one surface side of the printed material, it is preferable to use a material having transparency as described later.

  The concealing layer as an example contains a binder resin and a colorant. Examples of the binder resin include polyester resin, urethane resin, epoxy resin, phenol resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, and the like. Examples of the colorant include known colorants such as titanium oxide, zinc oxide, carbon black, iron oxide, iron yellow, ultramarine blue, hologram powder, aluminum powder, metallic pigment, and pearl pigment. The concealing layer may contain one kind of these binder resins or may contain two or more kinds. The same applies to the colorant.

  The method for forming the masking layer is not particularly limited, and a coating solution for the masking layer is prepared by dispersing or dissolving the binder resin, the colorant, and the additive added as necessary in an appropriate solvent. This is applied to the release layer 3 or an arbitrary layer provided on the release layer 3 by a conventionally known forming means such as a gravure coating method, a roll coating method, a screen printing method, a reverse roll coating method using a gravure plate. It can be formed by coating and drying.

  Although there is no limitation in particular about the thickness of a concealment layer, what is necessary is just to set suitably in consideration of the concealment property by a concealment layer. If the thickness of the concealing layer is less than 0.1 μm, the concealing property tends to decrease. In consideration of this point, the thickness of the concealing layer is preferably 0.1 μm or more. Although there is no limitation in particular about the preferable upper limit of the thickness of a concealing layer, it is about 5 micrometers.

(Release layer)
Further, a release layer (not shown) can be provided between the substrate 1 and the transfer layer 5. The release layer is an arbitrary configuration in the intermediate transfer medium 10 of one embodiment, and is a layer that does not constitute the transfer layer 5. That is, the layer remaining on the substrate 1 side when the transfer layer 5 is transferred onto the transfer target. By providing a release layer between the substrate 1 and the transfer layer 5, the transferability of the transfer layer 5 can be further improved in combination with the good transferability of the release layer 3 containing a cellulose resin. it can.

  Examples of the binder resin contained in the release layer include waxes, silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol, acrylic resin, heat-crosslinkable epoxy-amino resin, and heat-crosslinking. Alkyd-amino resin and the like. Further, the release layer may be composed of one kind of resin or may be composed of two or more kinds of resins. The release layer may be formed by using a cross-linking agent such as an isocyanate compound, a catalyst such as a tin-based catalyst, and an aluminum-based catalyst in addition to the releasable resin. The thickness of the release layer is generally in the range of 0.2 μm to 5 μm. The release layer is formed by dissolving or dispersing the resin in a suitable solvent to prepare a release layer coating solution, which is then applied to the substrate 1 by a gravure printing method, a screen printing method or a gravure plate. It can be formed by coating and drying by a conventionally known means such as a reverse coating method using sapphire.

<< Thermal transfer sheet >>
Next, an example of a thermal transfer sheet that can be used in combination with the intermediate transfer medium according to one embodiment of the present invention will be described with reference to the drawings.

  As shown in FIGS. 3 to 5, the thermal transfer sheet 100 as an example has a first color material layer (51) and a second color material layer (53) on one surface of the thermal transfer sheet base material 50 in a surface sequential manner. The structure provided in is exhibited. In the thermal transfer sheet 100 shown in FIG. 4, the first color material layer (51) includes a yellow color material layer 51Y, a magenta color material layer 51M, and a cyan color material layer 51C, and the second color material layer (53 ) Includes a yellow color material layer 53Y, a magenta color material layer 53M, and a cyan color material layer 53C. Moreover, the thermal transfer sheet 100 of the form shown to Fig.5 (a), (b) is the 1st color material layer (51), the heat seal layer 52, and the 2nd color material on one surface of the base material 50 for thermal transfer sheets. The layer (53) and the protective layer 55 are provided in the surface order. Further, in place of the form shown in FIGS. 5A and 5B, the first color material layer (51), the heat seal layer 52, and the second color material layer ( 53) are provided in a surface sequential manner, or a first color material layer (51), a second color material layer (53), and a protective layer 55 are provided in a surface sequential manner on one surface of the thermal transfer sheet substrate 50. The provided thermal transfer sheet can also be used. Moreover, the thermal transfer sheet of the form other than this, for example, the some thermal transfer sheet which each has each layer independently, can also be used.

(Base material for thermal transfer sheet)
The thermal transfer sheet base material 50 includes a first color material layer (51), a second color material layer (53), and the other surface of the base material 1 provided on one surface of the thermal transfer sheet base material 50. It is provided to hold the back layer provided on the top. The material of the base material 50 for the thermal transfer sheet is not particularly limited. However, when the thermal transfer image is formed on the receiving layer 4 or the release layer 3 of the intermediate transfer medium 10, it can withstand the heat applied to the thermal transfer sheet. It is desirable to have unobstructed mechanical properties. Examples of such a thermal transfer sheet substrate 50 include polyesters such as polyethylene terephthalate, polycarbonate, polyimide, polyetherimide, cellulose derivatives, polyethylene, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, nylon, and polyether. Examples include various plastic films or sheets of ether ketone. Moreover, the thickness of the base material 50 for thermal transfer sheets can be suitably set according to the material so that the strength and heat resistance are appropriate, and is usually in the range of 2.5 μm to 50 μm. The base material 1 of the intermediate transfer medium 10 and the thermal transfer sheet base material 50 of the thermal transfer sheet 100 may be the same or different.

(First color material layer)
The first color material layer (51) is a layer used to form a thermal transfer image (see the first image (20) in FIG. 6A) on the receiving layer 4 of the intermediate transfer medium 10. Hereinafter, the thermal transfer image formed on the receiving layer 4 of the intermediate transfer medium 10 using the first color material layer (51) may be referred to as a first image.

  Hereinafter, the case where the first color material layer (51) is the color material layer used in the sublimation type thermal transfer method and the case where it is the color material layer used in the heat melting type heat transfer method will be described separately. When the first image is formed on the receiving layer 4 of the intermediate transfer medium 10 using the sublimation thermal transfer method, the receiving layer 4 of the intermediate transfer medium 10 can receive a color material such as a sublimation dye. Contains resin.

"First color material layer used for sublimation thermal transfer system"
The first color material layer (51) used for the sublimation type thermal transfer system contains a binder resin and a color material component. Examples of the color material component include sublimable dyes and fluorescent dyes.

  A 1st color material layer (51) may be comprised from a single layer, and may be comprised from two or more layers. For example, when a monocolor image is formed as the first image on the receiving layer 4 of the intermediate transfer medium 10, the first color material layer (51) is simply formed as shown in FIGS. In the case where a full color image is formed as the first image on the receiving layer 4 of the intermediate transfer medium 10, as shown in FIGS. 4 and 5B, the yellow color may be formed. A first color obtained by arranging a plurality of color material layers containing sublimation dyes having different hues such as the material layer 51Y, the magenta color material layer 51M, and the cyan color material layer 51C on the same surface of the base material 50 for the thermal transfer sheet. It is good also as a material layer (51). Also, two of the color material layers containing sublimable dyes having different hues such as the yellow color material layer 51Y, the magenta color material layer 51M, and the cyan color material layer 51C are used as the thermal transfer sheet base material 50. The first color material layer (51) may be arranged on the same plane.

