JP2019064152A - Protective layer transfer sheet - Google Patents

Abstract

To provide a protective layer transfer sheet capable of obtaining a mat-like printed matter having good resistance to fingerprint adhesion.SOLUTION: In a protective layer transfer sheet 100 having a release layer 2 and a transfer layer 10 laminated in this order on one surface of a base material 1, the transfer layer 10 has a single layer structure formed of only the protective layer 5 or a laminated structure such that the protective layer 10 is positioned closest to the release layer 2, the release layer contains a binder resin and a filler, and the protective layer contains organofluorine compound particles.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a protective layer transfer sheet.

  A thermal transfer image is transferred onto a transfer target using a sublimation thermal transfer method, from the viewpoint of excellent transparency, high reproducibility of intermediate colors and high gradation, and easy formation of high quality images equivalent to conventional full color photographic images. It is widely used to form. As a printed matter on which a thermal transfer image is formed on a transferee, there are known digital photographs and ID cards used in many fields such as identification cards, driver's licenses, membership cards and the like.

  The formation of a thermal transfer image by a sublimation thermal transfer method is a thermal transfer sheet provided with a dye layer on one side of a substrate, and a thermal transfer sheet provided with a receptor layer on one side of another substrate, for example, a transferee. It is carried out by combining with an image receiving sheet. Specifically, the transferred material and the dye layer of the thermal transfer sheet are superposed, and energy is applied to the back side of the thermal transfer sheet by heating means such as a thermal head to transfer the dye of the dye layer onto the transferred material. It is done by In such a sublimation thermal transfer system, the transfer amount of the dye can be controlled by the amount of energy applied to the thermal transfer sheet, and density gradation is possible. Therefore, the thermal transfer image is very sharp, and transparency and half tone It is excellent in color reproducibility and tonality, and can form high-quality prints comparable to full-color photographic images.

  By the way, the thermal transfer image formed by the above-mentioned sublimation thermal transfer system has a defect that the durability is inferior since the coloring material is not a pigment but a dye having a relatively low molecular weight. Therefore, generally, for a thermal transfer image formed by a sublimation thermal transfer method, using a protective layer transfer sheet having a protective layer, the protective layer is transferred onto the thermal transfer image to improve the durability. There is.

  Recently, as a print on which a protective layer is transferred onto a thermal transfer image formed by a sublimation thermal transfer method, the surface does not have a gloss (sometimes referred to as a gloss), and for example, a coat. There is a demand for obtaining a print having a feeling of non-gloss like paper (hereinafter sometimes referred to as matte). In response to such a demand, for example, Patent Document 1 proposes a method of giving a matte impression to a print by embossing an embossed plate having an irregular surface and making the surface of the print uneven. ing. Hereinafter, a print having a matte feeling (non-glossy feeling) may be referred to as a matte-tone print, and a print having a glossiness (glossy) may be referred to as a gloss-like print.

  By the way, matte-like printed matter has a problem that fingerprints and the like are more likely to be attached to the surface than fingerprint-like printed matter (anti-fingerprint adhesion is low) and the attached fingerprints are easily noticeable .

JP, 2006-182012, A

  The present invention has been made in view of such a situation, and has as its main object to provide a protective layer transfer sheet capable of obtaining a matte tone print having good fingerprint resistance.

  The present invention for solving the above problems is a protective layer transfer sheet in which a transfer layer including a release layer and a protective layer is laminated in this order on one surface of a substrate, and the transfer layer is a transfer layer. A single-layer structure formed only of the protective layer, or a laminated structure in which the protective layer is located closest to the release layer, and the release layer contains a binder resin and a filler, The protective layer is characterized in that it contains a particulate organic fluorine compound.

  Moreover, the value (divided by the thickness (μm) of the release layer) of the ratio (mass%) of the mass of the filler to the mass of the binder resin contained in the release layer is greater than 0 and 40 or less. It may be in the range. Further, a value obtained by dividing the volume average particle diameter (μm) of the filler contained in the release layer by the thickness (μm) of the release layer is in the range of 0.5 to 9 inclusive. It is also good. Further, the ratio (mass%) of the mass of the filler to the mass of the binder resin contained in the release layer is divided by the volume average particle diameter (μm) of the filler contained in the release layer. The value may be 1.5 or more.

  According to the protective layer transfer sheet of the present invention, by transferring the transfer layer of the protective layer transfer sheet, it is possible to obtain a matte-tone print having good anti-fingerprint adhesion.

It is a schematic sectional drawing which shows an example of the protective layer transfer sheet of one Embodiment. It is a schematic sectional drawing which shows an example of the protective layer transfer sheet of one Embodiment. It is a schematic sectional drawing which shows an example of the protective layer transfer sheet of one Embodiment. It is a schematic sectional drawing which shows an example of a state when a transfer layer is transcribe | transferred on a to-be-transferred body using the protective layer transfer sheet of one Embodiment, (a) shows the state before transfer, (b) shows a transfer. It shows the state after. It is a schematic sectional drawing which shows an example of a state when a transfer layer is transcribe | transferred on a to-be-transferred body using the protective layer transfer sheet of one Embodiment, (a) shows the state before transfer, (b) shows a transfer. It shows the state after.

<< Protective Layer Transfer Sheet >>
Hereinafter, the protective layer transfer sheet 100 according to an embodiment of the present invention (hereinafter, referred to as a protective layer transfer sheet according to an embodiment) will be specifically described with reference to the drawings.

  As shown in FIGS. 1 to 3, the protective layer transfer sheet 100 according to one embodiment is a substrate 1 and a separation provided on one surface of the substrate 1 (the upper surface of the substrate 1 in the illustrated embodiment). It comprises a mold layer 2 and a transfer layer 10 provided on the release layer 2 (the upper surface of the release layer 2 in the illustrated embodiment). The transfer layer 10 is a layer which peels off at the interface with the release layer 2 by transferring energy to the protective layer transfer sheet 100 of one embodiment, and moves onto the transfer target. The transfer layer 10 has a single layer structure consisting only of a protective layer or a plurality of layers including a protective layer, and the transfer layer 10 in the form shown in FIG. 1 exhibits a single layer structure consisting only of the protective layer 5 The transfer layer 10 of the form shown in FIG. 2 has a laminated structure in which a protective layer 5 and an adhesive layer 6 are laminated in this order from the base 1 side (the release layer 2 side). The protective layer 5 constituting the transfer layer 10 is a layer located on the outermost surface when the transfer layer 10 is transferred onto the transfer target. Therefore, when the transfer layer 10 has a laminated structure, the protective layer 5 is located closest to the side of the substrate 1 (the release layer 2) among the layers constituting the transfer layer 10. Hereinafter, each structure of the protective layer transfer sheet 100 of one Embodiment is demonstrated.

