JP5297741B2 - Protective layer transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a protection layer transfer sheet capable of stably and satisfactorily carrying out protection layer transfer, and capable of exhibiting satisfactory durability of printed matter after the protection layer transfer. <P>SOLUTION: The protection layer transfer sheet has a heat-resistant lubricating layer, and is provided with a heat-transferable protection layer on a face opposite to a face provided with the heat-resistant lubricating layer of a base material sheet, the protection layer includes a separation layer and an adhesive layer sequentially from a base material sheet side, the separation layer contains, as main components, one kind or more of acrylic copolymer resins selected from the group comprising an acrylic copolymer resin copolymerized with a methacrylic ester (a) and a (meth)acrylic ester (b), an acrylic copolymer resin copolymerized with the methacrylic ester (a) and an acrylic ester (c), and an acrylic copolymer resin copolymerized with the methacrylic ester (a), the (meth)acrylic ester (b) and the acrylic ester (c), and the acrylic copolymer resin contains the (meth)acrylic ester (b) within a range of 0.1-1 mass%, and the acrylic ester (c) within a range of 0.1-8 mass%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a protective layer transfer sheet, and in particular, relates to a protective layer transfer sheet that can stably and satisfactorily transfer a protective layer, and has good durability of a printed product after the transfer of the protective layer.

  Conventionally, characters and images are formed on a transfer medium using a thermal transfer method. As the thermal transfer method, a thermal sublimation transfer method and a thermal fusion transfer method are widely used. Of these, the heat-sensitive sublimation transfer method uses a sublimation dye as a color material, and uses a heating device such as a thermal head or laser light whose heat is controlled according to image information, and uses a sublimation dye layer on the thermal transfer sheet. In this method, an image is formed by transferring the dye inside to a transfer medium such as a thermal transfer image receiving sheet. This heat-sensitive sublimation transfer system can control the amount of dye transfer in dot units by heating for a very short time. The image formed in this way is very clear because the coloring material used is a dye and is excellent in transparency, so the resulting image is excellent in halftone reproducibility and gradation, An extremely high-definition image can be obtained. For this reason, a high quality image comparable to a full-color silver salt photograph can be obtained. Because of these advantages, the thermal transfer technology of the heat-sensitive sublimation transfer system is widely used for business photographs, personal computer printers, video printers, and the like.

  However, the above-mentioned thermal sublimation transfer method can control the amount of dye transfer in dot units according to the amount of energy applied, so it is excellent in forming a gradation image, but the formed image is based on ordinary printing ink. Unlike the above, the coloring material is not a pigment but a dye having a relatively low molecular weight, and since there is no vehicle, there is a disadvantage that it is inferior in durability such as light resistance, weather resistance and abrasion resistance. In addition, an image formed by the heat-sensitive recording method has a vehicle, but it is still inferior in durability and in particular in abrasion resistance as compared with an image formed with ordinary printing ink.

  As a means to enhance the durability of printed matter by thermal transfer method, a protective layer transfer sheet having a thermal transfer resin layer (thermal transferable protective layer) is overlaid on the image obtained by sublimation thermal transfer method or hot melt recording method In addition, a method of forming a protective layer on an image by transferring a thermal transfer resin layer using a thermal head, a heating roll or the like is known. When a protective layer is provided on the image of the printed matter, the friction resistance, chemical resistance, solvent resistance, etc. of the image can be improved. Further, an ultraviolet absorber can be added in the protective layer to improve the light resistance of the image. Furthermore, a fluorescent whitening agent or the like can be added to the protective layer to impart a special function to the protective layer, such as preventing forgery or improving the whiteness of the printed material.

  As a protective layer transfer sheet, for example, as shown in Patent Documents 1 and 2, a release layer is formed on a substrate, an adhesive layer is provided on the release layer, and a release layer is formed on the thermal transfer image-receiving sheet. A configuration in which an adhesive layer is provided for stable transfer is known. Further, when the release layer is thermally transferred onto the thermal transfer image-receiving sheet, a heat-resistant slipping layer is provided on the other surface of the base material so that the base material of the protective layer transfer sheet is not damaged by heat.