  As the sublimable dye, those having a sufficient color density and not discolored by light, heat, temperature or the like are preferable. Examples of such sublimable dyes include diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, pyrazolomethine dyes, acetophenone azomethine, pyrazolo dyes. Azomethine dyes such as azomethine, imidazolazomethine, imidazoazomethine and pyridone azomethine, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, Benzeneazo dyes, pyridone azo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, disazo azo dyes, spiropyran Fee, India Linos Piropi run dyes, fluoran dye, rhodamine lactam-based dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone dyes, and the like. Specifically, red dyes such as MSRedG (Mitsui Toatsu Chemicals Co., Ltd.), Macrolex Red Violet R (Bayer Co., Ltd.), CeresRed 7B (Bayer Co., Ltd.), Samaron Red F3BS (Mitsubishi Chemical Co., Ltd.), etc. , Holon Brilliant Yellow 6GL (Clariant Co., Ltd.), PTY-52 (Mitsubishi Chemical Co., Ltd.), Macrolex Yellow 6G (Bayer Co., Ltd.) and other yellow dyes, Kayaset (registered trademark) Blue 714 (Nippon Kayaku Co., Ltd.) Co., Ltd.), Holon Brilliant Blue SR (Clariant), MS Blue 100 (Mitsui Toatsu Chemicals), C.I. I. And blue dyes such as Solvent Blue 63.

  As the binder resin for supporting the sublimable dye, those having heat resistance and appropriate affinity with the sublimable dye are preferable. Examples of such binder resins include cellulose resins such as nitrocellulose, cellulose acetate butyrate, and cellulose acetate propionate; vinyl resins such as polyvinyl acetate, polyvinyl butyral, and polyvinyl acetal; poly (meth) acrylate, An acrylic resin such as poly (meth) acrylamide; a polyurethane resin; a polyamide resin; a polyester resin;

  Examples of fluorescent dyes include diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, derivatives of triazole, carbazole, pyridine, naphthalic acid, imidazolone, dyes such as fluorescein and eosin, and compounds having a benzene ring such as anthracene. I can give you. The fluorescent dye has the property of absorbing energy by being stimulated by sunlight, electric light, ultraviolet light, and the like, and emitting light (fluorescence) by changing the energy to light during stimulation. The same applies to the fluorescent pigment described later.

  The binder resin for supporting the fluorescent dye includes vinyl resins such as polyvinyl acetate, polyvinyl butyral, and polyvinyl acetal, cellulose resins, melamine resins, polyester resins, polyamide resins, polyolefin resins, and polyurethane resins. Examples thereof include thermoplastic elastomers such as resin, acrylic resin, styrene resin, styrene-acrylic copolymer, ethylene-vinyl acetate copolymer, chlorinated polypropylene, chlorinated rubber, and styrene-butadiene rubber.

  There is no particular limitation on the content of the binder resin, the sublimation dye as the color material component, and the fluorescent dye in the first color material layer. The first color material layer (51) is used to form the intermediate transfer medium 10. It can be set as appropriate according to the image density required for the first image formed on the receiving layer 4.

  Moreover, the 1st color material layer (51) may contain additives, such as an inorganic particle and an organic fine particle, with binder resin and a color material component. Examples of the inorganic particles include talc, carbon black, aluminum, molybdenum disulfide, and the like, and examples of the organic fine particles include polyethylene wax and silicone resin fine particles. Moreover, the 1st color material layer (51) as an example may contain the mold release agent. Examples of the mold release agent include modified or unmodified silicone oil (including those referred to as silicone resins), phosphate esters, and fatty acid esters.

  As a method of forming the first color material layer (51) of the above-mentioned form, for example, a binder resin, a color material component, an additive added as necessary, and a release agent are dissolved or dispersed in an appropriate solvent. The first color material layer coating solution is prepared, and the first color material layer coating solution is prepared by a conventionally known coating means such as a gravure coater, roll coater, wire bar, etc. 50 or an arbitrary layer provided on the thermal transfer sheet substrate 50, and can be formed by drying. The thickness of the first color material layer (51) is generally in the range of 0.2 μm to 2.0 μm.

  When the receiving layer 4 does not contain a resin capable of receiving a coloring material such as a sublimation dye, the first image can be formed on the receiving layer 4 using a hot-melt type thermal transfer method. Note that the first image can also be formed on the receiving layer 4 containing a resin capable of receiving a coloring material such as a sublimable dye by using a hot-melt type thermal transfer method.

"The first color material layer used in the hot melt thermal transfer system"
The first color material layer (51) (hereinafter referred to as the first color material layer of the second form) used in the heat melting type thermal transfer system contains a binder and a colorant. The first color material layer (51) used in the hot melt type thermal transfer system plays a role as a so-called hot melt ink layer.

  Examples of the binder contained in the first color material layer (51) used in the thermal melting type thermal transfer method include a resin component or a wax component. Examples of the resin component include ethylene-vinyl acetate co-polymer. Polymer, ethylene-acrylic ester copolymer, polyethylene, polystyrene, polypropylene, polybutene, petroleum resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, vinylidene chloride resin, acrylic resin, methacrylic resin, polyamide , Polycarbonate, fluororesin, polyvinyl formal, polyvinyl butyral, acetyl cellulose, nitrocellulose, polyvinyl acetate, polyisobutylene, ethyl cellulose or polyacetal. Examples of the wax component include microcrystalline wax, carnauba wax, and paraffin wax. In addition, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, polyester wax, partially modified wax, fatty acid ester, fatty acid amide, etc. Can be mentioned.

  The colorant contained in the first color material layer (51) used in the hot melt thermal transfer method can be appropriately selected from conventionally known organic or inorganic pigments or dyes. It is preferable to have a high color density and not discolor or fade due to light, heat, or the like. Further, it may be a substance that develops color when heated or a substance that develops color when it comes into contact with a component applied to the surface of the transfer target. The color of the colorant is not limited to cyan, magenta, yellow, and black, and various colorants can be used. For example, a fluorescent pigment or the like can be used. Fluorescent pigments are mainly inorganic phosphor materials, mainly composed of crystals such as oxides, sulfides, silicates, phosphates, and tungstates such as Ca, Ba, Mg, Zn, and Cd. , Mn, Zn, Ag, Cu, Sb, Pb and the like, or a rare earth element such as lanthanoids added as an activator, and a pigment obtained by firing. Specific examples of these inorganic phosphor materials include, for example, oxides such as calcium tungstate and magnesium tungstate, or calcium sulfide / bismuth, zinc sulfide / silver, zinc sulfide / copper, zinc sulfide / gold / Sulfides such as aluminum, zinc oxide, zinc, yttrium europium vanadate, yttrium europium oxide, yttrium sulfate europium, yttrium sulfate terbium sulfate, gadolinium sulfate terbium sulfate, lanthanum sulfate terbium, acid bromide Examples thereof include phosphor materials such as lanthanum and terbium oxides.