(Base material)
The substrate 1 is an essential component of the protective layer transfer sheet 100 of the embodiment, and holds the release layer 2 and the transfer layer 10 located on one surface of the substrate 1. The material of the substrate 1 is not particularly limited, but those having mechanical properties that can withstand the heat applied when transferring the transfer layer 10 and have no trouble in handling are preferable. Examples of such a substrate 1 include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene Acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene -Ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene Various plastic films or sheets such as polyvinylidene fluoride and the like. Each of these materials can be used alone, but may be used as a laminate in combination with other materials. The thickness of the substrate 1 can be appropriately set according to the material so that the strength and heat resistance thereof become appropriate, preferably in the range of 0.5 μm to 50 μm, and more preferably in the range of 1 μm to 20 μm, The range of 1 μm to 10 μm is more preferable.

  Further, in the base 1, the surface on which the release layer 2 is provided may be subjected to an adhesion treatment. The adhesion between the substrate 1 and the release layer 2 can be improved by performing the adhesion treatment.

  As the adhesion treatment, for example, known resin surfaces such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet light treatment, surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, grafting treatment, etc. The modification technology can be applied as it is. Also, two or more of these treatments can be used in combination.

(Release layer)
As shown in FIGS. 1 to 3, the release layer 2 is provided on the base material 1. And, the release layer 2 contains a binder resin and a filler. The filler contained in the release layer 2 is the surface of the transfer layer 10 (protective layer 5) transferred onto the transferred body when the transfer layer 10 including the release layer is transferred onto the transferred body. Play a role in expressing the unevenness pattern. In addition, it is good also as a structure which provided arbitrary layers between the base material 1 and the mold release layer 2 (not shown). In the specification of the present application, when the release layer 2 contains a filler, not only the form in which the filler is present inside the surface of the release layer 2 without protruding from the surface of the release layer 2, but also the release The form in which the filler protrudes from the surface of the layer 2, that is, the form in which the filler is present so as to straddle the release layer 2 and the transfer layer 10 described later, or the form in which the substrate 1 and the release layer 2 are straddled The form in which the filler is present, or the form in which these are combined is also included. In addition, an optional layer is provided between the substrate 1 and the release layer 2 or between the release layer 2 and the transfer layer 10, and the filler is formed by straddling the optional layer and the release layer 2. The forms which exist are also included.

  According to the release layer 2 of the above embodiment, the surface of the transfer layer 10 (protective layer 5) transferred onto the transferred body exhibits a concavo-convex pattern corresponding to the shape of the filler contained in the release layer 2 It can be done. Then, by expressing the concavo-convex pattern on the surface of the transfer layer 10 after transfer onto the transfer target body, it is possible to impart a matte feeling to the printed matter obtained by transferring the transfer layer 10 onto the transfer target body.

  Although there is no particular limitation on the form of inclusion of the filler, for example, as shown in FIG. 4A, of the surfaces of the release layer 2, the surface located on the transfer layer 10 side (hereinafter referred to as one of the release layers 2 In the case where the filler is projected from the surface), as shown in FIG. 4B, the surface of the transfer layer 10 transferred onto the material to be transferred corresponds to the shape of the filler. The unevenness pattern can be expressed as it is.

  Further, the transfer of the transfer layer 10 onto the transfer target body is carried out by bringing the substrate 1 into contact with the heating means and applying energy from the heating means. At this time, a predetermined printing pressure is applied to the transfer portion of the transfer layer 10 transferred onto the transfer target by the heating unit. Therefore, a form (not shown) in which the filler is projected from a surface (hereinafter referred to as the other surface of the release layer 2) of the surfaces of the release layer 2 (hereinafter referred to as the other surface of the release layer 2). As shown in a), even when the filler is present inside the release layer 2 without protruding the filler from the surface of the release layer 2, as shown in FIG. At the time of transfer, a concavo-convex pattern can be developed on the surface of the transfer layer 10 after transfer onto the transfer target body so as to follow the shape of these fillers. More specifically, as shown in FIG. 5A, when the filler is present inside the release layer 2, the release pressure is applied by applying a predetermined printing pressure to the release layer by the heating means. The filler present inside the mold layer 2 is pushed into the side of the transfer layer 10 in contact with the mold release layer 2, thereby contacting the mold release layer 2 as shown in FIG. 5 (b). A concavo-convex pattern appears on the surface of the transfer layer 10 on the opposite side. FIG. 4A and FIG. 5A are schematic cross-sectional views showing the state before transferring the transfer layer. In the embodiment shown in FIGS. 4 and 5, the transfer layer 10 has a single-layer structure consisting of only a protective layer, but the same applies to the transfer layer 10 having a laminated structure.

  The type of filler is also not particularly limited, and inorganic particles, organic particles, and the like can be appropriately selected and used. Examples of the inorganic particles include calcium carbonate particles, aluminum oxide particles, zirconium oxide particles, magnesium oxide particles, titanium oxide particles, aluminum hydroxide particles, pseudoboehmanite particles, aluminum silicate particles, magnesium silicate particles, magnesium carbonate particles, mica particles Etc. Further, as the organic particles, for example, polyethylene wax particles, resin particles and the like can be mentioned. As a resin component which makes resin particles, for example, acrylic resin, urethane resin, silicone resin, nylon resin, styrene resin, organic fluorine compound, benzoguanamine-formaldehyde condensate, benzoguanamine-melamine-formaldehyde condensate, melamine-formaldehyde condensate, etc. Can be mentioned. Among them, acrylic resin particles can be preferably used. The release layer 2 may contain one type alone, or two or more types as a filler.

  There is no particular limitation on the shape of the filler, and any shape such as a spherical shape, a scaly shape, a flat shape, a spindle shape, a polygonal shape, a dome shape, and an irregular shape may be used.

