JP6123431B2 - Protective layer transfer sheet - Google Patents

Description

  The present invention relates to a protective layer transfer sheet.

  As a simple printing method, various thermal transfer recording methods are widely used. In each thermal transfer recording method, when obtaining a color image, a thermal transfer sheet in which a large number of color material layers of, for example, yellow, magenta, and cyan (black if necessary) are repeatedly provided in a surface sequence on a continuous base sheet. Is mainly used. In the thermal transfer recording method, the color material layer is melted and softened by heating and transferred onto the thermal transfer image-receiving sheet to form an image, and the sublimation dye in the color material layer is heated on the transfer material. It is roughly divided into a sublimation type thermal transfer system that shifts to form an image.

  Among them, the sublimation type thermal transfer system can control the amount of dye transfer by the amount of energy applied to the thermal transfer sheet, so density gradation is possible, so the image is very clear and the transparency and halftone color. High reproducibility and gradation can be formed, and high-quality printed products comparable to full-color photographic images can be formed.

  However, although the sublimation transfer method is excellent in forming a gradation image, the sublimation dye used for the formation of a printed matter has a relatively low molecular weight, and since there is no vehicle, it is inferior in durability. Have Thus, recently, attempts have been widely made to improve the durability of printed matter by forming a transferable protective layer on the printed matter. The transferable protective layer is formed on the printed material using a protective layer transfer sheet having a transferable protective layer that can be peeled off from the substrate, and is transferred onto the printed material using a thermal head or a heating roll. This is done by transferring the protective layer. As the transferable protective layer, a protective layer for protecting the printed material (sometimes referred to as a peeling layer) and an adhesive layer for the purpose of adhesion between the printed material and the transferable protective layer (called a heat seal layer) However, those laminated in this order from a base material are widely known. There is also known a transferable protective layer composed of one layer having both functions of a protective layer and an adhesive layer.

  Since the transferable protective layer of the protective layer transfer sheet is generally an electrical insulator, the protective layer transfer sheet is charged when the printed product and the protective layer transfer sheet are aligned and aligned. In addition to this, the protective layer transfer sheet is charged even when the roll-shaped protective layer transfer sheet is rewound and wound. When the protective layer transfer sheet is charged, a conveyance failure may occur due to sticking between the protective layer transfer sheet and the printed material. In order to solve such a problem, it is necessary that the protective layer transfer sheet has sufficient antistatic performance during transfer of the transferable protective layer.

  In addition, when the charged transferable protective layer is transferred onto the printed material, the printed material to which the transferable protective layer is transferred is also charged, and after the transferable protective layer is transferred, the image receiving tray is continuously fed from the printer. The prints that are ejected from each other cause sticking. The printed materials discharged on the image receiving tray are usually not stacked exactly on the previously discharged printed materials, but are stacked at random to some extent. Therefore, after continuous printing, it is necessary to take out a stack of prints from the image receiving tray and align the four corners of the stacked prints neatly, but if the prints are stuck, clean the four corners of the prints. In other words, it causes problems such as poor judgment. In addition to this, it also has an electrical effect on electronic parts used for electrical control of thermal transfer printers, etc., which may cause malfunctions and malfunctions. In addition, since the charged protective layer transfer sheet adsorbs dust, defects such as transfer omission of the transferable protective layer and foreign matter biting may occur in the printed matter due to the adsorbed dust. In order to solve such a problem, it is necessary that the printed matter to which the transferable protective layer is transferred has sufficient antistatic performance.

  Under such circumstances, for example, Patent Document 1 proposes a protective layer transfer sheet including an adhesive protective layer containing an antistatic agent. As the antistatic agent, conductive polymer type, surfactant type and conductive fine particle type antistatic agents are widely known.

JP 2001-199162 A

  However, a conductive polymer type antistatic agent widely known as an antistatic agent is very expensive and is not a preferable material in terms of cost. In addition, since it is difficult to sufficiently exert an antistatic effect with a small amount of addition of a surfactant type antistatic agent, it is necessary to add a large amount of antistatic agent. Therefore, in order to exert a sufficient antistatic effect in the protective layer transfer sheet disclosed in Patent Document 1, it is necessary to add a large amount of an antistatic agent, the stickiness of the transferable protective layer, and the protective layer integrated type In the thermal transfer sheet, the dye of the color material layer transferred to the back layer is re-transferred to the protective layer and contaminates the protective layer when it is rolled back during the manufacturing process or stored in a small volume state. Problems occur. In addition, since the conductive fine particle type antistatic agent needs to be added in a large amount in order to exert the antistatic effect, the smoothness of the transferable protective layer is lost, and the printed matter on which the transferable protective layer is transferred. This causes a decrease in glossiness and roughness.

  The present invention has been made in such a situation, and the antistatic performance at the time of transfer of the transferable protective layer without interfering with basic functions required for the transferable protective layer such as glossiness, storage stability and transferability. Or providing a protective layer transfer sheet that can impart antistatic performance to the printed material after transferring the transferable protective layer without interfering with the basic function of the transferable protective layer. Let it be the main issue.

The present invention for solving the above problems is a protective layer transfer sheet used in a thermal transfer recording method, wherein the protective layer transfer sheet is peeled from one side of the substrate from the substrate side by the thermal transfer recording method. and transferable protective layer is transferred onto the transfer medium is provided, wherein the transferable protective layer is composed of one or more layers, at least one of the layers constituting the transferable protective layer The layer is characterized by containing an ionic liquid.

  Moreover, in the case where the transferable protective layer is composed of two or more layers, among the layers constituting the transferable protective layer, the layer disposed at the position closest to the base material, and the base material Either one of the layers arranged at the farthest position, or both layers may contain the ionic liquid.

  According to the protective layer transfer sheet of the present invention, the antistatic performance during transfer of the transferable protective layer is improved without interfering with basic functions required for the transferable protective layer such as glossiness, storage stability and transferability. Alternatively, the antistatic property can be imparted to the printed matter after the transferable protective layer is transferred without interfering with the basic function of the transferable protective layer.

It is a schematic sectional drawing which shows an example of the protective layer transfer sheet used for this invention. It is a schematic sectional drawing which shows an example of the protective layer transfer sheet used for this invention.

  Hereinafter, the protective layer transfer sheet 10 of the present invention will be specifically described with reference to the drawings. As shown in FIGS. 1 and 2, the protective layer transfer sheet of the present invention has a configuration in which a transferable protective layer 2 that can be peeled from the base material 1 is provided on one surface of the base material 1. 1 is a schematic cross-sectional view showing an example of a protective layer transfer sheet including a transferable protective layer 2 having a laminated structure in which two or more layers are laminated, and FIG. 2 is composed of one layer. It is a schematic sectional drawing which shows an example of a protective layer transfer sheet provided with the transferable protective layer 2 of a single layer structure.