  There is no particular limitation on the content of the binder and the colorant in the first color material layer used in the hot-melt type thermal transfer method, and the first color material layer (51) is used to form on the receiving layer 4 of the intermediate transfer medium 10. It can be appropriately set according to the image density required for the first image formed in the above.

  As a method for forming the first color material layer (51) used in the heat melting type thermal transfer system, for example, a binder, a colorant, and an additive added as necessary are dissolved or dispersed in an appropriate solvent. The first color material layer coating liquid is prepared, and the first color material layer coating liquid is prepared by a conventionally known coating means such as a gravure coater, roll coater, wire bar, etc. Alternatively, it can be formed by coating and drying on an arbitrary layer provided on the thermal transfer sheet substrate 50, for example, a release layer. The thickness of the first color material layer (51) used in the heat melting type thermal transfer system is generally in the range of 0.5 μm to 10 μm.

(Second color material layer)
As shown in FIGS. 4 and 5, as the thermal transfer sheet 100 used in combination with the intermediate transfer medium 10 of the above-described embodiment, the first color material layer ( 51) and the thermal transfer sheet 100 in which the second color material layer (53) is provided in the surface order can also be used. The second color material layer (53) is formed by transferring the transfer layer 5 of the intermediate transfer medium 10 according to one embodiment onto the transfer target body, so that the thermal transfer image is formed on the release layer 3 that is positioned on the outermost surface. It is a layer for forming (refer to the 2nd picture (30) of Drawing 6 (b)). Hereinafter, the thermal transfer image formed on the release layer 3 of the intermediate transfer medium 10 using the second color material layer (51) may be referred to as a second image.

  As described above, in the intermediate transfer medium 10 according to one embodiment, the release layer 3 contains a cellulose resin, and the release layer 3 has a configuration capable of receiving a color material such as a sublimation dye. Therefore, according to the intermediate transfer medium 10 of one embodiment, it is possible to form a second image on the release layer 3 positioned on the outermost surface after the transfer layer 5 is transferred using a sublimation thermal transfer method. In addition, the second image can be formed by using a heat melting type thermal transfer system.

  That is, the second color material layer (53) may be a color material layer used for the sublimation type thermal transfer method or a color material layer used for the heat melting type thermal transfer method.

  For the second color material layer (53), the components described in the first color material layer (51) can be appropriately selected and used, and detailed description thereof is omitted here.

  In the above description, the thermal transfer sheet 100 including both the first color material layer (51) and the second color material layer (53) has been described. However, the first color material layer (51) includes the first color material layer (51). The receiving layer of the intermediate transfer medium 10 using the first thermal transfer sheet and the second thermal transfer sheet having the second color material layer (53) and the first thermal transfer sheet having the first color material layer (51). After the first image is formed on 4 and the transfer layer 5 of the intermediate transfer medium 10 is transferred onto the transfer object, the intermediate transfer medium is used by using the second thermal transfer sheet having the second color material layer (53). A second image can be formed on the release layer 3.

(Color material primer layer)
Between the thermal transfer sheet base material 50 and the color material layers 51 and 53, a color material primer layer (not shown) for the purpose of improving the adhesion between the thermal transfer sheet base material 50 and the color material layers 51 and 53 is provided. It may be provided.

  As the color material primer layer, a conventionally known color material primer layer in the field of thermal transfer sheet can be appropriately selected and used. The color material primer layer as an example is made of a resin material. Examples of the resin material constituting the color material primer layer include polyester resins, polyvinyl pyrrolidone resins, polyvinyl alcohol resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamides. Resin, polyamide resin, polyvinyl acetoacetal, polyvinyl butyral, and the like. Moreover, the color material primer layer may contain various additives such as organic particles and inorganic particles together with these resin components.

  There is also no particular limitation on the method for forming the color material primer layer, and a color material primer layer coating solution is prepared by dissolving or dispersing the resin components exemplified above and additives added as necessary in an appropriate solvent. Then, it is formed by applying and drying on the thermal transfer sheet substrate 50 by a conventionally known forming means such as a gravure coating method, a roll coating method, a screen printing method, or a reverse roll coating method using a gravure plate. can do. Although there is no limitation in particular about the thickness of a primer layer, Usually, it is the range of 0.02 micrometer or more and 1 micrometer or less.

(Protective layer)
Further, as the thermal transfer sheet 100 used in combination with the intermediate transfer medium 10 of one embodiment, the first color material layer (51), the second color material layer (53), It is also possible to use a thermal transfer sheet 100 (not shown) in which the protective layers 55 are provided in the surface order. According to the thermal transfer sheet 100 of this form, after the second image is formed on the release layer 3 of the intermediate transfer medium 10 using the second color material layer (53) of the thermal transfer sheet 100, the second image is formed on the second image. By transferring the protective layer 55 of the thermal transfer sheet 100, a printed matter having excellent durability can be obtained.

  Examples of the material constituting the protective layer 55 include polyester resins, polycarbonate resins, acrylic resins, ultraviolet absorbing resins, epoxy resins, polystyrene resins, polyurethane resins, acrylic urethane resins, and resins obtained by modifying these resins with silicone, A mixture of these resins, ionizing radiation curable resin, ultraviolet absorbing resin and the like can be mentioned.

  Moreover, the protective layer containing ionizing radiation curable resin can be used suitably as a binder of a protective layer at the point which is especially excellent in plasticizer resistance and abrasion resistance. The ionizing radiation curable resin is not particularly limited and can be appropriately selected from conventionally known ionizing radiation curable resins. For example, a radical polymerizable polymer or oligomer can be crosslinked by irradiation with ionizing radiation. Cured, added with a photopolymerization initiator as required, and polymerized and cross-linked with an electron beam or ultraviolet light can be used. A protective layer containing an ultraviolet absorbing resin is excellent in imparting light resistance to a printed material.

  As the ultraviolet absorbing resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorbent to a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, addition-polymerizable double-reactive organic UV absorbers such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines, etc. Examples include a bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, etc.), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, a reactive group such as an isocyanate group, and the like.

  If necessary, for example, colorants such as lubricants, plasticizers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, dyes, pigments, etc. Additives and the like may be added. As a method for forming the protective layer, one or two or more of the resin materials exemplified above are dissolved or dispersed in an appropriate solvent to prepare a protective layer coating solution, which is used as the substrate 1 or It can be formed on an arbitrary layer provided on the substrate 1 by applying and drying by a conventionally known means such as a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. The thickness of the protective layer is usually in the range of 0.1 to 50 μm, preferably in the range of 1 to 20 μm.