  The content of the filler contained in the release layer 2 and the thickness of the release layer 2 are not particularly limited, but the ratio (% by mass) of the mass of the filler to the mass of the binder resin contained in the release layer 2 ) Divided by the thickness (μm) of the release layer 2 is in the range of more than 0 and 40 or less, and further in the range of 0.3 or more and 30 or less, and particularly in the range of 5 or more and 15 or less It is preferable to satisfy the following relationship. In the case where the release layer contains two or more fillers, the description given as the mass of the filler may be read as the total mass of the two or more fillers. The same applies to the case where the release layer contains two or more binder resins, and the description of the mass of the binder resin may be replaced with the total mass of the two or more binder resins. According to the release layer 2 satisfying this relationship, it is possible to express a sufficient uneven pattern on the surface of the transfer layer 10 transferred onto the transfer target. Thereby, sufficient matte feeling can be given to a printed matter. The thickness of the release layer 2 is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.55 μm to 4.5 μm.

  Also, the particle diameter of the filler is not particularly limited, but the value obtained by dividing the volume average particle diameter (μm) of the filler by the thickness (μm) of the release layer is in the range of more than 0 and 40 or less. It is preferable to set the volume average particle diameter of the filler and the thickness of the parting layer 2 to satisfy the relationship within the range of 0.5 to 9, particularly within the range of the relationship of 1 to 2. In addition, when the release layer contains 2 or more types of fillers, the volume average particle diameter of the said filler is replaced with the volume average particle diameter which averaged the volume average particle diameter of the said 2 or more types of fillers. Just do it. For example, when the release layer contains filler A having a volume average particle diameter of X μm and filler B having a volume average particle diameter of Y μm, (X + Y) / 2 is the volume average particle diameter. According to the release layer 2 satisfying this relationship, it is possible to impart a sufficient matte feeling to the printed matter by using the protective layer transfer sheet of one embodiment provided with the release layer 2. The volume average particle diameter of the filler is preferably in the range of 0.1 μm to 9.5 μm, and more preferably in the range of 0.1 μm to 4.5 μm. In addition, "volume average particle diameter" means the particle diameter measured based on JIS-Z-8819-2 (2001), and particle size distribution and particle size distribution measuring device (Nanotrack particle size distribution measuring device Nikkiso It is a value when it measures using (stock).

  Moreover, the value which divided the ratio (mass%) of the mass of the filler with respect to the mass of the binder resin which the release layer 2 contains by the volume average particle diameter (μm) of the filler which the release layer 2 contains is It is preferable to satisfy the relationship in the range of more than 0 and 40 or less, and further in the range of 1.5 or more and 20 or less, and particularly in the range of 4.5 or more and 9.5 or less. According to the release layer 2 satisfying this relationship, it is possible to impart a sufficient matte feeling to the printed matter by using the protective layer transfer sheet of one embodiment provided with the release layer 2. The volume average particle size of the preferred filler is as described above.

  The content of the filler relative to the total mass of the release layer 2 is not particularly limited, but is preferably in the range of 1% by mass to 25% by mass, and more preferably in the range of 5% by mass to 15% by mass.

  The release layer 2 of the preferred embodiment has a volume average particle diameter of the filler in the above-mentioned preferred range in the range of 1% by mass to 25% by mass, particularly 5% by mass, based on the total mass of the release layer 2 A value obtained by dividing the volume average particle diameter (μm) of the filler by the thickness (μm) of the release layer satisfies the above-mentioned preferable relationship. According to the protective layer transfer sheet 100 of an embodiment provided with the release layer 2 of a preferable form, a high matte feeling can be given to printed matter using a protective layer transfer sheet.

  The binder resin contained in the release layer 2 is not particularly limited, and, for example, various silicone-modified resins such as waxes, silicone wax, silicone resin, silicone-modified acrylic resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol, Acrylic resin, acrylic-styrene copolymer, thermosetting epoxy-amino copolymer, and thermosetting alkyd-amino copolymer (thermosetting amino alkyd resin), melamine resin, cellulose resin, urea resin A binder resin which can make the transferability of the transfer layer 10 good, such as resin, polyolefin resin, cellulose resin, etc. can be suitably used. The release layer 2 may contain one type as a binder resin, or may contain two or more types.

  The content of the binder resin relative to the total mass of the release layer 2 is not particularly limited, but is preferably in the range of 75% by mass to 99% by mass, and more preferably in the range of 80% by mass to 95% by mass.

  There is also no particular limitation on the method of forming the release layer 2, and, for example, a release layer coating liquid in which a binder resin, a filler, and various additives used as necessary are dispersed or dissolved in an appropriate solvent is used. The coating liquid can be prepared and applied and dried on the substrate 1 or any layer provided on the substrate 1. Examples of the coating method include a gravure printing method, a screen printing method, a reverse coating method using a gravure plate, and the like. Moreover, the application method other than this can also be used. The same applies to the coating methods of various coating liquids described later.

(Transfer layer)
As shown in FIGS. 1 to 3, a transfer layer 10 is provided on the release layer 2. The transfer layer 10 has a single-layer structure consisting of only the protective layer 5 (see FIG. 1) or a laminated structure in which the protective layer 5 is positioned closest to the release layer 2 (FIG. 2). reference). In addition, the transfer layer 10 of the form shown in FIG. 2 has a laminated structure in which the protective layer 5 and the adhesive layer 6 are laminated in this order from the release layer 2 side. The transfer layer 10 of the form shown in FIG. 3 includes both a single layer structure and a laminated structure, and the description of the protective layer 5 is omitted.

  As described above, according to the protective layer transfer sheet 100 of one embodiment, the presence of the release layer 2 containing the filler for causing the surface of the transfer layer 10 after transfer to express the concavo-convex pattern, A matte feeling can be imparted to a print obtained by transferring the transfer layer 10 onto a transferee.

  In describing the superiority of the protective layer transfer sheet according to one embodiment, fingerprints of a general matte print, fingerprints of sebum, etc. (hereinafter referred to as fingerprints) will be described. A general matte-tone print has an inherent problem that fingerprints tend to adhere to the surface as compared with a gloss-tone print. That is, the problem of low fingerprint adhesion is inherent in the general matte print. This problem is presumed to be due to the surface condition of the matte print, that is, the uneven shape of the surface. Furthermore, due to the difference in glossiness, general matte-toned prints are more noticeable when the fingerprints are attached than when fingerprints are attached to the surface of the gloss-toned print, which also indicates that the matte-toned print The printed matter is required to have good anti-fingerprint adhesion.