(Base material)
The substrate 1 is not particularly limited as long as it has a certain degree of heat resistance and strength, and a conventionally known material can be appropriately selected and used. As such a substrate 1, for example, a polyethylene terephthalate film, a 1,4-polycyclohexylenedimethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide having a thickness of about 0.5 μm to 50 μm, preferably about 1 μm to 10 μm. Film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane, cellulose derivatives such as cellulose acetate, polyethylene film, polyvinyl chloride film, nylon film, polyimide film, ionomer film, etc. . Furthermore, each of these materials can be used alone, but may be used as a laminate in combination with other materials.

  The base material 1 may be subjected to an adhesion treatment on the surface on which the transferable protective layer 2 is formed. By performing the adhesion treatment, adhesion between the base material 1 and the transferable protective layer 2 or an arbitrary layer provided between the base material 1 and the transferable protective layer 2 can be improved. In addition, this adhesion treatment can also be performed between the release layer 11 and the adhesive layer 12, which will be described later as an embodiment of the layer constituting the transfer layer 2.

  Examples of the adhesion treatment include known resin surfaces such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, and grafting treatment. The reforming technique can be applied as it is. Two or more of these treatments can be used in combination.

(Transferable protective layer)
As shown in FIGS. 1 and 2, a transferable protective layer 2 is provided on the substrate 1. The transferable protective layer 2 is obtained by superposing the protective layer transfer sheet 10 of the present invention and the printed material, and heating the side of the substrate 1 on which the transferable protective layer 2 is not provided by a heating means such as a thermal head. Thus, it is a layer that is peeled off from the substrate 1 and transferred onto the printed material.

  The transferable protective layer 2 may have a laminated structure in which two or more layers are laminated as shown in FIG. 1, and a single layer structure constituted by one layer as shown in FIG. It may be one that takes

  Here, the protective layer transfer sheet 10 of the present invention is characterized in that at least one layer constituting the transferable protective layer 2 composed of one or more layers contains an ionic liquid. . The ionic liquid has a property that an antistatic effect can be exhibited with a small addition amount as compared with a conventionally known antistatic agent. Therefore, according to the protective layer transfer sheet 10 of the present invention in which at least one layer constituting the transferable protective layer 2 contains an ionic liquid, functions required for the transferable protective layer 2, such as durability, The protective layer transfer sheet 10 can be provided with excellent antistatic performance without interfering with various functions such as transferability and glossiness.

  Specifically, according to the protective layer transfer sheet 10 of one embodiment of the present invention, the antistatic performance during transfer of the transferable protective layer 2 is improved without interfering with the functions required of the transferable protective layer 2. Can be made. Thereby, while satisfying the durability, transferability, and glossiness of the transferable protective layer 2, poor conveyance due to sticking between the protective layer transfer sheet and the printed matter, and dust adsorption on the protective layer transfer sheet. Prevention can be prevented. Further, according to the protective layer transfer sheet 10 of one embodiment of the present invention, the antistatic performance is imparted to the printed material to which the transferable protective layer 2 has been transferred without interfering with the functions required of the transferable protective layer 2. can do. As a result, it is possible to prevent the transferable protective layer 2 from being transferred and sticking the prints continuously discharged from the printer to the image receiving tray. Moreover, according to the protective layer transfer sheet 10 of one embodiment of the present invention, the antistatic performance during transfer of the transferable protective layer 2 can be improved without interfering with the functions required of the transferable protective layer 2. In addition, it is possible to impart antistatic performance to the printed material to which the transferable protective layer 2 has been transferred.

  In addition, since the ionic liquid is bound to each other by an electrostatic interaction force, the ionic liquid has almost no vapor pressure even if it is a liquid. Therefore, it can be said that the ionic liquid is not scattered in the atmosphere and is excellent in terms of environment.

  In addition, in order to impart antistatic performance to the transferable protective layer 2, when the layer constituting the transferable protective layer contains a conventionally known solid antistatic agent such as conductive fine particles, the transferable protection is achieved. Problems such as the surface of the transferable protective layer roughened by the antistatic agent protruding from the surface of the layer, resulting in a decrease in the glossiness of the printed material on which the transferable protective layer was transferred, or the roughness of the printed material May occur. In addition, when a surfactant type antistatic agent is contained in the transferable protective layer, the transferable protective layer is likely to be dyed by the dye of the color material layer, and the color material layer and the transferable protective layer are sequentially arranged. In the case of the protective layer transfer sheet integrated with the color material layer provided in the substrate, the dye kicked (transferred) to the opposite side of the substrate is backed (retransferred) to the transferable protective layer. There may be a problem of contamination. In order to prevent these problems, it is necessary to reduce the content of the antistatic agent. However, if the content of the conventionally known antistatic agent is decreased, sufficient charge is applied to the transferable protective layer. Preventive performance cannot be imparted.

<Ionic liquid>
The ionic liquid is generally a salt composed of a cation and an anion, and refers to a liquid that has a melting point of 100 ° C. or lower, that is, 100 ° C. or lower.

Examples of the cation constituting the ionic liquid include triethylpentylammonium, cyclohexyltrimethylammonium, methyltri-n-octylammonium, tetrabutylammonium, tetrabutylphosphonium, tributylhexadecylphosphonium, tributyl (2-methoxyethyl) phosphonium, and tributylmethyl. Ammonium, tributylmethylphosphonium, triethylsulfonium, trimethylpropylammonium, 1-butyl-1-methylpiperidinium, hydroxyethylpiperazine, 2-methylpiperazine, N-ethylmorpholine, N.N.dimethylethanolamine, N.N. Dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyl Tildiethanolamine, N- (β-aminoethyl) ethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N, N-diethylisopropanolamine, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1,3-dimethylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium 1-hexyl-3-methylimidazolium, 1-methyl-3-n-octylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-4-methylpyridinium, 1-butyl-3-methyl Pyridinium, 1-butylpyridinium, 1-ethyl-3- (hydroxymethyl) pyrid Um, 1-ethyl-3-methylpyridinium, 1-ethyl pyridinium, 1-butyl-1-methyl pyrrolidinium, and the like 1-methyl-1-propyl pyrrolidinium.

  The cation is not limited as long as it can constitute an ionic liquid, and a cation other than the cations exemplified above can also be used.

  The anion constituting the ionic liquid is not limited as in the case of the cation, and anions other than those exemplified below can also be used.