  Moreover, a layer having a peelability (not shown) may be provided between the thermal transfer sheet substrate 50 and the protective layer 55 to improve the transferability of the protective layer 55. Examples of the material of the layer having peelability include waxes, silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol, acrylic resin, heat-crosslinkable epoxy-amino resin, and heat-crosslinkable alkyd. -An amino resin etc. can be mentioned. Moreover, the peeling layer 3 of the intermediate transfer medium 10 of the above-described embodiment can be used as the layer having peelability. In addition, a layer containing “other resin” described in the peeling layer 3 of the intermediate transfer medium of the one embodiment can be used.

  Although there is no particular limitation on the method for forming the layer having peelability, a coating liquid is prepared by dissolving or dispersing the above resin in an appropriate solvent, and this is applied to the gravure printing method and screen on the substrate 50 for thermal transfer sheet. It can be formed by applying and drying by a conventionally known means such as a printing method or a reverse coating method using a gravure plate. The thickness of the peelable layer is preferably in the range of 0.5 μm to 5 μm.

  As shown in FIG. 5, as the thermal transfer sheet 100 used in combination with the intermediate transfer medium 10 of the above-described embodiment, a first color material layer (51), a heat seal layer 52, and a second color material layer (53). Can also be used. The heat seal layer is provided so as to be peelable from the thermal transfer sheet substrate 50, and is a layer that is transferred onto the transfer layer 5 in a stage before the transfer layer of the intermediate transfer medium is transferred onto the transfer target. .

  Before the transfer layer 5 of the intermediate transfer medium 10 according to one embodiment is transferred onto the transfer medium using a thermal transfer sheet having the heat seal layer 52, the heat seal layer 52 is previously placed on the transfer layer 5 of the intermediate transfer medium. By transferring, the adhesiveness between the transfer target and the transfer layer 5 of the intermediate transfer medium 10 can be improved.

  Examples of the binder resin contained in the heat seal layer include an ultraviolet absorber copolymer resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, a polyester resin, a polycarbonate resin, a butyral resin, and a polyamide resin. And vinyl chloride resin. The heat seal layer may contain one kind of binder resin alone or may contain two or more kinds.

  The heat seal layer in a preferred form contains a binder resin having a number average molecular weight (Mn) lower than the number average molecular weight (Mn) of the binder resin contained in the receiving layer 4 of the intermediate transfer medium 10. In particular, a binder resin satisfying the condition that it is lower than the number average molecular weight (Mn) of the binder resin contained in the receiving layer 4 of the intermediate transfer medium 10 and having a number average molecular weight (Mn) of 4000 to 32000 is used. Contains. According to the heat transfer sheet 100 including a heat seal layer of a preferred form, the heat seal layer is transferred onto the transfer layer 5 of the intermediate transfer medium 10, and the transfer layer 5 onto which the heat seal layer has been transferred is transferred onto the transfer target 200. It is possible to further improve the adhesiveness when transferred. The number average molecular weight (Mn) of the binder resin contained in the receiving layer 4 of the intermediate transfer medium 10 referred to here is a number average molecular weight (Mn) which is a preferable binder resin contained in the receiving layer 4. Means a binder resin having the largest content among the binder resins of 8000 to 32000.

  There is no particular limitation on the method for forming the heat seal layer, and a binder resin and an ultraviolet absorber, an antioxidant, a fluorescent brightening agent, an inorganic or organic filler component, a surfactant, and a release agent that are added as necessary. And the like can be formed by applying and drying the heat-sealable layer coating liquid on the thermal transfer sheet substrate 50 by a method such as gravure coating or gravure reverse coating. Although there is no limitation in particular about the thickness of a heat seal layer, the range of 0.5 micrometer or more and 10 micrometers or less is preferable, and the range of 0.8 micrometer or more and 2 micrometers or less is more preferable.

  Further, in order to improve the transferability of the heat seal layer onto the transfer layer of the intermediate transfer medium 10, a release layer (not shown) can be provided between the heat transfer sheet substrate 50 and the heat seal layer. . The release layer is a layer that remains on the thermal transfer sheet substrate 50 side when the heat seal layer is transferred onto the transfer layer 5 of the intermediate transfer medium 10. As the release layer, the configuration of the release layer described in the intermediate transfer medium 10 can be appropriately selected and used, and detailed description thereof is omitted here.

(Back layer)
Further, a back layer (not shown) can be provided on the other surface of the thermal transfer sheet substrate 50.

  There is no limitation on the material of the back layer, for example, cellulose resins such as cellulose acetate butyrate and cellulose acetate propionate, vinyl resins such as polyvinyl butyral and polyvinyl acetal, polymethyl methacrylate, polyethyl acrylate, polyacrylamide And acrylic resins such as acrylonitrile-styrene copolymers, polyamide resins, polyamideimide resins, polyester resins, polyurethane resins, and natural or synthetic resins such as silicone-modified or fluorine-modified urethane, or a mixture thereof.

  The back layer may contain a solid or liquid lubricant. Examples of the lubricant include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorine And surfactants, organic carboxylic acids and derivatives thereof, metal soaps, fluorine resins, silicone resins, fine particles of inorganic compounds such as talc and silica. The mass of the lubricant with respect to the total mass of the back layer is in the range of 5 to 50% by mass, preferably in the range of 10 to 40% by mass.

  There is no particular limitation on the method for forming the back layer, and a resin, a lubricant added as necessary, and the like are dissolved or dispersed in an appropriate solvent to prepare a back layer coating solution. It can form by apply | coating and drying on the base material 50 for thermal transfer sheets by conventional coating means, such as a gravure coater, a roll coater, and a wire bar. The thickness of the back layer is preferably in the range of 1 μm to 10 μm.

<< Method for forming printed matter >>
Next, a method for forming a printed product according to the present invention will be described. A method for forming a printed matter according to an embodiment of the present invention (hereinafter referred to as a method for forming a printed matter according to an embodiment) is a method for forming a printed matter 300 using the intermediate transfer medium 10, and includes a first substrate. (1) An intermediate transfer medium preparation step of preparing an intermediate transfer medium 10 on which a transfer layer 5 is provided so as to be peelable from the first base material (1), and a first on the second base material (50). A thermal transfer sheet preparation step of preparing the thermal transfer sheet 100 in which the color material layer (51) and the second color material layer (53) are provided in the surface order; and a transfer target preparation step of preparing the transfer target 200; The transfer layer 5 of the intermediate transfer medium 10 prepared in the intermediate transfer medium preparation step has a release layer 3 located closest to the first substrate (1) among the layers constituting the transfer layer, and the first substrate The receiving layer 4 is positioned farthest from the material (1), and the release layer 3 A first image forming step of forming a first image (20) on the receiving layer 4 of the intermediate transfer medium using the first color material layer (51) of the thermal transfer sheet 100, comprising a rosin-based resin; After the first image forming step, the intermediate transfer medium is transferred using the transfer layer transfer step of transferring the transfer layer 5 of the intermediate transfer medium 10 onto the transfer target 200 and the second color material layer (53) of the thermal transfer sheet 100. The method further includes a second image forming step of forming a second image (30) on the ten release layers 3.