(Protective layer)
Therefore, in the protective layer transfer sheet 100 of one embodiment, the protective layer 5 positioned on the outermost surface when the transfer layer 10 is transferred onto the transfer target contains a binder resin and a particulate organic fluorine compound. It is characterized by Hereinafter, the particulate organic fluorine compound may be referred to as organic fluorine compound particles.

  According to the protective layer transfer sheet 100 of one embodiment in which the protective layer 5 constituting the transfer layer 10 contains the organic fluorine compound particles, the protective layer 5 can be provided with good fingerprint resistance. As a result, by using the protective layer transfer sheet 100 of one embodiment, it is possible to obtain a print having good fingerprint resistance on the surface. Further, as described above, the presence of the release layer 2 containing the above-described filler can impart a matte feeling to the printed matter obtained by the transfer of the transfer layer 10. That is, according to the protective layer transfer sheet 100 of one embodiment, by transferring the transfer layer 10 onto the transfer-receiving material, it is possible to obtain a matte print having excellent anti-fingerprint adhesion.

  Although the mechanism by which good anti-fingerprint adhesion is expressed in the protective layer 5 concerned by containing the organic fluorine compound particles in the protective layer 5 is not clear at present, the organic particles among various particles are The fact that the fluorine compound particles contribute to the improvement of the fingerprint adhesion resistance of the protective layer 5 is also apparent from the results of the examples and the comparative examples described later.

  Furthermore, anti-fingerprint removability can be imparted to the protective layer 5 by forming the protective layer 5 containing organic fluorine compound particles. Thereby, even when a fingerprint adheres to the printed matter obtained using the protective layer transfer sheet 100 of one embodiment, the adhered fingerprint can be easily removed.

  As the organic fluorine compound particles, for example, PTFE (polytetrafluoroethylene) particles, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) particles, FEP (tetrafluoroethylene-hexafluoropropylene copolymer) particles, ETFE (Tetrafluoroethylene-ethylene copolymer) particles, PVDF (polyvinylidene fluoride) particles, PCTFE (polychlorotrifluoroethylene) particles, ECTFE (chlorotrifluoroethylene-ethylene copolymer) particles, and the like. Also, organic fluorine compound particles other than this may be used. The protective layer 5 may contain one type alone or two or more types as the organic fluorine compound particles.

  The content of the organic fluorine compound particles is not particularly limited, but the content of the organic fluorine compound particles with respect to the total mass of the protective layer 5 is preferably 1% by mass or more, and more preferably 2% by mass or more. By making content of an organic fluorine compound particle into the said preferable content, the further improvement of fingerprint-proof adhesiveness can be aimed at. The upper limit value may be appropriately set according to the content of the binder resin described later, and is preferably 15% by mass, more preferably 10% by mass.

  The particle diameter of the organic fluorine compound particles is not particularly limited, and may be any shape such as spherical shape, scaly shape, flat shape, spindle shape, polygonal shape, dome shape, and irregular shape.

  In addition, as the organic fluorine compound particles, the protective layer 5 is an organic fluorine compound particle having a volume average particle diameter in the range of 0.1 μm to 10 μm, or a primary average particle diameter in the range of 0.1 μm to 3 μm. It is preferable to contain organic fluorine compound particles. By making the protective layer 5 containing the organic fluorine compound particles having a volume average particle diameter or a primary average particle diameter in the above-mentioned preferable range, it is possible to further improve the fingerprint adhesion resistance given to the protective layer 5. .

  The binder resin contained in the protective layer 5 is not particularly limited, and may be appropriately determined in consideration of durability such as plasticizer resistance and abrasion resistance. As such a binder resin, for example, polyester resin, acrylic resin, polycarbonate resin, phenoxy resin, ultraviolet absorbing resin, epoxy resin, polystyrene resin, polyurethane resin, acrylic urethane resin, etc. The resin which carried out silicone modification | denaturation of each resin, the mixture of these each resin, ionizing radiation curable resin, ultraviolet-ray absorptive resin etc. are mentioned. The protective layer 5 may contain 1 type as binder resin, and may contain 2 or more types.

  The ionizing radiation curable resin can be suitably used as a binder resin for the protective layer in that it is particularly excellent in plasticizer resistance and scratch resistance. The ionizing radiation curable resin can be appropriately selected and used from conventionally known ionizing radiation curable resins. For example, a radically polymerizable polymer or oligomer is crosslinked and cured by ionizing radiation irradiation, and as necessary, A photopolymerization initiator may be added and polymerized and crosslinked by electron beam or ultraviolet light. The protective layer 5 containing the ultraviolet absorbing resin is excellent in imparting light resistance to the printed matter.

  As the ultraviolet absorbing resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber to a thermoplastic resin or the above ionizing radiation curable resin can be used. More specifically, it is possible to add an addition polymerizable double bond to a conventionally known non-reactive organic ultraviolet absorber such as a salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, and hindered amine. Examples thereof include those having a reactive group such as 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 or an isocyanate group.

  85 mass% or more is preferable with respect to the total mass of the protective layer 5, and, as for content of the binder resin for providing durability to the said protective layer, 90 mass% or more is more preferable. By making content of binder resin into a preferable range, sufficient durability can be provided to the protective layer 5, and drop-off | omission of organic fluorine compound particle can be prevented. The upper limit value may be determined in consideration of the content of the organic fluorine compound particles.

  In addition, as shown in FIG. 1, when the transfer layer 10 has a single-layer structure including only the protective layer 5, the protective layer 5 contains a component having adhesion between the transfer target and the transfer layer 10. Is preferred. When measures are taken to ensure the adhesion to the transfer layer 10 on the side of the transferee, the protective layer 5 does not contain a component having adhesion, and the transferee and the transfer layer 10 Can be attached closely. About the component which has adhesiveness, the component etc. which are demonstrated by the contact bonding layer mentioned later can be selected suitably, and can be used.