Examples of the anion constituting the ionic liquid include AlCl ₄ −, Al ₂ Cl ₇ −, BF ₄ −, PF ₆ −, F (HF) n−, CF ₃ COO—, and CH ₃ CH ₂ OSO ₃ —CF _{3. SO 3 - (TfO), (} CF 3 SO 2) 2 N- (TFSI), (CF 3 SO 2) 3 C- (TFSM), HN (Tf) 2, NO 3 -, (NC) 2 N-, CH ₃ COO—, Br—, Cl—, I—, (CH ₃ O) ₂ OPO—, linear alkylbenzene sulfonic acid, dialkyl succinate sulfonic acid, α-sulfo fatty acid methyl ester, α-olefin sulfonic acid, alkane Sulfonic acid type (sulfonate type) anion such as sulfonic acid, fatty acid type anion such as higher fatty acid, sulfuric acid ester such as alkyl sulfate ester, glycol ether sulfate ester, alkyl ether sulfate ester Le type (sulfate type) anion, and (mono) phosphoric acid ester type such as alkyl phosphate (phosphate type) anion.

  Examples of ionic liquids include ionic liquids containing N-ethylethanolamine and alkylbenzene sulfonic acid, and ionic liquids containing N-ethylethanolamine and glycol ether sulfate, N-ethylethanolamine and dialkyl succinate sulfonic acid. Etc. can be illustrated. The ionic liquid may be used alone or in combination of two or more. Further, the ionic liquid may contain two or more kinds of cations and / or two or more kinds of anions. Further, the transferable protective layer 2 may contain one ionic liquid alone or a combination of two or more ionic liquids.

  The melting point of the ionic liquid is not particularly limited, but it is preferable that at least one layer constituting the transferable protective layer 2 contains an ionic liquid having a melting point of 5 ° C. or lower. According to the ionic liquid having a melting point of 5 ° C. or less, good antistatic performance can be surely exhibited during transfer of the transferable protective layer using the protective layer transfer sheet of the present invention.

  Generally, the guaranteed operating temperature of a printer used for transferring a transferable protective layer is often set between 5 ° C and 40 ° C, and the protective layer transfer sheet has a temperature within a range of 5 ° C to 40 ° C. Good antistatic performance is required. Accordingly, when the transferable protective layer 2 contains an ionic liquid having a melting point of 5 ° C. or lower, the ionic liquid can be reliably present in a liquid state within the range of the operation guarantee temperature. It is possible to reliably prevent the conveyance failure due to the adhesion of the protective layer transfer sheet and the printed material, and the charging of the transferable protective layer to electrically affect electronic parts, causing malfunctions and malfunctions. .

  Hereinafter, the case where the transferable protective layer 2 is a transferable protective layer 2 having a laminated structure composed of two or more layers, and the transfer of a single layer structure where the transferable protective layer 2 is composed of one layer. The protective protective layer 2 will be described in detail.

"Transferable protective layer with laminated structure"
The transferable protective layer 2 in the form shown in FIG. 1 has a configuration in which a release layer 11 and an adhesive layer 12 are laminated in this order from the substrate 1 side. In the transferable protective layer 2 of this form, the release layer 11 is disposed at a position closest to the substrate 1 among the layers constituting the transferable protective layer 2, and the adhesive layer 12 constitutes the transferable protective layer 2. It arrange | positions in the position furthest from the base material 1 among the layers. According to the transferable protective layer 2 of this form, when the transferable protective layer 2 is transferred onto the print product, the print product and the adhesive layer 12 are in direct contact with each other, so that the transferable protection provided on the print product is provided. The release layer 11 is located on the outermost surface of the layer 2. In other words, the adhesive layer 12 is disposed at a position closest to the surface of the printed material, and the release layer 11 is disposed at a position farthest from the surface of the printed material.

  In the configuration shown in FIG. 1, the ionic liquid may be contained in the release layer 11 or in the adhesive layer 12. Further, one or two or more arbitrary layers are provided between the release layer 11 and the adhesive layer 12 or between the substrate 1 and the release layer 11, and the ionic liquid is contained in the arbitrary layer. May be. Regardless of which layer contains the ionic liquid, antistatic performance can be imparted to both the protective layer transfer sheet 10 and the printed material to which the transferable protective layer 2 has been transferred. Hereinafter, preferred embodiments of the transferable protective layer 2 containing an ionic liquid will be described.

  When the main purpose is to provide antistatic performance when the transferable protective layer 2 is transferred to a printed material or to provide high antistatic performance to the protective layer transfer sheet 10 before transferring the transferable protective layer 2 In the case of focusing on the conveyance failure due to sticking of the protective layer transfer sheet and the printed material, and prevention of dust adsorption on the protective layer transfer sheet, among the layers constituting the transferable protective layer 2, It is preferable that the layer arrange | positioned in the position furthest from the base material 1 contains the ionic liquid. In other words, the layer disposed on the outermost surface of the protective layer transfer sheet 10 preferably contains an ionic liquid. When the layer arranged on the outermost surface of the protective layer transfer sheet 10 contains an ionic liquid, the antistatic performance can be directly imparted to the outermost surface of the protective layer transfer sheet 10. For example, in the protective layer transfer sheet 10 having the form shown in FIG. 1, the adhesive layer 12 preferably contains an ionic liquid.

  On the other hand, when the main object is to impart high antistatic performance to the printed material to which the transferable protective layer 2 has been transferred, specifically, when the main purpose is to improve the handling of the printed material, Of the layers constituting the protective layer 2, it is preferable that an ionic liquid is contained in a layer disposed at a position closest to the substrate 1. Of the layers constituting the transferable protective layer 2, the layer disposed at the position closest to the substrate 1 is the layer positioned on the outermost surface of the print product when the transferable protective layer 2 is transferred onto the print product. It becomes. Therefore, after transferring the transferable protective layer 2 to the printed matter, the layer located on the outermost surface of the printed matter contains an ionic liquid, so that the surface of the printed matter to which the transferable protective layer 2 is transferred is prevented from being charged directly. Performance can be imparted. For example, in the protective layer transfer sheet 10 shown in FIG. 1, the release layer 11 preferably contains an ionic liquid.

  Note that this does not limit the layer containing the ionic liquid. For example, even when the ionic liquid is contained only in the layer disposed at the position closest to the base material 1, Antistatic performance can be imparted to the outermost surface of the layer transfer sheet. Further, even when the ionic liquid is contained only in the layer disposed at the position farthest from the base material 1, the antistatic performance is imparted to the surface of the printed material on which the transferable protective layer 2 has been transferred. Can do.