  According to the method of forming a printed matter of one embodiment, the transfer layer on which the first image is formed is transferred onto the transfer target with good transferability, and the second image is formed on the transferred transfer layer. Can be obtained. In addition, according to the method for forming a printed matter of one embodiment, the printed matter 300 having a three-dimensionality in which the first image (20) and the second image (30) are arranged at a predetermined interval in the thickness direction. Can be obtained. Hereafter, each process of the formation method of the printed matter of one Embodiment is demonstrated.

<Intermediate transfer medium preparation process>
The intermediate transfer medium preparation step is a step of preparing an intermediate transfer medium 10 in which the transfer layer 5 is provided on the first base material (1) as shown in FIGS. Then, in the method for forming a printed matter according to one embodiment, the transfer layer 5 of the intermediate transfer medium 10 prepared in this step includes the release layer 3 positioned closest to the first substrate (1), and the first substrate. The receiving layer 4 located farthest from the material (1) is included, and the release layer 3 contains a cellulosic resin. According to the method for forming a printed matter of one embodiment in which the intermediate transfer medium 10 having the release layer having this feature is used, the transfer layer 5 is transferred onto the transfer target 200 with good transferability in a transfer layer transfer step described later. Can be transferred.

  As the intermediate transfer medium 10 prepared in this step, the intermediate transfer medium 10 described in the above embodiment can be used as it is, and detailed description thereof is omitted here.

<Thermal transfer sheet preparation process>
In the thermal transfer sheet preparation step, as shown in FIGS. 4 and 5, the first color material layer (51) and the second color material layer (53) are sequentially arranged on one surface of the second base material (50). It is the process of preparing the thermal transfer sheet 100 provided in. As the thermal transfer sheet 100 prepared in this step, various thermal transfer sheets described as the thermal transfer sheet 100 that can be used in combination with the intermediate transfer medium 10 of the above embodiment can be appropriately selected and used. The detailed description of is omitted.

<Step of preparing a transfer object>
There is no limitation on the material to be transferred prepared in this step, and for example, plain paper, fine paper, tracing paper, plastic film, vinyl chloride, vinyl chloride-vinyl acetate copolymer, polycarbonate are mainly used. The plastic card etc. which are comprised can be mentioned. What has a predetermined image as a to-be-transferred body can also be used. In addition, by using a transfer object having transparency as the transfer object 200, the thermal transfer image formed in the thermal transfer image forming process can be visually recognized from the front surface side and the back surface side of the printed product 300 to be finally formed. Is possible.

  Next, the process of forming the printed product 300 using the intermediate transfer medium 10, the thermal transfer sheet 100, and the transfer target 200 prepared as described above will be specifically described with reference to FIGS. FIG. 6 is a process diagram for explaining a method of forming a printed material according to an embodiment, and (a) to (d) are all schematic cross-sectional views.

<First image forming step>
In this step, the intermediate transfer medium 10 prepared above and the thermal transfer sheet 100 are overlapped so that the transfer layer 5 of the intermediate transfer medium 10 and the first color material layer (51) of the thermal transfer sheet 100 face each other. Using a heating device such as a thermal head, the first image (20) is formed on the transfer layer 5 of the intermediate transfer medium 10, in other words, on the receiving layer 4, as shown in FIG. 6 (a). It is a process. The first image (20) may be an image formed by using a sublimation type thermal transfer method, or may be an image formed by a hot melt type thermal transfer method.

<Transfer layer transfer process>
The transfer target 200 prepared above and the transfer layer 5 of the intermediate transfer medium 10 on which the first image (20) is formed are superimposed so as to face each other, and as shown in FIG. In this step, the transfer layer 5 on which the first image (20) is formed is transferred onto the substrate 200. In the method for forming a printed material according to one embodiment, since the release layer 3 constituting the transfer layer 5 and positioned at the transfer interface contains a cellulose resin, the transfer layer 5 is formed on the transfer target 200. Transferability when transferring can be improved.

  There is no particular limitation on the method for transferring the transfer layer 5 on which the first image (20) has been formed onto the transfer target 200. In addition to a method using a heating device such as a thermal head, for example, a hot stamp method or a heat roll A method or the like can be used. Further, the transfer layer 5 can be transferred by other methods.

<Second image forming step>
In this step, the transfer target 200 and the thermal transfer sheet 100 are transferred onto the transfer target 200, the transfer layer 5 on which the release layer 3 is located on the outermost surface, and the second color material layer (53) of the thermal transfer sheet 100. And a second image (30) on the transfer layer 5, in other words, on the release layer 3, as shown in FIG. 6C, using a heating device such as a thermal head. Is a step of forming. Through this step, the first image (20) and the second image (30) are provided on the transfer target 200, and the first image (20) and the second image (30) are predetermined in the thickness direction. The prints 300 arranged at intervals are obtained.

  The second image (30) may be formed at a position overlapping with a part or all of the first image (20) formed on the receiving layer 4 in the thickness direction, or a part of the first image (20). Or may be formed at a position that does not overlap with the whole in the thickness direction (in the form shown in FIG. 6, a part of the first image (20) and the second image (30) overlap with each other in the thickness direction. In the form shown in (1), the first image (20) and the second image (30) do not overlap in the thickness direction). In addition, the 1st image (20) and the 2nd image (30) are the thickness direction by forming the 2nd image (30) in the position which overlaps with a part or all of the 1st image (20) in the thickness direction. Thus, it is possible to improve the apparent density of the thermal transfer image in the overlapping portion.

<< Modification of Forming Method of Printed Material >>
FIGS. 7A to 7E are modified embodiments of the method of forming a printed material according to one embodiment, and a transfer layer is detachable from the first base material (1) on the first base material (1). An intermediate transfer medium preparation step for preparing the intermediate transfer medium 10 provided with 5, and a first color material layer (51), a heat seal layer 52, and a second color material layer (53) on the second base material (50). Transfer of the intermediate transfer medium 10 that is prepared in the intermediate transfer medium preparation process, including a thermal transfer sheet preparation process that prepares the thermal transfer sheet 100 provided in a surface-sequential manner and a transfer target preparation process that prepares the transfer target 200 The layer 5 is a laminate in which the release layer 3 is located closest to the first base material (1) and the receiving layer 4 is located farthest from the first base material (1) among the layers constituting the transfer layer. As shown in FIG. 7 (a), the release layer 3 has a structure and contains a cellulose resin. A first image forming step of forming the first image (20) on the receiving layer 4 of the intermediate transfer medium using the first color material layer (51) of the thermal transfer sheet 100, as shown in FIG. After the first image forming step, a heat seal layer transfer step for transferring the heat seal layer 52 of the thermal transfer sheet 100 onto the transfer layer on which the first image (20) is formed, as shown in FIG. FIG. 7D shows a step of transferring the transfer layer 5 on which the first image (20) is formed on the transfer target 200 so that the transfer target 200 and the heat seal layer 52 are in direct contact with each other. ), A second image forming step of forming a second image (30) on the release layer 3 of the intermediate transfer medium 10 using the second color material layer (53) of the thermal transfer sheet 100 is included. It is a feature. According to the modification of the method for forming a printed material according to one embodiment, the transfer layer 5 is transferred onto the transfer target 200 via the heat seal layer 52, thereby bonding the transfer target 200 and the transfer layer 5. The property can be improved.