  In the protective layer 5, various silicone oils, polyethylene wax, zinc stearate, zinc stearyl phosphate, calcium stearate, metal stearates such as magnesium stearate, fatty acid amide, polyethylene wax, carnauba wax, if necessary. , Release agents such as paraffin wax, benzophenones, benzotriazoles, benzoates, triazines, triazines, titanium oxides, known ultraviolet absorbers such as titanium oxide, zinc oxide, hindered amines, light stabilizers such as Ni chelates, hindered phenols You may contain antioxidants, such as a type | system | group, sulfur type, phosphorus type, lactone type etc., etc. The protective layer 5 may contain 1 type alone as an additive, and may contain 2 or more types.

  There is no particular limitation on the method of forming the protective layer 5, and a coating liquid for protective layer is prepared by dispersing or dissolving a binder resin, organic fluorine compound particles, and various additives used as needed in an appropriate solvent. The coating liquid can be formed on the release layer 2 by coating and drying.

  The thickness of the protective layer 5 is not particularly limited, but is usually in the range of 0.1 μm to 50 μm, and preferably in the range of 0.5 μm to 10 μm.

(Adhesive layer)
As shown in FIG. 2, the transfer layer 10 may have a laminated structure in which a protective layer 5 and an adhesive layer 6 are laminated in this order from the base 1 side (the release layer 2 side). According to the transfer layer 10 of this embodiment, the protective layer 5 does not contain a component for imparting adhesion to the transferee (component having adhesion), and the transfer layer 10 adheres to the transferee Can be given. That is, the functions of durability and adhesion can be separated into the protective layer 5 and the adhesive layer 6, and the functions required for both layers can be enhanced.

  There is no limitation in particular about the component which has an adhesion layer, For example, polyolefin resin, such as urethane resin, alpha-olefin-maleic anhydride resin, polyester resin, acrylic resin, epoxy resin, urea resin, melamine resin And phenolic resins, vinyl acetate resins, cyanoacrylate resins and the like. Among them, reactive resins of acrylic resins and modified resins are preferably used. The adhesive is preferably cured using a curing agent, because the adhesive strength is improved and the heat resistance is also improved. As a curing agent, an isocyanate compound is generally used, but aliphatic amines, cyclic aliphatic amines, aromatic amines, acid anhydrides and the like can be used.

  The thickness of the adhesive layer 6 is preferably in the range of 0.5 μm to 10 μm. There is no particular limitation on the method of forming the adhesive layer, and for example, a coating solution for the adhesive layer is prepared by dispersing or dissolving the adhesive exemplified above and the additive added as needed in an appropriate solvent. The coating liquid can be formed by coating and drying on the protective layer 5 or any layer provided on the protective layer 5.

(Dye layer)
As shown in FIG. 3, the dye layer 7 may be provided on the surface of the substrate 1 in a surface sequential manner with the transfer layer 10 described above. In the protective layer transfer sheet 100 in the form shown in FIG. 3, a single dye layer 7 is provided on one side of the substrate 1. In addition, on one surface of the substrate, a plurality of dye layers, for example, a yellow dye layer, a magenta dye layer, a cyan dye layer, a black dye layer, etc. may be provided surface-sequentially as needed. A single dye layer (not shown) may be provided on one side of the substrate 1. In addition, when the dye layer 7 and the transfer layer 10 are “one unit”, “one unit” can be repeatedly provided on one surface of the substrate 1.

  According to the protective layer transfer sheet of the form shown in FIG. 3, the formation of the thermal transfer image on the transferred body and the transfer of the transfer layer 10 onto the formed thermal transfer image are carried out using one protective layer transfer sheet 100. It can be carried out.

  The dye layer 7 as an example contains a binder resin and a sublimable dye. There is no limitation in particular about the binder resin which the dye layer 7 contains, The binder resin conventionally well-known in the field | area of a dye layer can be selected suitably, and can be used. Examples of the binder resin for the dye layer 7 include ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxycellulose resin, methyl cellulose resin, cellulose resin such as cellulose acetate resin, polyvinyl alcohol resin, polyvinyl acetate resin, polyvinyl butyral resin, polyvinyl aceto Examples include acetal resins, vinyl resins such as polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylates and poly (meth) acrylamides, polyurethane resins, polyamide resins, polyester resins, and the like.

  The content of the binder resin is not particularly limited, but the content of the binder resin with respect to the total mass of the dye layer 7 is preferably 20% by mass or more. By setting the content of the binder resin to 20% by mass or more with respect to the total mass of the dye layer, the sublimation dye can be sufficiently retained in the dye layer 7, and as a result, the storage stability can be improved. There is no particular limitation on the upper limit value of the content of the binder resin, and it may be appropriately set according to the content of the sublimable dye and any additive.

  The sublimable dye contained in the dye layer 7 is not particularly limited, but it is preferable that the dye has a sufficient coloring density and is not discolored or discolored by light, heat, temperature or the like. Examples of dyes include diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazo methine, imidazolazo azomethine, imidazo azomethine and pyridone azomethine Azomethine dyes, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzeneazo dyes, pyridone azo, thiophene azo, isothiazole Azo dyes such as azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, disazo, spiropyran dyes, indolinospiropyran dyes, fluoran Dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone dyes. Specifically, red dyes such as MS Red G (Mitsui Toatsu Chemicals Co., Ltd.), Macrolex Red Violet R (Bayer Corp.), Ceres Red 7 B (Bayer Corp.), Samaron Red F3 BS (Mitsubishi Chemical Corp.) etc., Holon Brilliant Yellow dyes such as Yellow 6GL (Clariant), PTY-52 (Mitsubishi Chemical Co., Ltd.), Macrolex Yellow 6G (Bayer), Kayaset (registered trademark) Blue 714 (Nippon Kayaku Co., Ltd.), Holon Brilliant Blue SR (Clariant), MS Blue 100 (Mitsui Toatsu Chemicals, Inc.), C.I. I. And blue dyes such as Solvent Blue 63.

  The content of the sublimation dye is preferably in the range of 50% by mass to 350% by mass, and more preferably in the range of 80% by mass to 300% by mass, with respect to the total mass of the binder resin. By making content of a sublimation dye into the said preferable range, the printing density and the further improvement of preservability can be aimed at.