Patent Document 3 discloses a protective layer transfer sheet in which a release layer, a primer layer, and a heat seal layer are laminated on a base sheet.
JP-A-4-35988 Japanese Patent Laid-Open No. 4-142988 JP 2006-228772 A

  However, in the above-mentioned conventional protective layer transfer sheet, the surface temperature due to the difference in the thermal transfer printer model, the environmental temperature in which the printer is placed, and the accumulated heat of the thermal head at the start of printing and continuous printing When the energy applied in the transfer of the protective layer varies due to the difference in the above, there has been a problem that a change in the peeling force during the transfer of the protective layer to the transfer medium is large, resulting in poor peeling of the protective layer transfer.

  Therefore, the present invention has been made in view of such a situation, and has a heat-resistant slip layer on one surface of the base sheet, and the heat-resistant slip layer of the base sheet is provided. In a protective layer transfer sheet provided with a heat transferable protective layer on at least a part of the surface opposite to the surface, even when the energy applied in the protective layer transfer increases, peeling during transfer of the protective layer to the transfer target Provided is a protective layer transfer sheet in which an increase in force is suppressed, transfer of the protective layer can be performed stably and satisfactorily, and durability (abrasion resistance and plasticizer resistance) of the printed material after transfer of the protective layer is good. For the purpose.

The protective layer transfer sheet of the present invention has a heat-resistant slip layer on one surface of the base sheet, and at least a part of the surface of the base sheet opposite to the surface on which the heat-resistant slip layer is provided. , in the protective layer transfer sheet provided with thermally transferable protective layer, the protective layer is peeled off layer from the substrate sheet side, includes an adhesive layer sequentially, the release layer, main methacrylic acid ester (a) (meth) the acrylic copolymer resins obtained by copolymerization of acrylic acid (b) acrylic acid ester (c) containing as a main component,
Prior Symbol methacrylate (a) and (meth) acrylic copolymer resin obtained by copolymerizing an acrylic acid (b) acrylic acid ester (c), the (meth) acrylic acid (b) is 0.1 -1 mass% and the said acrylic ester (c) are contained in the range of 0.1-8 mass%. When the specific acrylic copolymer resin is used for the release layer, even if the energy applied in the transfer of the protective layer due to various fluctuations in the thermal transfer printer, fluctuations in environmental temperature, etc. increases, the substrate sheet and the release layer The peeling failure of the protective layer transfer can be prevented without increasing the peeling force.

  According to the protective layer transfer sheet of the present invention, even if the energy applied in the protective layer transfer increases due to fluctuations in conditions such as the printer model, environmental temperature, and the surface temperature of the thermal head, the transferred object When transferring the protective layer to the protective layer, the protective layer can be transferred stably and satisfactorily without the peeling force being so high. In addition, by using the protective layer transfer sheet of the present invention, the protective layer is transferred to a printed material on which an image has been formed on a transfer medium using a thermal transfer method, whereby an image formed product having excellent durability can be obtained.

  The protective layer transfer sheet of the present invention has a heat-resistant slip layer on one surface of the base sheet, and at least a part of the surface of the base sheet opposite to the surface on which the heat-resistant slip layer is provided. In addition, in the protective layer transfer sheet provided with a heat transferable protective layer, the protective layer includes a release layer and an adhesive layer in that order from the base sheet side, and the release layer comprises the methacrylate ester (a) and (meth) acrylic. Acrylic copolymer resin obtained by copolymerizing acid (b), an acrylic copolymer resin obtained by copolymerizing methacrylic acid ester (a) and acrylic acid ester (c), and methacrylic acid ester (a) and ( Containing at least one acrylic copolymer resin selected from the group consisting of acrylic copolymer resins obtained by copolymerizing (meth) acrylic acid (b) and acrylic ester (c) as a main component, Acrylic copolymer resin Te, wherein (meth) acrylic acid (b) 0.1 to 1 wt%, and the acrylic acid ester (c) is characterized in that comprises in the range of 0.1 to 8 wt%. In the present invention, “(meth) acryl” includes both “acryl” and “methacryl”.

  FIG. 1 is a schematic cross-sectional view showing one embodiment of a protective layer transfer sheet 1 of the present invention, in which a release layer 3 and an adhesive layer 4 are sequentially laminated on one surface of a substrate sheet 2. The heat resistant slipping layer 5 is formed on the other surface of the sheet 2. The two layers of the release layer 3 and the adhesive layer 4 are the protective layer 6. For example, the protective layer 6 is heated by a thermal head from the heat-resistant slipping layer 5 of the protective layer transfer sheet 1. The image is transferred to a transfer object on which characters and the like are formed.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2 and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye, three colors of yellow dye layer Y, magenta dye layer M and cyan dye layer C, and further after cyan dye layer C, A protective layer 6 in which two layers of a release layer 3 and an adhesive layer 4 are laminated is repeatedly formed in the surface order. This form is a thermal transfer sheet in which three color dye layers and a protective layer are integrated.