  In a modified embodiment of the method for forming a printed material according to one embodiment, a thermal transfer sheet (see FIG. 5) having a heat seal layer 52 is used as the thermal transfer sheet 100, and the transfer layer 5 on which the first image (20) is formed is used. It includes a step of transferring the heat seal layer 52 onto the transfer layer 5 in a stage before transfer onto the transfer target 200, and in the transfer layer transfer step, the transfer target 200 and the heat seal layer 52 are in direct contact with each other. In this way, the transfer layer 5 on which the first image (20) is formed is transferred onto the transfer target 200, which is different from the method for forming a print in the above embodiment. In terms of Therefore, descriptions of the first image forming step (see FIG. 7A) and the second image forming step (see FIG. 7D) are omitted.

<Heat seal layer transfer process>
In this step, after the first image forming step, the transfer layer 5 of the intermediate transfer medium 10 (the transfer layer 5 having the first image (20) formed on the receiving layer 4), the heat seal layer 52 of the thermal transfer sheet 100, and In the process of transferring the heat seal layer 52 onto the transfer layer 5 on which the thermal transfer image 20 is formed, as shown in FIG. 7B, using a heating device such as a thermal head. is there. The method for transferring the heat seal layer 52 is not particularly limited. For example, a hot stamp method or a heat roll method can be used in addition to a method using a heating device such as a thermal head. Further, the heat seal layer 52 can be transferred by other methods.

<Transfer layer transfer process>
In this step, the transfer target 200 prepared above and the heat seal layer 52 transferred onto the transfer layer 5 of the intermediate transfer medium 10 are overlapped to face each other, as shown in FIG. In this process, the transfer layer 5 on which the first image (20) is formed is transferred onto the transfer target 200 so that the transfer target 200 and the heat seal layer 52 are in direct contact with each other.

<Protective layer transfer process>
As shown in FIGS. 6D and 7E, in the second image forming process, the method for forming a printed material according to one embodiment is the second on the transfer layer 5, in other words, on the release layer 3. A step of transferring the protective layer 55 onto the second image (30) after forming the image (30) may be further included. The transfer of the protective layer 55 may be performed using a thermal transfer sheet 100 having a protective layer together with the first color material layer and the second color material layer, as shown in FIG. The protective layer transfer sheet having only the layer 55 may be used.

  The first image (20) and the second image (30) are formed by thermal transfer having a first color material layer (51) and a second color material layer (53) as shown in FIGS. The sheet may be used, or the first thermal transfer sheet having the first color material layer (51) and the second thermal transfer sheet having the second color material layer (53) may be used. Specifically, the first thermal transfer sheet having the first color material layer (51) and the second thermal transfer sheet having the second color material layer (53) are respectively set in the printer, and the first thermal transfer sheet is set. The first image (20) may be used to form the second image (30) using the second thermal transfer sheet. The 1st thermal transfer sheet said here is common in the thermal transfer sheet of various embodiment demonstrated above except the point which does not have the 2nd color material layer (53). The same applies to the second thermal transfer sheet.

  In addition, one or both of the first thermal transfer sheet and the second thermal transfer sheet have a heat seal layer 52, and the transfer layer 5 of the intermediate transfer medium 10 (the first layer on the receiving layer 4). The transfer layer 5) on which the image (20) is formed and the first heat transfer sheet or the heat seal layer 52 of the second heat transfer sheet are overlapped so that the heat transfer image 20 (first image (20)) is superimposed. The heat seal layer 52 may be transferred onto the formed transfer layer 5. Alternatively, a thermal transfer sheet having a heat seal layer may be separately prepared, and the heat seal layer may be transferred using the separately prepared thermal transfer sheet.

  Further, the first image (20) and the second image (30) may be images formed using a sublimation type thermal transfer method, or may be images formed using a thermal melting type thermal transfer method. Good. When the first image (20) is formed on the receiving layer 4 using the sublimation thermal transfer method, the intermediate layer having the receiving layer 4 containing a resin capable of receiving a coloring material such as a sublimation dye. The transfer medium 10 may be prepared. Since the release layer 3 contains a cellulosic resin capable of receiving a coloring material such as a sublimation dye, a thermal transfer image using a sublimation type thermal transfer method or a thermal melting type thermal transfer method is formed on the release layer 3. Either can be formed.

  Next, an Example is given and this invention is demonstrated further more concretely. Hereinafter, unless otherwise specified, “part” and “%” are based on mass.

(Preparation of intermediate transfer medium 1)
A polyethylene terephthalate film having a thickness of 16 μm was used as a base material, and a release layer coating liquid 1 having the following composition was applied to one surface of the base material so that the thickness upon drying was 1 μm, and then dried. Formed. Next, on the release layer, an intermediate layer coating solution having the following composition was applied and dried so that the thickness upon drying was 1.5 μm, thereby forming an intermediate layer. Next, the receiving layer coating liquid 1 having the following composition is applied on the intermediate layer so as to have a dry thickness of 2 μm, dried to form a receiving layer, and the release layer is formed on one surface of the substrate. Then, an intermediate transfer medium 1 provided with a transfer layer in which an intermediate layer and a receiving layer were laminated in this order was prepared.

<Peeling layer coating solution 1>
-16.9 parts of vinyl chloride-vinyl acetate copolymer resin (Solvine (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
Cellulose acetate butyrate resin (Mn: 30000) 1.0 part (CAB381-0.5 Eastman Chemical Co., Ltd.)
・ 0.8 parts of silicone oil (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
・ 0.8 parts of silicone oil (X-24-510 Shin-Etsu Chemical Co., Ltd.)
・ Silicon oil 0.5 parts (KF-352A Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

<Intermediate layer coating solution>
・ Polyester resin 30 parts (Byron 200 Toyobo Co., Ltd.)
・ Methyl ethyl ketone 35 parts ・ Toluene 35 parts

<Receptive layer coating solution 1>
・ 20 parts of vinyl chloride vinyl acetate copolymer resin (Solvine (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
・ Silicone oil 1 part (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone 79 parts

(Preparation of intermediate transfer medium 2)
Instead of the release layer coating solution 1, 1.0 part of cellulose acetate butyrate resin (CAB381-0.5 Eastman Chemical Co., Ltd.) (Mn: 30000) in the release layer coating solution 1 was added to cellulose acetate. All examples except that the release layer was formed using the release layer coating liquid 2 changed to 1.0 part of propionate resin (Mn: 25000) (CAP482-0.5 Eastman Chemical Co., Ltd.) In the same manner as in Example 1, an intermediate transfer medium 2 was prepared.

(Preparation of intermediate transfer medium 3)
The receiving layer coating solution 1 is changed to a receiving layer coating solution 2 having the following composition, and the back layer coating solution having the following composition is formed on the other surface of the substrate with a thickness of 1 μm when dried. An intermediate transfer medium 3 was prepared in the same manner as in Example 1 except that the back layer was formed by coating and drying.