  Further, the ionic liquid may be contained in both the layer disposed at the position closest to the substrate 1 and the layer disposed at the position farthest from the substrate 1. According to this configuration, sufficient antistatic performance can be imparted to both the protective layer transfer sheet 10 and the printed material to which the transferable protective layer 2 has been transferred. For example, in the form shown in FIG. 1, it is preferable that the ionic liquid is contained in both the release layer 11 and the adhesive layer 12. Further, all layers constituting the transferable protective layer 2 may contain an ionic liquid.

  Of the layers constituting the transferable protective layer 2, the layer containing the ionic liquid may contain a conventionally known antistatic agent together with the ionic liquid within the range not impairing the gist of the present invention. Good. As explained above, the ionic liquid can exhibit excellent antistatic performance with a small addition amount. Accordingly, when used in combination with an ionic liquid and a conventionally known antistatic agent, the content of the conventionally known antistatic agent can be greatly reduced, and a large amount of a conventionally known antistatic agent is added. The antistatic performance can be further improved by the synergistic effect of the ionic liquid and the conventionally known antistatic agent while preventing various problems that may occur.

  Hereinafter, the peeling layer 11 and the adhesive layer 12 will be briefly described. In addition, it does not limit at all about the component which comprises the peeling layer 11 and the contact bonding layer 12, A conventionally well-known thing can be suitably selected and used in the field | area of a protective layer transfer sheet. Note that the release layer 11 may be referred to as a protective layer, and the adhesive layer 12 may be referred to as a heat seal layer.

(Peeling layer)
The binder resin constituting the release layer includes methacrylate ester copolymer, vinyl chloride / vinyl acetate copolymer, polyester resin, polycarbonate resin, acrylic resin, ultraviolet absorbing resin, epoxy resin, polystyrene resin, polyurethane resin, acrylic resin. Examples thereof include urethane resins, resins obtained by modifying these resins with silicone, mixtures of these resins, ionizing radiation curable resins, ultraviolet absorbing resins, and the like. Among these, acrylic resins and ionizing radiation curable resins can be suitably used because they are particularly excellent in scratch resistance. These binder resins are preferable in that they are excellent in scratch resistance and can impart scratch resistance to the printed material to which the transferable protective layer 2 has been transferred.

  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. The ultraviolet absorbing resin is particularly excellent in that light resistance is imparted to the printed matter.

  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 polymerization to conventionally known non-reactive organic ultraviolet absorbers such as salicylates, benzophenones, benzotriazoles, triazines, substituted acrylonitriles, nickel chelates, hindered amines, etc. And a reactive group such as an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group, which are functional double bonds (for example, vinyl group, acryloyl group, methacryloyl group, etc.).

  The release layer 11 can also contain various release agents for improving the transferability (peelability) of the transferable protective layer 2 from the substrate 1. Various release agents include waxes, silicone waxes, silicone resins, silicone modified resins, fluorine resins, fluorine modified resins, polyvinyl alcohol, acrylic resins, heat crosslinkable epoxy-amino resins and heat crosslinkable alkyd-amino resins. Can be mentioned.

  The release layer is formed by adding the binder resin exemplified above, and if necessary, an ultraviolet absorber, an antioxidant, a fluorescent brightener, an inorganic or organic filler component, a surfactant, a release agent, etc. A layer coating solution can be prepared, and this can be formed on the substrate 1 or an arbitrary layer by coating and drying by a method such as gravure coating or gravure reverse coating. Moreover, what is necessary is just to prepare the coating liquid for peeling layers containing an ionic liquid, when making the peeling layer 11 contain an ionic liquid.

  The thickness of the release layer 11 is preferably about 0.2 μm to 20 μm, although it depends on the type of binder resin that forms the release layer 11.

(Adhesive layer)
As the binder resin constituting the adhesive layer 12, a binder resin having high adhesion to the printed material can be appropriately selected and used. Examples of such binder resins include conventionally known heat-sensitive adhesives, acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, epoxy resins, polyester resins, polycarbonate resins, and butyral. Examples thereof include a resin, a polyamide resin, and a vinyl chloride resin.

  The adhesive layer 12 was formed by adding the binder resin exemplified above, and if necessary, an ultraviolet absorber, an antioxidant, a fluorescent brightener, an inorganic or organic filler component, a surfactant, a release agent, and the like. An adhesive layer coating solution can be prepared, and this can be formed on the release layer 11 or an arbitrary layer by coating and drying using a method such as gravure coating or gravure reverse coating. Moreover, what is necessary is just to prepare the coating liquid for contact bonding layers containing an ionic liquid, when making the contact bonding layer 12 contain an ionic liquid.

  Although there is no limitation in particular about the thickness of the contact bonding layer 12, it is preferable that the coating amount at the time of drying is about 0.1 micrometer-20 micrometers.

"Single layer transferable protective layer"
The transferable protective layer 2 in the form shown in FIG. 2 has a configuration in which the transferable protective layer 2 composed of one layer is provided on the substrate 1. In this embodiment, the transferable protective layer 2 having a single layer structure contains an ionic liquid.

  The transferable protective layer 2 having a single-layer structure has functions required for the transferable protective layer, such as peelability from the substrate 1, adhesion to the printed material, scratch resistance, and durability such as plasticizer resistance. (Hereinafter, this layer may be referred to as an adhesive release layer). In this embodiment, the adhesive release layer 2A contains an ionic liquid. According to the transferable protective layer 2 having a single-layer structure of the present embodiment, antistatic performance can be imparted before and after the transfer of the transferable protective layer 2, similarly to the transferable protective layer 2 having the laminated structure. In particular, according to the transferable protective layer 2 having a single-layer structure, the adhesive release layer 2A is located on the outermost surface of the protective layer transfer sheet 10 and on the outermost surface of the printed material to which the transferable protective layer 2 has been transferred. Therefore, sufficient antistatic performance can be imparted to both the protective layer transfer sheet 10 and the printed material to which the transferable protective layer 2 has been transferred.

(Adhesive release layer)
Examples of the binder resin constituting the adhesive release layer 2A that is the transferable protective layer 2 having a single-layer structure include release properties from the substrate 1, adhesion to the printed material, scratch resistance, and plasticizer resistance. There is no particular limitation as long as it is determined in consideration of durability and the like. For example, by using a combination of the binder resins described in the release layer 11 and the adhesive layer 12, an adhesive release layer that satisfies the peelability from the base material 1, the adhesiveness to the printed material, and the durability can be obtained. be able to. The adhesive release layer 2 </ b> A may contain various additives described in the release layer 11 and the adhesive layer 12.