(Dye primer layer)
Also, a dye primer layer (not shown) can be provided between the substrate 1 and the dye layer 7. There is no limitation in particular about the component contained in a dye primer layer, For example, polyester-based resin, polyvinyl pyrrolidone resin, polyvinyl alcohol resin, hydroxyethyl cellulose, polyacrylic acid ester-based resin, polyvinyl acetate resin, polyurethane-based resin, acryl-styrene Copolymers, polyacrylamide resins, polyamide resins, polyether resins, polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinylacetals such as polyvinyl acetoacetal and polyvinyl butyral, etc. It can be mentioned.

  The dye primer layer may also contain colloidal inorganic pigment ultrafine particles. Examples of colloidal inorganic pigment ultrafine particles include silica (colloidal silica), alumina, or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate thereof, pseudoboehmite etc.), aluminum silicate, silica silicate Magnesium, magnesium carbonate, magnesium oxide, titanium oxide and the like can be mentioned. In particular, colloidal silica and alumina sol are preferably used. The size of these colloidal inorganic pigment ultrafine particles is 100 nm or less, preferably 50 nm or less in primary average particle diameter.

(Back layer)
Moreover, you may provide a back layer (not shown) in the other surface of the base material 1. FIG. In addition, a back layer is the arbitrary structure in the protective layer transfer sheet of one Embodiment.

  The back layer can be formed by appropriately selecting a conventionally known thermoplastic resin or the like. As such a thermoplastic resin, for example, polyester resins, polyacrylate resins, polyvinyl acetate resins, acrylic-styrene copolymers, polyurethane resins, polyethylene resins, polypropylene resins, etc. Polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polyimide resin, polyamide imide resin, polycarbonate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin and polyvinyl aceto Examples include polyvinyl acetal resins such as acetal resins, and silicone modified products thereof. Among them, from the viewpoint of heat resistance etc., polyamide imide resin or its silicone modified product can be preferably used. Also, these resins may be cured by a curing agent. As a hardening agent, an isocyanate type hardening agent etc. are mentioned, for example.

  Moreover, in addition to the above-mentioned thermoplastic resin, in the back layer, for the purpose of improving slip property, mold release agent such as wax, higher fatty acid amide, phosphoric acid ester compound, metal soap, silicone oil, surfactant, etc., fluorocarbon resin And various additives such as inorganic particles such as silica, clay, talc, calcium carbonate etc. are preferably contained, and it is particularly preferable that at least one of phosphoric acid ester or metal soap is contained. .

  For the back layer, for example, a coating solution for the back layer is prepared by dispersing or dissolving the above-mentioned thermoplastic resin and various additives added as necessary in a suitable solvent. It can form by apply | coating and drying on the other side of. The thickness of the back layer is preferably in the range of 0.1 μm or more and 5 μm or less, and more preferably in the range of 0.3 μm or more and 2 μm or less, from the viewpoint of improvement in heat resistance and the like.

(Subject)
As a transferred body to which the transfer layer 10 of the protective layer transfer sheet 100 of one embodiment is transferred, for example, a thermal transfer image receiving sheet, plain paper, wood free paper, tracing paper, plastic film, vinyl chloride, vinyl chloride-vinyl acetate Examples thereof include copolymers and plastic cards mainly composed of polycarbonate. Further, it is also possible to use one having a predetermined image as a transferee. Further, the transferred body may be colored or may be transparent.

(Transfer method of transfer layer)
There is no particular limitation on the method of transferring the transfer layer onto the transfer target, and for example, it can be performed using a thermal transfer printer having a heating device such as a thermal head, or a heating means such as a hot stamp or a heat roll.

  Next, the present invention will be more specifically described by way of examples and comparative examples. Hereinafter, unless otherwise noted, parts or% are on a mass basis, and indicate the composition before conversion to solid content.

Example 1
On a 4.5 μm thick polyethylene terephthalate (PET) film, the release layer coating solution 1 of the following composition is applied and dried to a dry thickness of 1.1 μm to form a release layer did. Then, on this release layer, the protective layer coating solution 1 having the above composition was applied and dried so as to have a dry thickness of 1 μm to form a protective layer. Then, a coating solution for an adhesive layer having the following composition is applied and dried on the protective layer to a dry thickness of 1 μm, whereby a release layer, a protective layer, and an adhesive layer are formed on the substrate. The thermal transfer sheet of Example 1 obtained by laminating in this order was obtained. Hereinafter, the term “transfer layer” means a laminate of a protective layer and an adhesive layer.

<Coating fluid for release layer 1>
Acrylic resin filler (volume average particle diameter: 2 μm) 5 parts Modified acrylic resin (solid content: 50%) 80 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 15 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

<Coating fluid 1 for protective layer>
Acrylic resin 65 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Corporation)
・ Acrylic-styrene-based copolymer 30 parts (DIANAL (registered trademark) BR-52 Mitsubishi Chemical Corporation)
Organic fluorine compound (primary particle diameter: 0.2 to 0.4 μm) 3 parts (FLUON (registered trademark) J172JE Asahi Glass Co., Ltd.)
Dispersant 2 parts (DISPERBYK 180 BYK)
-240 parts of methyl ethyl ketone, 60 parts of normal propyl acetate

<Coating fluid for adhesive layer>
· Reactive UV absorber-MMA copolymer (ratio 30: 70) 63 parts (Tg: 90 ° C., Mw: 20000-40000)
-PMMA 14 parts (Dianal (registered trademark) BR-83 Mitsubishi Chemical Corporation)
・ Vinyl chloride-vinyl acetate copolymer 13 parts (Solvane (registered trademark) CNL Nisshin Chemical Co., Ltd.)
・ Ultraviolet absorber 10 parts (Tinuvin 928 BASF Japan Ltd.)
-Methyl ethyl ketone 240 parts-Normal propyl acetate 60 parts The said reaction type ultraviolet absorber-the reaction type ultraviolet absorber which makes a MMA copolymer is a reaction type ultraviolet absorber (RUVA-93 Otsuka Chemical Co., Ltd.).