  FIG. 3 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2, and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye is passed through a primer layer 7 and three colors of yellow dye layer Y, magenta dye layer M, and cyan dye layer C, and a release layer 3. The protective layer 6 in which two layers of the adhesive layer 4 are laminated is repeatedly formed in the surface order. In this form, a protective layer 6 in which three color dye layers are provided on a base material sheet via a primer layer, and after the cyan dye layer C, two layers of a release layer 3 and an adhesive layer 4 are laminated. However, it is the structure formed repeatedly by the surface sequential. This form is a thermal transfer sheet in which three color dye layers and a protective layer are integrated.

  FIG. 4 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2, and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye, a yellow dye layer Y, a magenta dye layer M, a cyan dye layer C, a black heat-meltable ink layer BK, and A protective layer 6 in which two layers of a release layer 3 and an adhesive layer 4 are laminated is repeatedly formed in the surface order. This form is a thermal transfer sheet in which a three-color dye layer and a black one-color heat-meltable ink layer are combined to integrate a four-color heat-transferable color material layer and a protective layer.

  FIG. 5 is a schematic cross-sectional view showing one embodiment of the protective layer transfer sheet 1 of the present invention. A release layer 3, a primer layer 7, and an adhesive layer 4 are sequentially formed on one surface of the substrate sheet 2. It is the structure which laminated | stacked and formed the heat-resistant slipping layer 5 in the other surface of the base material sheet 2. FIG. The protective layer 6 is composed of the release layer 3, the primer layer 7 and the adhesive layer 4. For example, the protective layer 6 is heated by a thermal head from the heat-resistant slipping layer 5 of the protective layer transfer sheet 1. Transferred to the transfer body.

  FIG. 6 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2 and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye, three colors of yellow dye layer Y, magenta dye layer M and cyan dye layer C, and further after cyan dye layer C, A protective layer 6 in which three layers of a release layer 3, a primer layer 7, and an adhesive layer 4 are laminated is repeatedly formed in the surface order. This form is a thermal transfer sheet in which three color dye layers and a protective layer are integrated.

  FIG. 7 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2 and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye is passed through a primer layer 7 and three colors of yellow dye layer Y, magenta dye layer M, and cyan dye layer C, and a release layer 3, a protective layer 6 in which three layers of a primer layer 7 and an adhesive layer 4 are laminated is repeatedly formed in the surface order. In this form, three color dye layers are provided on a base sheet via a primer layer, and after the cyan dye layer C, three layers of a release layer 3, a primer layer 7, and an adhesive layer 4 are laminated. Further, the protective layer 6 is repeatedly formed in the surface order. This form is a thermal transfer sheet in which three color dye layers and a protective layer are integrated.

FIG. 8 is a schematic cross-sectional view showing another embodiment of the protective layer transfer sheet 1 of the present invention, in which a heat-resistant slipping layer 5 is formed on one surface of the base sheet 2 and the base sheet 2 On the other side, as a heat transferable color material layer, a dye layer containing a sublimation dye, a yellow dye layer Y, a magenta dye layer M, a cyan dye layer C, a black heat-meltable ink layer BK, and A protective layer 6 in which three layers of a release layer 3, a primer layer 7, and an adhesive layer 4 are laminated is repeatedly formed in the surface order. This form is a thermal transfer sheet in which a three-color dye layer and a black one-color heat-meltable ink layer are combined to integrate a four-color heat-transferable color material layer and a protective layer.
The heat transferable color material layer is not limited to the form in which the above-described heat transferable color material layers are integrated. In addition to Y, M, C, and BK, a heat transferable color material layer having a different hue may be added. The layer and the protective layer can be appropriately changed.

Hereinafter, each layer constituting the protective layer transfer sheet of the present invention will be described in detail.
(Base material sheet)
As the base material sheet 2 of the protective layer transfer sheet used in the present invention, any material may be used as long as it has a conventionally known degree of heat resistance and strength, for example, 0.5 to 50 μm, preferably 1 to 10 μm. More preferably, a polyethylene terephthalate film having a thickness of 2 to 6 μm, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide 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 And the like. Among the above, a polyester film made of polyethylene terephthalate, polyethylene naphthalate, or a mixture thereof is preferable, and a polyethylene terephthalate film is more preferable.