  Moreover, when making the transferable protective layer 2 into the transferable protective layer of a single layer structure, the said layer contains the ionic liquid. As for the ionic liquid, those described for the transferable protective layer having the above laminated structure can be used as they are, and detailed description thereof is omitted here.

  Although there is no limitation in particular about the thickness of 2 A of adhesive peeling layers, it is preferable that the coating amount at the time of drying is about 0.1 micrometer-20 micrometers.

  In the transferable protective layer having the laminated structure and the transferable protective layer having the single-layer structure described above, the ionic liquid is in the range of 1% by mass to 20% by mass with respect to all the components of the layer containing the ionic liquid. It is preferably contained in the range of 2% by mass to 12% by mass, more preferably 4% by mass to 10% by mass. In particular, by containing an ionic liquid in the range of 4 mass% or more and 10 mass% or less, the antistatic performance of the transferable protective layer 2 during transfer can be improved, and the transferable protective layer 2 is transferred. Antistatic performance can be imparted to the printed matter. In addition, when the content of the ionic liquid in the transferable protective layer 2 is less than 1% by mass, the antistatic performance tends to decrease, and when it exceeds 20% by mass, the content of the ionic liquid in the layer containing the ionic liquid The proportion of the binder resin decreases, and the peelability from the substrate 1 required for the transferable protective layer, the adhesion to the printed material, and the durability imparted to the printed material tend to decrease.

(Release layer)
A release layer (not shown) for improving the release property of the transferable protective layer 2 may be provided between the substrate 1 and the transferable protective layer 2. The release layer is an arbitrary layer in the protective layer transfer sheet 10 of the present invention. Examples of the resin forming 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-crosslinkable alkyd. -Amino resin etc. are mentioned. 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 about 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 a bismuth.

(Back layer)
Further, as shown in FIGS. 1 and 2, the heat resistance, the running performance of the thermal head during printing, and the like are improved on a surface different from the surface on which the transferable protective layer 2 of the substrate 1 is provided. A back layer 5 may be provided. In addition, the back surface layer 5 is an arbitrary structure in the protective layer transfer sheet 10 of the present invention.

  The back layer 5 can be formed by appropriately selecting a conventionally known thermoplastic resin or the like. Examples of the thermoplastic resin include polyester resins, polyacrylate resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins, and other polyolefin resins, polystyrene resins. Polyvinyl acetal resins such as polyvinyl chloride resins, polyether resins, polyamide resins, polyimide resins, polyamide imide resins, polycarbonate resins, polyacrylamide resins, polyvinyl chloride resins, polyvinyl butyral resins, polyvinyl acetoacetal resins And the like, and these silicone-modified products.

  Moreover, it is preferable that the back surface layer 5 contains a lubricant for improving slipperiness with the thermal head. The lubricant is an arbitrary configuration in the back layer 5. Examples of the lubricant include phosphoric acid esters, fatty acid esters, metal soaps, Wax, graphite powder, fluorine-modified graft polymers, fluorine-modified block polymers, silicone oils, silicone-modified graft polymers, silicone polymers such as silicone-modified block polymers, and the like. It can be appropriately selected and used. Among the above-mentioned lubricant components, phosphate ester, fatty acid ester, metal soap, and Wax can be particularly preferably used in the present invention.

  Examples of the metal soap include polyvalent metal salts of alkyl phosphate esters, polyvalent metal salts of fatty acids, metal salts of alkyl carboxylic acids, and the like, and known additives for plastics can be used. In the present invention, zinc stearate and / or zinc stearyl phosphate can be preferably used.

  Examples of the phosphate ester include (1) a phosphoric acid monoester or diester of a saturated or unsaturated higher alcohol having 6 to 20 carbon atoms, and (2) a phosphoric acid monoester of a polyoxyalkylene alkyl ether or polyoxyalkylene alkyl allyl ether. Ester or diester, (3) phosphoric acid monoester or diester of the above-mentioned saturated or unsaturated higher alcohol alkylene oxide adduct (average number of added moles of 1 to 8), (4) alkylphenol having an alkyl group of 8 to 12 carbon atoms Alternatively, phosphoric acid monoester or diester of alkyl naphthol can be used. Examples of the saturated or unsaturated higher alcohol in the above (1) and (3) include cetyl alcohol, stearyl alcohol, oleyl alcohol and the like. Examples of the alkylphenol in the above (3) include nonylphenol, dodecylphenol, diphenylphenol and the like.

For example, the back layer 5 is formed by applying a coating liquid obtained by dispersing or dissolving the above-described thermoplastic resin and various additives added in an appropriate solvent onto the base material 1 on a gravure printing method or a screen printing method. It can be formed by applying and drying by a known means such as a reverse roll coating printing method using a gravure plate. The thickness of the back layer 5, from the viewpoint of improvement of heat resistance and the like, it is preferable that the coating amount after drying is 2 g / m ² or less, to 0.1g / m ² ~1.5g / m ² Is more preferable.

(Back primer layer)
A back primer layer (not shown) may be provided between the substrate 1 and the back layer 5. The back primer layer is a layer provided in order to improve the adhesion between the substrate 1 and the back layer 5 and is an arbitrary layer. Examples of the back primer layer include polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, polyvinyl alcohol resin, and polyvinylpyrrolidone resin. Can be mentioned.

  Moreover, the back surface layer 5 and the back surface primer layer provided on the other surface side of the substrate 1 may contain a conventionally known antistatic agent, or may contain the ionic liquid described above. Good. By incorporating an antistatic agent in these layers, a further improvement in antistatic performance in the protective layer transfer sheet 10 can be expected due to a synergistic effect with the transferable protective layer 2 containing the ionic liquid.

  The protective layer transfer sheet 10 of the present invention has been described above. However, the protective layer transfer sheet 10 of the present invention can take various modifications without departing from the spirit of the present invention. For example, a color material layer-integrated protective layer transfer sheet in which a transferable protective layer 2 containing an ionic liquid and a color material layer (not shown) are provided in the same order on the same surface of the substrate 1 can be used. .

  Hereinafter, the present invention will be described with reference to examples and comparative examples. “Part” in the text is based on mass unless otherwise specified.

Example 1
A polyethylene terephthalate film having a thickness of 4.5 μm is used as a substrate, and a release layer coating liquid 1 having the following composition is applied thereon so that the coating amount when dried is 1.5 g / m ² to protect transferability. A release layer constituting the layer was formed. Next, an adhesive layer coating liquid 1 having the following composition was applied on the release layer so that the coating amount when dried was 1.5 g / m ² to form an adhesive layer constituting a transferable protective layer. Further, a back layer coating liquid having the following composition is applied on a surface different from the surface on which the transferable protective layer of the substrate is formed so that the coating amount when dried is 1.0 g / m ^2. By forming, the protective layer transfer sheet of Example 1 was obtained.