(Example 2)
In place of the coating solution 1 for protective layer, 3 parts of an organic fluorine compound (Fluon (registered trademark) L172JE Asahi Glass Co., Ltd.) in the coating solution 1 for protective layer is added to an organic fluorine compound (primary average particle diameter: 0. (2 to 0.4 μm) (Fluon (registered trademark) L173JE Asahi Glass Co., Ltd.) 3 parts, except that the protective layer was formed using the coating solution 2 for a protective layer, all were the same as Example 1 The protective layer transfer sheet of Example 2 was obtained.

(Example 3)
Instead of the coating solution 1 for a protective layer, 3 parts of an organic fluorine compound (Fluon (registered trademark) L172JE Asahi Glass Co., Ltd.) in the coating solution 1 for a protective layer is replaced with an organic fluorine compound (volume average particle diameter: 3.3. 5 μm) (Lublon (registered trademark) L2 Daikin Industries, Ltd.) 3 parts of the same procedure as in Example 1 except that the protective layer was formed using the coating solution 3 for a protective layer Three protective layer transfer sheets were obtained.

(Example 4)
Instead of Coating Liquid 1 for Protective Layer, 3 parts of an organic fluorine compound (Fluon (registered trademark) L172JE Asahi Glass Co., Ltd.) in Coating Liquid 1 for protective layer, an organic fluorine compound (volume average particle diameter: 5 μm) (Lublon (registered trademark) L5 Daikin Industries, Ltd.) The procedure was the same as in Example 1 except that the protective layer was formed using Coating Liquid 4 for Protective Layer, which was changed to 3 parts. A protective layer transfer sheet was obtained.

(Example 5)
Instead of the coating liquid 1 for release layer, using the coating liquid 2 for release layer of the following composition, the coating liquid 2 for release layer is applied to a thickness of 0.5 μm at the time of drying · All the same as Example 1 except that the release layer was dried to form a release layer, and the protective layer was formed using the protective layer coating solution 3 of the above composition instead of the protective layer coating solution 1. Thus, a protective layer transfer sheet of Example 5 was obtained.

<Coating fluid 2 for release layer>
Acrylic resin filler (volume average particle diameter: 2 μm) 10 parts Modified acrylic resin (solid content: 50%) 76 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 14 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Example 6)
Instead of the coating liquid 1 for release layer, using the coating liquid 3 for release layer of the following composition, the coating liquid 3 for release layer is applied and dried so that the thickness at the time of drying is 5 μm. In the same manner as in Example 1, except that the release layer was formed, and the protective layer coating liquid 3 was used instead of the protective layer coating liquid 1 to form a protective layer. The protective layer transfer sheet of Example 6 was obtained.

<Coating fluid 3 for release layer>
Acrylic resin filler (volume average particle diameter: 2 μm) 0.4 parts Modified acrylic resin (solid content: 50%) 84 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 16 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Example 7)
The coating liquid 1 for release layer is changed to the coating liquid 4 for release layer having the following composition to form a release layer, and the coating liquid 1 for protective layer is a coating liquid for protective layer of the above composition. A protective layer transfer sheet of Example 7 was obtained in the same manner as in Example 1 except that the protective layer was changed to 3 to form a protective layer.

<Coating fluid 4 for release layer>
Acrylic resin filler (volume average particle diameter: 5 μm) 5 parts Modified acrylic resin (solid content: 50%) 80 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 15 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Example 8)
The coating liquid 1 for release layer is changed to the coating liquid 5 for release layer having the following composition to form a release layer, and the coating liquid 1 for protective layer is coated with the coating liquid for protective layer of the above composition. A protective layer transfer sheet of Example 8 was obtained in the same manner as Example 1 except that the protective layer was changed to 3 to form a protective layer.

<Coating fluid 5 for release layer>
Acrylic resin filler (volume average particle diameter: 10 μm) 5 parts Modified acrylic resin (solid content: 50%) 80 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 15 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Example 9)
The coating liquid 1 for release layer is changed to the coating liquid 6 for release layer having the following composition to form a release layer, and the coating liquid 1 for protective layer is coated with the coating liquid for protective layer of the above composition. A protective layer transfer sheet of Example 9 was obtained in the same manner as in Example 1 except that the protective layer was changed to 3 to form a protective layer.

<Coating fluid for release layer 6>
· Silicone resin fine particles (volume average particle diameter: 2 μm) 5 parts · Modified acrylic resin (solid content: 50%) 80 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 15 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Comparative example 1)
A protective layer is formed on a 4.5 μm thick polyethylene terephthalate (PET) film by applying and drying a protective layer coating solution A having the following composition to a dry thickness of 1 μm. Comparative Example in which the protective layer and the adhesive layer are laminated in this order on the substrate by applying and drying the adhesive layer coating liquid having the above composition such that the thickness at the time of drying is 1 μm. A thermal transfer sheet of 1 was obtained.

<Coating fluid A for protective layer>
Acrylic resin 67.5 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Corporation)
-Acrylic-styrene-based copolymer 32.5 parts (DIANAL (registered trademark) BR-52 Mitsubishi Chemical Corporation)
-240 parts of methyl ethyl ketone, 60 parts of normal propyl acetate

(Comparative example 2)
The protective layer transfer sheet of Comparative Example 2 is the same as Comparative Example 1 except that the protective layer is formed using the protective layer coating solution 3 of the above composition instead of the protective layer coating solution A. Obtained.

(Comparative example 3)
Instead of the coating liquid 1 for release layer, a release layer is formed using the coating liquid A for release layer of the following composition, and instead of the coating liquid 1 for protective layer, for the protective layer of the above composition A protective layer transfer sheet of Comparative Example 3 was obtained in the same manner as Example 1 except that the protective layer was formed using the coating liquid A.

<Coating fluid A for release layer>
-Modified acrylic resin (solid content: 50%) 84 parts (CELTOP 226 Daicel Chemical Industries, Ltd.)
・ Acetylacetonate aluminum (solid content: 10%) 16 parts (CELTOP CAT-A Daicel Chemical Industries, Ltd.)
-8 parts of methyl ethyl ketone-8 parts of normal propyl acetate

(Comparative example 4)
Instead of the coating liquid 1 for release layer, a release layer is formed using the coating liquid A for release layer of the above composition, and instead of the coating liquid 1 for protective layer, for the protective layer of the above composition A protective layer transfer sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the protective layer was formed using Coating Composition 3.