(Peeling layer)
The release layer 3 in the protective layer transfer sheet of the present invention is an acrylic copolymer resin obtained by copolymerizing a methacrylic acid ester (a) and (meth) acrylic acid (b), a methacrylic acid ester (a) and an acrylic acid ester. From acrylic copolymer resin obtained by copolymerizing (c) and acrylic copolymer resin obtained by copolymerizing methacrylic acid ester (a), (meth) acrylic acid (b) and acrylic acid ester (c) 1 or more types of acrylic copolymer resin selected from the group which consists of as a main component, In each said acrylic copolymer resin, the said (meth) acrylic acid (b) is 0.1-1 mass%, and The acrylic ester (c) is contained in the range of 0.1 to 8% by mass. Note that the content as the main component means that the amount of the acrylic copolymer resin in the total amount of the release layer is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass. % Is included.

  As the methacrylic acid ester (a), it is preferable to use a methacrylic acid alkyl ester. Examples of the methacrylic acid ester (a) include methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. Among these, it is preferable to use methyl methacrylate.

  Examples of (meth) acrylic acid (b) include acrylic acid and methacrylic acid. Moreover, it is preferable to use an acrylic acid alkyl ester as the acrylic acid ester (c). Examples of the methacrylic acid ester (a) include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Of these, methyl acrylate and ethyl acrylate are preferably used.

  In the acrylic copolymer resins used in the present invention, in each acrylic copolymer resin, the (meth) acrylic acid (b) is 0.1 to 1% by mass, and the acrylic ester (c) is 0.00. It is contained in the range of 1 to 8% by mass. In each acrylic copolymer resin, when the (meth) acrylic acid (b) exceeds 1% by mass or the acrylic ester (c) exceeds 8% by mass, the energy applied in the transfer of the protective layer There is a possibility that a change in the peeling force between the base material sheet and the peeling layer due to the fluctuation becomes large, resulting in a defective peeling of the protective layer transfer, or a deterioration in the durability of the printed material. On the other hand, if the amount of the (meth) acrylic acid (b) or the acrylate ester (c) is too small in each acrylic copolymer resin, there is a possibility that a problem may occur in adhesion.

  Among them, an acrylic copolymer resin and a methacrylic acid ester obtained by copolymerizing 99.0 to 99.9% by weight of a methacrylic acid ester (a) and 0.1 to 1.0% by weight of a (meth) acrylic acid (b). (A) Acrylic copolymer resin obtained by copolymerizing 92 to 99% by mass and acrylic acid ester (c) 1 to 8% by mass, and methacrylic acid ester (a) 91 to 99% by mass and (meth) acrylic acid (B) One or more acrylics selected from the group consisting of acrylic copolymer resins obtained by copolymerizing 0.1 to 1.0% by mass and acrylic acid ester (c) 0.1 to 8% by mass It is preferable to use a copolymer resin. More preferably, an acrylic copolymer resin obtained by copolymerizing methacrylic acid ester (a) 99.2 to 99.8% by mass and (meth) acrylic acid (b) 0.2 to 0.8% by mass, Acrylic copolymer resin obtained by copolymerizing 93 to 98% by mass of acid ester (a) and 2 to 7% by mass of acrylic acid ester (c), and 92 to 98% by mass of methacrylic acid ester (a) and (meth) One selected from the group consisting of acrylic copolymer resins obtained by copolymerizing acrylic acid (b) 0.1 to 0.8% by mass and acrylic acid ester (c) 1.2 to 7.2% by mass It is desirable to use the above acrylic copolymer resin.

  Further, it is an acrylic copolymer resin obtained by copolymerizing a methacrylic acid ester (a), a (meth) acrylic acid (b) and an acrylic acid ester (c), wherein the (meth) acrylic acid (b) is 0. Among them, those containing 0.1 to 1% by mass and the acrylic ester (c) in the range of 0.1 to 8% by mass are preferable from the viewpoint of good adhesion of the protective layer transfer sheet.

  Examples of the synthesis method of the acrylic copolymer resin include known polymerization methods such as a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method. Of these, the suspension polymerization method is preferred.