  In the ionic liquid used in the following release layer coating solution, adhesive layer coating solution, or release layer / adhesive layer coating solution, the cation “BMP” is 1-butyl-1-methylpyrrolidinium. The cation “HMI” means 1-hexyl-3-methylimidazolium, the anion “TFSI” means bis (trifluoromethanesulfonyl) imide, and the anion “TF” means trifluoromethanesulfonate. Yes.

<Peeling layer coating solution 1>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220 Toyobo Co., Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 1.25 parts ・ Toluene 34.38 parts ・ Methyl ethyl ketone 34.37 parts

<Coating liquid 1 for adhesive layer>
・ Polyester resin 22.5 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Back layer coating liquid)
・ 2.5 parts of polyvinyl butyral resin (S-REC BX-1, Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 1.2 parts (Pricesurf A208N, Daiichi Kogyo Seiyaku Co., Ltd.)
・ 0.4 parts of talc (Microace P-3, Nippon Talc Industry Co., Ltd.)
-Polyisocyanate (solid content 75%) 5.1 parts (Bernock D750, Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 45.4 parts ・ Toluene 45.4 parts

(Example 2)
A protective layer transfer sheet of Example 2 was obtained in the same manner as Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 2 having the following composition.

<Peeling layer coating solution 2>
・ Acrylic resin 20.14 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Ultraviolet absorber copolymer acrylic resin (solid content 40%) 25.18 parts (PUVA-50M-40TM, Otsuka Chemical Co., Ltd.)
-Ionic liquid (cation: BMP, anion: TFSI) 1.26 parts-Toluene 26.71 parts-Methyl ethyl ketone 26.71 parts

(Example 3)
A protective layer transfer sheet of Example 3 was obtained in the same manner as Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 3 having the following composition.

<Peeling layer coating solution 3>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
-Ionic liquid (cation: BMP, anion: TFSI) 3.33 parts-Toluene 33.34 parts-Methyl ethyl ketone 33.33 parts

Example 4
A protective layer transfer sheet of Example 4 was obtained in the same manner as Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 4 having the following composition.

<Peeling layer coating solution 4>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 0.46 parts ・ Toluene 34.77 parts ・ Methyl ethyl ketone 34.77 parts

(Example 5)
Instead of the release layer coating liquid 1, 1.25 parts of the ionic liquid (cation: BMP, anion: TFSI) of the release layer coating liquid 1 is replaced with 1.25 of the ionic liquid (cation: HMI, anion: TFSI). A protective layer transfer sheet of Example 5 was obtained in the same manner as in Example 1 except that the peeling layer coating solution 5 changed to the part was used.

(Example 6)
Instead of the release layer coating solution 1, 1.25 parts of the release layer coating solution 1 ionic liquid (cation: BMP, anion: TFSI) 1.25 parts ionic liquid (cation: BMP, anion: TF) 1.25 A protective layer transfer sheet of Example 6 was obtained in the same manner as in Example 1 except that the peeling layer coating solution 6 changed to the part was used.

(Example 7)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the following composition, and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution 2 having the following composition. In the same manner as described above, a protective layer transfer sheet of Example 7 was obtained.

<Coating liquid 7 for release layer>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
・ Toluene 35 parts ・ Methyl ethyl ketone 35 parts

<Coating liquid 2 for adhesive layer>
・ Polyester resin 21.5 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 1 part ・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Example 8)
The release layer coating solution 1 is changed to the release layer coating solution 7 having the above composition, and the adhesive layer coating solution 1 is replaced with a polyester resin (Byron 290 Toyobo Co., Ltd.). ) All in the same manner as in Example 1 except that 21.5 parts were changed to 21.5 parts of acrylic resin (Dianar BR-83, Mitsubishi Rayon Co., Ltd.). A protective layer transfer sheet of Example 8 was obtained.

Example 9
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution 4 having the following composition. In the same manner as described above, a protective layer transfer sheet of Example 9 was obtained.

<Coating liquid 4 for adhesive layer>
・ Polyester resin 20 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 2.5 parts ・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Example 10)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution 5 having the following composition. In the same manner as described above, a protective layer transfer sheet of Example 10 was obtained.

<Coating liquid 5 for adhesive layer>
・ Polyester resin 22.13 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 0.375 parts ・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Example 11)
The release layer coating solution 1 is changed to the release layer coating solution 7 having the above composition, and the adhesive layer coating solution 1 is replaced with an ionic liquid (cation: BMP, anion: The protective layer of Example 11 was the same as Example 1 except that 1 part of TFSI was used as the adhesive layer coating solution 6 in which 1 part of the ionic liquid (cation: HMI, anion: TFSI) was used. A transfer sheet was obtained.

(Example 12)
The release layer coating solution 1 is changed to the release layer coating solution 7 having the above composition, and the adhesive layer coating solution 1 is replaced with an ionic liquid (cation: BMP, anion: The protective layer of Example 12 was the same as Example 1 except that the adhesive layer coating solution 7 in which 1 part of TFSI was changed to 1 part of ionic liquid (cation: BMP, anion: TF) was used. A transfer sheet was obtained.

(Example 13)
A protective layer transfer sheet of Example 13 was obtained in the same manner as Example 1 except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution 2 having the above composition.

(Example 14)
Using a polyethylene terephthalate film having a thickness of 4.5 μm as a base material, a coating solution for a release layer and an adhesive layer having the following composition was applied thereon so that the coating amount when dried was 1.5 g / m ² , A transferable protective layer consisting only of a release layer and adhesive layer was formed. Further, a back layer coating liquid having the above composition is applied on a surface different from the surface on which the transferable protective layer of the base material is formed so that the coating amount when dried is 1.0 g / m ^2. By forming, the protective layer transfer sheet of Example 14 was obtained.

<Peeling layer and adhesive coating solution>
・ Acrylic resin 21.4 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.1 part (Byron 220, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
・ Ionic liquid (cation: BMP, anion: TFSI) 1 part ・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Comparative Example 1)
A protective layer transfer sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition.

(Comparative Example 2)
A protective layer transfer sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution A having the following composition.