(Comparative example 5)
A protective layer transfer sheet of Comparative Example 5 is prepared in the same manner as in Example 1 except that the protective layer is formed using the protective layer coating solution B having the following composition, instead of the protective layer coating solution 1. Obtained.

<Coating fluid B for protective layer>
Acrylic resin 65 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Corporation)
・ Acrylic-styrene-based copolymer 30 parts (DIANAL (registered trademark) BR-52 Mitsubishi Chemical Corporation)
-Talc 3 parts (Micro Ace (registered trademark) P-3 Nippon Talc Co., Ltd.)
Dispersant 2 parts (DISPERBYK 180 BYK)
-240 parts of methyl ethyl ketone, 60 parts of normal propyl acetate

(Comparative example 6)
A protective layer transfer sheet of Comparative Example 6 is prepared in the same manner as in Example 1 except that the protective layer is formed using the protective layer coating solution A having the above composition instead of the protective layer coating solution 1. Obtained.

(Creating a print)
A sublimation type thermal transfer printer (DS820, Dai Nippon Printing Co., Ltd.) and a genuine ribbon of the printer, on a genuine image receiving paper of the sublimation type thermal transfer printer as a transfer target, of 0/255 gradation (image gradation) A black solid image was printed to obtain an image formed product. Then, the protective layer transfer sheet of each example and comparative example is cut and attached to the protective layer area of the genuine ribbon, and each example is formed on the image-formed product obtained above using the sublimation thermal transfer printer. The transfer layer of the protective layer transfer sheet of the comparative example and the comparative example was transferred, and the printed matter of each example and the comparative example was obtained.

(Matte feeling evaluation)
The surface of the printed matter of each of the Examples and Comparative Examples obtained by forming the above-mentioned printed matter is measured using a gloss meter (Gloss meter VG7000 (Nippon Denshoku Co., Ltd.)) (measurement angle: 20 °) The gloss was evaluated according to the following evaluation criteria: The evaluation results are shown in Table 1.

"Evaluation criteria"
A: The glossiness is less than 10%.
B: The glossiness is in the range of 10% to less than 15%.
C: The glossiness is in the range of 15% or more and less than 20%.
NG: The glossiness is 20% or more.

(Anti-fingerprint adhesion evaluation)
The printed matter of each of Examples and Comparative Examples formed above by pressing (500 g load) a pseudo fingerprint liquid (artificial fingerprint liquid) containing triolein and fine particles with an indenter (contact surface is a circle with a diameter of 12 mmφ) The artificial fingerprint of 0.04 mg was attached per 1 mm ^{2 on} the surface of The hue of the printed matter in each of the Examples and Comparative Examples before and after the artificial fingerprint was attached was measured using Spectrolino (X-Rite) (D65 light source, viewing angle 2 °), and ΔE ^* was calculated based on the following color difference calculation formula ^. The fingerprint resistance was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1. The hue was measured nine times each. The smaller the value of ΔE ^*, the better the anti-fingerprint adhesion.

(Color difference calculation formula)
ΔE ^* = ((difference of L ^* value before and after attachment of artificial fingerprint) ² + (difference of a ^* value before and after attachment of artificial fingerprint) ² + (difference of b ^* value before and after attachment of artificial fingerprint) ² ) ^1/2
Incidentally, L ^* a ^* b ^* means CIE1976, L ^* a ^* b ^* defined in the color system (JIS-Z-8729 (1980 )) L * a * b *.

"Evaluation criteria"
A: ΔE ^* is less than 7.
B: ΔE ^* is in the range of 7 or more and less than 7.5.
C: ΔE ^* is in the range of 7.5 to less than 8.
NG: ΔE ^* is 8 or more.

(Anti-fingerprint removability evaluation)
A wiping item (Kimwipe (registered trademark)) is wound around the indenter site of a wear tester TYPE F manufactured by Haydon Co., and the printed matter of each example and comparative example in which an artificial fingerprint is adhered by the above-mentioned fingerprint resistance evaluation. On the other hand, the artificial fingerprint was wiped by reciprocating it 500 g in weight, 10 cm wide × 20. Spectrolino (X-Rite Co., Ltd.) (D65 light source, visual field) The hue of the printed matter of each Example and Comparative Example before attaching the artificial fingerprint and the hue of the printed matter of each Example and Wiped Example after wiping the artificial fingerprint The measurement was performed using the angle 2 °), ΔE ^* was calculated based on the above color difference calculation formula, and the anti-fingerprint adhesion was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1. In the color difference calculation formula, the description “before and after attaching artificial fingerprint” is read as “before attaching an artificial fingerprint and after wiping an artificial fingerprint”. The hue was measured nine times each. The smaller the value of ΔE ^*, the better the anti-fingerprint wipeability.

"Evaluation criteria"
A: ΔE ^* is less than 3.5.
B: ΔE ^* is in the range of 3.5 or more and less than 3.75.
C: ΔE ^* is in the range of 3.75 to less than 4.
NG: ΔE ^* is 4 or more.

DESCRIPTION OF SYMBOLS 1 ... Base material 5 ... Protective layer 6 ... Adhesive layer 7 ... Dye layer 10 ... Transfer layer 100 ... Protective layer transfer sheet

Claims (4)

A protective layer transfer sheet comprising a release layer and a transfer layer laminated in this order on one side of a substrate,
The transfer layer has a single-layer structure consisting only of the protective layer, or a laminated structure in which the protective layer is located closest to the release layer,
The release layer contains a binder resin and a filler,
The protective layer contains a particulate organic fluorine compound,
A protective layer transfer sheet characterized by   The ratio (mass%) of the mass ratio (mass%) of the filler to the mass of the binder resin contained in the release layer is within a range of greater than 0 and 40 or less. The protective layer transfer sheet according to claim 1, wherein   The value obtained by dividing the volume average particle diameter (μm) of the filler contained in the release layer by the thickness (μm) of the release layer is in the range of 0.5 to 9 inclusive. The protective layer transfer sheet according to claim 1 or 2, characterized in that   A value obtained by dividing the ratio (% by mass) of the mass of the filler to the mass of the binder resin contained in the release layer by the volume average particle diameter (μm) of the filler contained in the release layer. Is 1.5 or more, The protective layer transfer sheet in any one of the Claims 1 thru | or 3 characterized by the above-mentioned.

Images