<Receptive layer coating solution 2>
Polyester resin (Mn: 6000) 19.4 parts (Byron (registered trademark) GK810 Toyobo Co., Ltd.)
・ Silicon oil 0.6 parts (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

<Back layer coating liquid>
・ 1.8 parts of polyvinyl butyral resin (ESREC (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
・ 5.5 parts of polyisocyanate (Bernock (registered trademark) D750, Dainippon Ink & Chemicals, Inc.)
・ Phosphate surfactant 1.6 parts (Pricesurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・ Talc 0.35 parts (Microace (registered trademark) P-3 Nippon Talc Industry Co., Ltd.)
・ Toluene 18.5 parts ・ Methyl ethyl ketone 18.5 parts

(Preparation of intermediate transfer medium 4)
An intermediate transfer medium 4 was prepared in the same manner as in Example 1 except that the receiving layer coating solution 1 was changed to a receiving layer coating solution 3 having the following composition to form a receiving layer.

<Receptive layer coating solution 3>
・ 20 parts of vinyl chloride vinyl acetate copolymer resin (Solvine (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
・ Silicone oil 2 parts (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone 78 parts

(Preparation of intermediate transfer medium A)
An intermediate transfer medium A was prepared in the same manner as in Example 1 except that instead of the release layer coating solution 1, the release layer was formed by changing to the release layer coating solution A having the following composition.

<Coating liquid A for release layer>
-17.9 parts of vinyl chloride-vinyl acetate copolymer resin (Solvine (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
・ 0.8 parts of silicone oil (X-22-3000T Shin-Etsu Chemical Co., Ltd.)
・ 0.8 parts of silicone oil (X-24-510 Shin-Etsu Chemical Co., Ltd.)
・ Silicon oil 0.5 parts (KF-352A Shin-Etsu Chemical Co., Ltd.)
・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

(Preparation of thermal transfer sheet 1)
As a base material, a polyethylene terephthalate film with an easy-adhesion layer having a thickness of 5 μm is used, and on the easy-adhesion layer side of the base material, a yellow color material layer coating liquid, a magenta color material layer coating liquid having the following composition, The cyan color material layer coating solution was applied and dried so that the thickness when dried was 0.5 μm, and a yellow color material layer, a magenta color material layer, and a cyan color material layer were formed in this order in the order of planes. Next, a heat-resistant slipping layer coating liquid having the following composition is applied to the surface of the substrate opposite to the easy-adhesion layer so that the thickness upon drying is 1 μm and dried to form a heat-resistant slipping layer. Thus, a yellow color material layer, a magenta color material layer, and a cyan color material layer are provided in the surface order on one surface side which is the easy adhesion layer side of the base material, and a back surface layer is provided on the other surface side of the base material. The provided thermal transfer sheet 1 was prepared.

<Coating solution for yellow color material layer>
・ 5 parts of Solvent Yellow 93 ・ 4 parts of polyvinyl acetoacetal resin
(KS-5 Sekisui Chemical Co., Ltd.)
・ Toluene 50 parts ・ Methyl ethyl ketone 50 parts

<Coating liquid for magenta color material layer>
・ Disper Thread 60 3 parts ・ Dispers Violet 26 3 parts ・ Polyvinylacetoacetal resin 5 parts
(KS-5 Sekisui Chemical Co., Ltd.)
・ Toluene 50 parts ・ Methyl ethyl ketone 50 parts

<Cyan color material layer coating solution>
-Solvent Blue 63 3 parts-Disperse Blue 354 2.5 parts-Polyvinylacetoacetal resin 5 parts (KS-5 Sekisui Chemical Co., Ltd.)
・ Toluene 50 parts ・ Methyl ethyl ketone 50 parts

<Coating fluid for heat resistant slipping layer>
・ 1.8 parts of polyvinyl butyral resin (ESREC (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
・ 5.5 parts of polyisocyanate (Bernock (registered trademark) D750, Dainippon Ink & Chemicals, Inc.)
・ Phosphate surfactant 1.6 parts (Pricesurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・ Talc 0.35 parts (Microace (registered trademark) P-3 Nippon Talc Industry Co., Ltd.)
・ Toluene 18.5 parts ・ Methyl ethyl ketone 18.5 parts

(Preparation of thermal transfer sheet 2)
In the thermal transfer sheet 1 created above, a release layer coating liquid having the following composition was applied on the easy-adhesion layer side of the substrate so that the thickness upon drying was 1 μm, and dried to form a release layer. . Next, the heat-sealing layer coating liquid 1 having the following composition on the release layer is applied and dried so as to have a thickness of 2 μm when dried, thereby forming a heat-sealing layer. The yellow color material layer, the magenta color material layer, the cyan color material layer, and the heat seal layer are provided in the surface order on one surface side, and the back surface layer is provided on the other surface side of the substrate. The obtained thermal transfer sheet 2 was prepared.

<Release layer coating solution>
・ Epoxy group-containing silicone-modified acrylic resin 16 parts (Cell Top (registered trademark) 226 Daicel Corporation)
Aluminum catalyst (solid content 10%) 3 parts (Cell Top (registered trademark) CAT-A Daicel Corporation)
・ Toluene 20 parts ・ Methyl ethyl ketone 20 parts

<Coating fluid for heat seal layer>
・ Acrylic resin 16 parts ・ Vinyl chloride-vinyl acetate copolymer resin 4 parts ・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

(Preparation of thermal transfer sheet 3)
As a base material, a polyethylene terephthalate film with a 5 μm-thick easy-adhesion layer is used, and on the easy-adhesion layer side of this base material, a sublimable fluorescent color material layer coating liquid having the following composition has a thickness of 0 when dried. The thermal transfer sheet 3 was created by applying and drying to a thickness of 0.5 μm to form a sublimable fluorescent color material layer. Next, the heat-resistant slipping layer coating liquid having the above composition is applied to the surface of the substrate opposite to the easy-adhesive layer so that the thickness upon drying is 1 μm and dried to form a heat-resistant slipping layer. Thus, a thermal transfer sheet 3 was prepared in which a sublimable fluorescent color material layer was provided on one surface side of the base material which is the easy adhesion layer side, and a back layer was provided on the other surface side of the base material.

<Coating liquid for sublimation fluorescent color material layer>
・ Ubitex OB 2 parts ・ Polyvinylacetoacetal resin 4 parts
(KS-5 Sekisui Chemical Co., Ltd.)
・ Toluene 50 parts ・ Methyl ethyl ketone 50 parts

(Preparation of thermal transfer sheet 4)
In the thermal transfer sheet 1 prepared above, a protective layer coating solution having the following composition was applied and dried on the easy adhesion layer side of the substrate so that the thickness when dried was 1 μm, and a protective layer was formed. Next, an adhesive layer coating liquid having the following composition is applied onto the protective layer so that the thickness upon drying is 1 μm, and the adhesive layer is formed by drying, whereby one of the base material on the easy adhesive layer side is formed. A yellow color material layer, a magenta color material layer, a cyan color material layer, and a laminate of a protective layer and an adhesive layer are provided in a surface sequence on the surface side, and a back layer is provided on the other surface side of the substrate. The thermal transfer sheet 4 provided with was prepared.