<Coating liquid A for release layer>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
-Needle-like conductive antimony-containing tin oxide powder (Sb-doped SnO ₂ , long axis: 0.2 to 2.0 μm, short axis: 0.2 to 2.0 μm) 1.3 parts (FS-10P, Ishihara Sangyo ( stock))
・ Toluene 33.7 parts ・ Methyl ethyl ketone 33.69 parts

(Comparative Example 3)
Instead of the release layer coating solution 1, the needle-like conductive antimony-containing tin oxide powder (Sb-doped SnO ₂ , major axis: 0.2 to 2.0 μm, minor axis: 0. 2 to 2.0 μm) (FS-10P Ishihara Sangyo Co., Ltd.) Comparison was made in the same manner as in Example 1 except that 1.3 parts of the coating liquid B for release layer was changed to 2.61 parts. The protective layer transfer sheet of Example 3 was obtained.

(Comparative Example 4)
A protective layer transfer sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution C having the following composition.

<Coating liquid C for release layer>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
Anionic surfactant (solid content 50%) 5.22 parts (Electro Stripper ME-2, Kao Corporation)
・ Toluene 32.39 parts ・ Methyl ethyl ketone 32.39 parts

(Comparative Example 5)
A protective layer transfer sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution D having the following composition.

<Coating liquid D for release layer>
・ Acrylic resin 29.7 parts (Dianar BR-87, Mitsubishi Rayon Co., Ltd.)
・ Polyester resin 0.3 part (Byron 220, Toyobo Co., Ltd.)
-Anionic surfactant (solid content 50%) 6.67 parts (Electro Stripper ME-2, Kao Corporation)
・ Toluene 31.67 parts ・ Methyl ethyl ketone 31.66 parts

(Comparative Example 6)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution A having the following composition. In the same manner as described above, a protective layer transfer sheet of Comparative Example 6 was obtained.

<Coating liquid A for adhesive layer>
・ Polyester resin 21.5 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
· Acicular conductive antimony-containing tin oxide powder (Sb-doped SnO _2, major axis: 0.2 to 2.0 [mu] m, minor axis: 0.2 to 2.0 [mu] m) 1 part (FS-10P, manufactured by Ishihara Sangyo Kaisha, Ltd. )
・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Comparative Example 7)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution B having the following composition. In the same manner as described above, a protective layer transfer sheet of Comparative Example 7 was obtained.

<Coating liquid B for adhesive layer>
Polyester resin 20.5 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
-Needle-like conductive antimony-containing tin oxide powder (Sb-doped SnO ₂ , long axis: 0.2 to 2.0 μm, short axis: 0.2 to 2.0 μm) 2 parts (FS-10P, Ishihara Sangyo Co., Ltd.) )
・ Toluene 37.5 parts ・ Methyl ethyl ketone 37.5 parts

(Comparative Example 8)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition, and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution C having the following composition. In the same manner as described above, a protective layer transfer sheet of Comparative Example 8 was obtained.

<Coating liquid C for adhesive layer>
Polyester resin 20.5 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
Anionic surfactant (solid content 50%) 4 parts (Electro Stripper ME-2 Kao Corporation)
・ Toluene 36.5 parts ・ Methyl ethyl ketone 36.5 parts

(Comparative Example 9)
Example 1 except that the release layer coating solution 1 was changed to the release layer coating solution 7 having the above composition and the adhesive layer coating solution 1 was changed to the adhesive layer coating solution D having the following composition. In the same manner, a protective layer transfer sheet of Comparative Example 9 was obtained.

<Coating liquid D for adhesive layer>
・ Polyester resin 20 parts (Byron 290, Toyobo Co., Ltd.)
・ UV absorber 2.5 parts (Tinubin 928, BASF Japan Ltd.)
Anionic surfactant (solid content 50%) 5 parts (Electro Stripper ME-2, Kao Corporation)
・ Toluene 36.25 parts ・ Methyl ethyl ketone 36.25 parts

(Glossiness evaluation)
The protective layer transfer sheet of each example and comparative example is cut and pasted on the protective layer of a genuine ribbon of a sublimation type transfer printer (DS40 manufactured by DNP Photolcio Co., Ltd.), and a solid black image is printed on a genuine thermal transfer image receiving paper with a DS40 printer. (Maximum density image of yellow, magenta, cyan (tone values are all 255 gradations)) and solid white image (lowest density image of yellow, magenta, cyan (tone values are all 0 gradations)) In addition, prints of Examples 1 to 14 and Comparative Examples 1 to 9 in which a transferable protective layer was provided on the black solid image and the white solid image were obtained. For each of the printed matter of each Example and Comparative Example, the glossiness (light reflection angle is 45 ° condition) of the surface of the transferable protective layer provided on the black solid image and the white solid image is measured with a gloss meter (Japan). Dentsu Kogyo Kogyo Co., Ltd. (GlossMeter VG2000) was measured and evaluated based on the following evaluation criteria. The evaluation results are also shown in Table 1. The glossiness is measured on the surface of the transferable protective layer provided on the black solid image and the surface of the transferable protective layer provided on the white solid image. The glossiness is evaluated in the black of Comparative Example 1. The glossiness of the surface of the transferable protective layer provided on the solid image was compared with the glossiness of the surface of the transferable protective layer provided on the black solid image of each Example and Comparative Example. By comparing the glossiness of the surface of the transferable protective layer provided on one white solid image and the glossiness of the surface of the transferable protective layer provided on the white solid image of each Example and Comparative Example went.
<Evaluation criteria>
○: The glossiness of the surface of the transferable protective layer provided on the black solid image and the glossiness of the surface of the transferable protective layer provided on the white solid image are both −5% or more of the glossiness of Comparative Example 1 Δ : The glossiness of the surface of the transferable protective layer provided on the black solid image and the glossiness of the surface of the transferable protective layer provided on the white solid image are both −5 to −10% of the glossiness of Comparative Example 1. Or any one glossiness is in the range of −5 to −10% of the glossiness of Comparative Example 1, and the other glossiness is −5% or more of the glossiness of Comparative Example 1 ×: The glossiness of Comparative Example 1 is one of or both of the glossiness of the surface of the transferable protective layer provided on the black solid image and the glossiness of the surface of the transferable protective layer provided on the white solid image. -10% or less of degree