  As a specific method for producing the acrylic copolymer resin by the suspension polymerization method, for example, a monomer mixture, a dispersing agent, a polymerization initiator, a chain transfer agent, etc. are added and suspended in an aqueous medium. The suspension can be heated and polymerized, and the suspension after polymerization can be filtered, washed, dehydrated and dried.

  Examples of the dispersant used in the production by the suspension polymerization method include poly (meth) acrylic acid alkali metal salts, (meth) acrylic acid alkali metal salts and (meth) acrylic acid ester copolymers, (meta ) From a sulfoalkyl acrylate alkali metal salt and (meth) acrylic acid ester copolymer, polystyrene sulfonic acid alkali metal salt, styrene sulfonic acid alkali metal salt and (meth) acrylic acid ester copolymer, or combinations of these monomers And polyvinyl alcohol having a saponification degree of 70 to 100%, methylcellulose, and the like. These may be used alone or in combination of two or more. Of these, a copolymer of an alkali metal salt of (alkyl) sulfoalkyl (meth) acrylate and a (meth) acrylic acid ester having good dispersion stability during suspension polymerization is preferred.

  Moreover, when manufacturing by suspension polymerization method, an inorganic electrolyte can be used together for the purpose of improving the dispersion stability during suspension polymerization. Examples of the inorganic electrolyte include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium sulfate, manganese sulfate and the like. These may be used alone or in combination of two or more.

  Examples of the polymerization initiator used for producing the acrylic copolymer resin include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2, Azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobisisobutyrate; lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, t-hexylperoxy 2-ethyl Hexanoate, t-butylperoxy 2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroper Oxide, t-hexyl hydro And organic peroxides such as peroxides; inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate; These may be used alone or in combination of two or more.

  Examples of the chain transfer agent used when producing the acrylic copolymer resin include alkyl mercaptans such as n-butyl mercaptan, sec-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and n-octadecyl mercaptan. Thioglycolic acid esters such as 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, trimethylolpropane tris (thioglycolate); 2-ethylhexyl β-mercaptopropionate, 3-methoxybutyl β-mercaptopropionate, And mercaptopropionic acid esters such as trimethylolpropane tris (β-thiopropionate). These may be used alone or in combination of two or more.

  The release layer contains various additives such as wax, inorganic fine particles, or organic fine particles, ultraviolet absorbers, antioxidants, and fluorescent brighteners, as long as the effects of the present invention and the transparency of the protective layer are not impaired. It may be included. Examples of the wax include polyethylene wax, polyester wax, polystyrene powder, olefin powder, microcrystalline wax, carnapa wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, wool Examples thereof include wax, shellac wax, candelilla wax, petrolactam, partially modified wax, fatty acid ester, fatty acid amide, and the like, and the abrasion resistance and foil breakability of the release layer are improved.

  Silica, alumina, titania, calcium carbonate, etc. can be used as the inorganic fine particles of the above additives. Examples of the organic fine particles include styrene fine particles, acrylic fine particles, melamine resin fine particles, and the like. The addition of these fine particles is effective for improving the foil cutting property and preventing rainbow unevenness. In order to further improve the light resistance and weather resistance of the image of the transfer target covered with the protective layer, an ultraviolet absorber can be added. As the ultraviolet absorber, conventionally known organic ultraviolet rays can be used. Absorbents such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, hindered amines and the like can be widely used. Also, for example, addition polymerizable double bonds such as vinyl groups, acryloyl groups, and methacryloyl groups, or functional groups such as alcoholic hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups are introduced into these ultraviolet absorbers. An ultraviolet absorbing resin may be contained in the release layer.

The release layer is prepared by dissolving the acrylic copolymer resin and, if necessary, the additive on the surface of the base sheet opposite to the side on which the heat-resistant slip layer is provided, with an appropriate solvent, a solvent such as water, or Disperse to prepare a release layer coating solution, which is applied by a forming means such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, and is formed by drying. Can do. The coating amount of the release layer, in the dry ^{state, 0.1g / m 2 ~10g / m} 2, and preferably from ^{0.5g / m 2 ~5g / m 2} .

(Adhesive layer)
The adhesive layer 4 used in the present invention is formed on the release layer provided in the protective layer transfer sheet of the present invention and contains a thermoplastic resin. The adhesive layer has a function of adhering the protective layer and the transferred material when the protective layer is formed on the transferred material such as a thermal transfer image receiving sheet using the protective layer transfer sheet of the present invention. is there.