<Coating liquid for protective layer>
・ Polyester resin 20 parts ・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

(Creation of prints)
The intermediate transfer medium shown in Table 1 below and the thermal transfer sheet were used as a combination of each example and comparative example. In Table 1, the thermal transfer sheet in the condition A column is a thermal transfer sheet used for forming a thermal transfer image on the receiving layer located on the outermost surface of each intermediate transfer medium, and the thermal transfer sheet in the condition B column is the intermediate transfer sheet. Transfer layer of medium (in Examples 1-3, 5 and Comparative Example 1, a laminate in which a release layer, an intermediate layer, and a receiving layer are laminated in this order from the substrate side, and in Example 4, a substrate Used to form a thermal transfer image on the release layer located on the outermost surface after transfer of the release layer, intermediate layer, receptor layer, and heat seal layer in this order) Means a sheet.

(Formation of Thermal Transfer Image 1 Using Thermal Transfer Sheet in Condition A Column)
The intermediate transfer medium shown in Table 1 below and the thermal transfer sheet shown in the Condition A column are combined, and in the combination of Examples 1 to 4 and Comparative Example 1 with the following printer, energy corresponding to the image pattern is applied, The thermal transfer image 1 is formed by sequentially transferring the color material components contained in the color material layers (yellow, magenta, cyan color material layers) of each thermal transfer sheet to the receiving layer of the intermediate transfer medium. In the thermal transfer image 1, the energy corresponding to the image pattern is applied, and the color material component contained in the color material layer (sublimation fluorescent color material layer) of the thermal transfer sheet is transferred to the receiving layer of the intermediate transfer medium. Formed.
In the combination of Example 4, the heat seal layer was transferred onto the thermal transfer image 1 under the printing conditions of 200/255 gradation by the following printer.

(Transfer of transfer layer)
After the thermal transfer image 1 is formed, a card made of polyvinyl chloride as a transfer medium is used under the conditions of 20 ° C., 50% environment, 40 ° C., 80% environment, 180 ° C., 2 inch / sec using a card laminator (SIP). On the (PVC card) (Dai Nippon Printing Co., Ltd.), the transfer layer including the receiving layer on which the thermal transfer image 1 was formed was transferred.

(Peeling evaluation)
After transferring the transfer layer, the peelability when the transfer layer transferred onto the transfer material is peeled from the thermal transfer sheet shown in the condition A column of Table 1 is visually confirmed, and the following evaluation is performed. Peeling evaluation was performed based on the criteria. The evaluation results are shown in Table 2.

[Evaluation criteria]
◯: There is no fusion between the transfer object and the thermal transfer sheet in the condition A column, and it can be peeled off without any problem.
NG: The material to be transferred and the thermal transfer sheet in the condition A column are thermally fused.

(Formation of Thermal Transfer Image 2 Using Thermal Transfer Sheet in Condition B)
After transferring the transfer layer, the intermediate transfer medium onto which the transfer layer is transferred and the thermal transfer sheet shown in the condition B column are combined, and the energy corresponding to the image pattern is applied by the following printer to transfer the transferred transfer layer. The color material components contained in the color material layers (yellow, magenta, cyan color material layer) of each thermal transfer sheet were sequentially transferred to the release layer located on the outermost surface to form a thermal transfer image 2.
In the combinations of Examples 4 and 5, after the thermal transfer image 2 was formed, the protective layer was transferred onto the thermal transfer image 2 under the printing conditions of 200/255 gradation by the following printer.

(Image formation evaluation)
In the formation of the thermal transfer image 2, it was visually confirmed whether the thermal transfer image 2 could be formed on the release layer located on the outermost surface after transfer, and image formation evaluation was performed based on the following evaluation criteria. The evaluation results are also shown in Table 2.

[Evaluation criteria]
○: A thermal transfer image could be formed.
NG: A thermal transfer image could not be formed.

(Printer)
Thermal head: KEE-57-12GAN2-STA (Kyocera Corporation)
Heating element average resistance: 3303 (Ω)
Main scanning direction printing density: 300 (dpi)
Sub-scanning direction printing density: 300 (dpi)
1 line cycle: 3.0 (msec.)
Printing start temperature: 35 (℃)
Pulse duty ratio: 85 (%)
Printing voltage: 18.0 (V)

DESCRIPTION OF SYMBOLS 10 ... Intermediate transfer medium 1 ... Base material, 1st base material 3 ... Release layer 4 ... Receiving layer 5 ... Transfer layer 100 ... Thermal transfer sheet 50 ... Base for thermal transfer sheet Material, second base material 51 ... first color material layer 53 ... second color material layer 55 ... protective layer 20A ... first image 20B ... second image 200 ... transferred Body 300 ... Print

Claims (4)

An intermediate transfer medium having a transfer layer provided on a substrate so as to be peelable from the substrate,
The transfer layer includes a release layer located closest to the substrate and a receiving layer located farthest from the substrate;
The intermediate transfer medium, wherein the release layer contains a cellulose resin.   The intermediate transfer medium according to claim 1, wherein the cellulose resin is one or both of a cellulose acetate butyrate resin and a cellulose acetate propionate resin. A method of forming a print using an intermediate transfer medium,
An intermediate transfer medium preparation step of preparing an intermediate transfer medium provided with a transfer layer on the first base material so as to be peelable from the first base material;
A thermal transfer sheet preparation step of preparing a thermal transfer sheet in which the first color material layer and the second color material layer are provided in the surface order on the second substrate;
A transferred object preparation step of preparing a transferred object;
Including
The transfer layer of the intermediate transfer medium prepared in the intermediate transfer medium preparation step includes a release layer positioned closest to the first substrate and a receiving layer positioned farthest from the first substrate. And the release layer contains a cellulosic resin,
A first image forming step of forming a first image on the receiving layer of the intermediate transfer medium using the first color material layer of the thermal transfer sheet;
A transfer layer transfer step of transferring the transfer layer of the intermediate transfer medium onto the transfer target after the first image forming step;
A second image forming step of forming a second image on the release layer of the intermediate transfer medium using the second color material layer of the thermal transfer sheet;
A method for forming a printed matter, further comprising: The thermal transfer sheet is a thermal transfer sheet in which the first color material layer, the heat seal layer, and the second color material layer are provided in the surface order on the second base material,
A heat seal layer transfer step of transferring the heat seal layer of the thermal transfer sheet onto the transfer layer on which the first image is formed after the first image forming step;
In the transfer layer transfer step, the transfer layer on which the first image is formed is transferred onto the transfer target body so that the transfer target body and the heat seal layer are in direct contact with each other. The method for forming a printed matter according to claim 3.

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