(Surface electrical resistance evaluation 1)
The surface electrical resistance value (Ω / □) on the transferable protective layer side of the protective layer transfer sheet of each example and comparative example was measured using a surface electrical resistance meter (Hiresta IP MCP-HT250, manufactured by Mitsubishi Yuka Co., Ltd.). Measurement was performed under the following conditions, and surface electrical resistance was evaluated based on the following evaluation criteria. The surface electrical resistance value was measured in an environment of 20 ° C. and 60%. The evaluation results are shown in Table 1. Note that Ω / □ is a unit indicating a surface electrical resistance value per unit area. The evaluation results are also shown in Table 1. When the evaluation is an evaluation of Δ or more, it is possible to demonstrate a handling property with no problem in use, and it is possible to prevent a printing defect due to dust.
<Measurement conditions>
PROBE TYPE: HR
SUPPLY VOLTAGE: 500V
TIMER: 10 sec
<Evaluation criteria>
◎: Less than 1.0 × 10 11 ◯: 1.0 × 10 11 or more, 1.0 × 10 less than 12 12 Δ: 1.0 × 10 12 or more, 5.0 × 10 Less than 12th power ×: 5.0 × 10 12th power or more

(Surface electrical resistance evaluation 2)
Surface electrical resistance on the side of the transferable protective layer of the prints of the examples and comparative examples obtained by the above glossiness evaluation (printed prints provided with a transferable protective layer on a solid black image and a solid white image) The value (Ω / □) was measured using a surface electrical resistance meter (Hiresta IP MCP-HT250 manufactured by Mitsubishi Oil Chemical Co., Ltd.) under the same conditions as in the surface electrical resistance evaluation 1, and the surface electrical resistance evaluation 1 and The surface electrical resistance was evaluated based on the same evaluation criteria. The evaluation results are also shown in Table 1.

(Preservation evaluation)
Store the genuine ribbon magenta part of the sublimation transfer printer (DS40 manufactured by DNP Photolcio Co., Ltd.) and the back layer, apply 20 kg / cm ² load, and store for 96 hours at 40 ° C and 90% humidity. The dye was transferred (kick) to the back layer. In addition, the back layer used for the kick of dye used the thing of the same composition as the back layer of the protective layer transfer sheet of each said Example and a comparative example.

The back layer and the adhesive layer of the protective layer transfer sheet of each example and comparative example were overlaid with the dye layer kicked by the above method, using a constant load compression tester (manufactured by Toyo Seiki Seisakusho), A load of 20 kgf / cm ² was applied and stored in an environment of 60 ° C. and 20% RH for 24 hours to forcibly retransfer (back) the dye. Thereafter, the adhesive layer on which the dye has re-transferred (backed) and the image-receiving surface of a genuine image-receiving paper of a sublimation type transfer printer (DS40 manufactured by DNP Photolcio Inc.) are overlapped, and a laminating tester (Lamipacker LPD2305PRO, manufactured by Fuji Pla Co., Ltd.) The transferable protective layer was transferred at a processing temperature of 110 ° C. and a processing speed of 1 m / min. Subsequently, the transferable protective layer was peeled off from the image receiving paper, and the hue of the transfer part was measured using GRETAG Spectrolino (D65 light source, viewing angle 2 °) manufactured by Gretag, and evaluated based on the following criteria.

(Color difference calculation formula)
ΔE ^* = ((difference between L ^* values before and after facing) ² + (difference between a ^* values before and after facing) ² + (difference between b ^* values before and after facing) ² ) ^1/2
Incidentally, L ^* a ^* b ^* means CIE1976, L ^* a ^* b ^* defined in the color system ^{(JIS Z8729 1980) L * a} * b *.

(Evaluation criteria)
○: Color difference ΔE ^* between the transfer product transferred from the unpreserved protective layer and the transfer product transferred from the backed transferable protective layer is less than 1.0 Δ: Transfer product from the transfer of the non-preserved protective layer and the back The color difference ΔE ^* of the transferred product to which the transferred protective protective layer is transferred is 1.0 or more and less than 2.0 ×: the transferred product to which the unpreserved protective layer is transferred, and the transferred product to which the transferred protective protective layer is transferred Color difference ΔE ^* of 2.0 or more

(Transferability evaluation)
The protective layer transfer sheet of each example and comparative example was cut and pasted on the magenta part of the genuine ribbon of a sublimation transfer printer (DS40 manufactured by DNP Photo Lucio Co., Ltd.), and the sublimation transfer printer (DS40 manufactured by DNP Photo Lucio Co., Ltd.) was applied. Then, yellow is the highest density (gradation value is 255 gradations), and the magenta gradation value is changed by 25 gradations from 255 to 130 gradations, and the cut and pasted protective layer transfer sheet is printed. When finished, the printing was stopped. As a result, prints of Examples and Comparative Examples were obtained in which the transferable protective layer with the print gradation changed was transferred onto the yellow maximum density image. In this printed matter, it was judged visually at which gradation the transferable protective layer was transferred, and the adhesiveness was evaluated based on the following evaluation criteria. In addition, it can be said that adhesiveness is so favorable that a transferable protective layer transfers with low gradation. The adhesive evaluation results are also shown in Table 1.

<Evaluation criteria>
○: The transferable protective layer was transferred at a gradation of 255 to 155.
Δ: The transferable protective layer was transferred with 255 to 180 gradations.
X: The transferable protective layer was transferred with 255 to 205 gradations.

  As is clear from Table 1, according to the protective layer transfer sheet of each example, the transferability can be achieved without interfering with the basic functions required for the protective layer transfer sheet, such as glossiness, storability and transferability. It was possible to improve the antistatic performance during transfer of the protective layer, or to improve the antistatic performance of the printed material on which the transferable protective layer was transferred. According to one embodiment, the antistatic performance during transfer of the transferable protective layer and the antistatic performance of the printed material to which the transferable protective layer has been transferred are simultaneously improved without disturbing the basic performance. I was able to. On the other hand, in the protective layer transfer sheet of the comparative example, the basic performance cannot be satisfied with respect to the sheet having improved antistatic performance, and the basic performance can be satisfied. The antistatic performance has not been improved. This also reveals the superiority of the protective layer transfer sheet of the present invention.

DESCRIPTION OF SYMBOLS 10 ... Protective layer transfer sheet 1 ... Base material 2 ... Transferable protective layer 11 ... Release layer 12 ... Adhesive layer 2A ... Adhesive release layer 5 ... Back layer

Claims (2)

A protective layer transfer sheet used in a thermal transfer recording method,
The protective layer transfer sheet is provided on one surface of the base material with a transferable protective layer that is peeled off from the base material side by a thermal transfer recording method and transferred onto the transfer target .
The transferable protective layer is composed of one or more layers,
The protective layer transfer sheet, wherein at least one of the layers constituting the transferable protective layer contains an ionic liquid. In the case where the transferable protective layer is composed of two or more layers,
Among the layers constituting the transferable protective layer, either one of the layer disposed at the position closest to the substrate and the layer disposed at the position furthest from the substrate, or both layers The protective layer transfer sheet according to claim 1, comprising the ionic liquid.

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