The thermoplastic resin used for the adhesive layer in the present invention is not particularly limited as long as it has adhesiveness by heating. Examples of such thermoplastic resins include ethylene-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate copolymer resins, maleic acid-modified vinyl chloride-vinyl acetate copolymer resins, polyamide resins, polyester resins, polyethylene resins, ethylene -Isobutyl acrylate copolymer resin, butyral resin, polyvinyl acetate and its copolymer resin, ionomer resin, acid-modified polyolefin resin, acrylic / methacrylic (meth) acrylic resin, acrylic ester resin, ethylene・ (Meth) acrylic acid copolymer, ethylene / (meth) acrylic ester copolymer, polymethyl methacrylate resin, cellulose resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, Nord resin, vinyl resin, maleic resin, alkyd resin, polyethylene oxide resin, urea resin, melamine resin, melamine alkyd resin, silicone resin, rubber resin, styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene A thermoplastic resin such as a block copolymer (SIS), a styrene ethylene butylene styrene block copolymer (SEBS), or a styrene ethylene propylene styrene block copolymer (SEPS) can be used. Among the above, it is preferable to use a composition that can be heat-sealed at a temperature of 180 ° C. or lower.

Moreover, the additive demonstrated by the said peeling layer can be similarly used for the said contact bonding layer other than the said thermoplastic resin. Adhesive layer can be dried after coating amount is applied in an amount of ^{0.1g / m 2 ~10g / m 2} , in terms of imparting excellent adhesion, etc., coating amount after drying 0 It is preferable to apply in an amount of 0.5 g / m ^{2 to} 5.0 g / m ² .

(Heat resistant slipping layer)
The heat-resistant slipping layer 5 in the present invention is a surface on which a dye layer of the base sheet is provided for the purpose of preventing thermal fusion between a heating device such as a thermal head and the base sheet and running smoothly. Provide on the opposite side. Examples of the resin forming the heat-resistant slipping layer include cellulose resins such as ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose butyrate, and nitrocellulose; polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, Vinyl resins such as polyvinyl acetal and polyvinyl pyrrolidone; Acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, and acrylonitrile-styrene copolymer; Aromatic polyamide resin, polyimide resin, polyamideimide resin; Resin; Coumarone indene resin; Polyester resin; Polyurethane resin; Natural or synthetic resins such as silicone-modified or fluorine-modified urethane are used alone or as a mixture It is.

  From the viewpoint of further improving the heat resistance of the heat resistant slipping layer, the heat resistant slipping layer of the present invention is preferably formed from a composition containing an isocyanate compound and a hydroxyl group-containing resin. The isocyanate compound and the hydroxyl group-containing resin are usually present as a polymer polymerized in the layer to form a crosslinked resin layer. The hydroxyl group-containing resin is not particularly limited as long as it can react with an isocyanate compound. Examples of such a hydroxyl group-containing resin include polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polyester polyol, acrylic polyol, polyether polyol, urethane polyol, and polyester. Among them, polyvinyl butyral is preferably used in the present invention.

  As said isocyanate compound, if it is used for the synthesis | combination of a conventionally well-known coating material, an adhesive agent, a polyurethane, etc., it will not specifically limit, for example. Examples of such isocyanate compounds include polyisocyanates such as diisocyanate and triisocyanate. Specific examples of the polyisocyanate used in the present invention include paraphenylene diisocyanate, 1-chloro-2,4-phenyl diisocyanate, 2-chloro-1,4-phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6- Toluene diisocyanate, hexamethylene diisocyanate, 4,4′-biphenylene diisocyanate, triphenylmethane triisocyanate, 4,4 ′, 4 ″ -trimethyl-3,3 ′, 2′-triisocyanate-2,4,6-tri And phenyl cyanurate.

Or it is preferable that a heat resistant slipping layer contains a polyamide-imide resin from the point which improves the heat resistance of a heat resistant slipping layer more. Specifically, as described in JP-A-2001-334760, a binder obtained by mixing a specific amount of a polyamideimide resin and a polyamideimide silicone resin having a Tg of 200 ° C. or higher by differential thermal analysis, A heat-resistant slipping layer in which a specific amount of a polyvalent metal salt of an alkyl phosphate and a filler (filler) is mixed is preferable. The mixing ratio of the polyamideimide resin and the polyamideimide silicone resin is preferably in the range of 1 to 5 to 5 to 1, particularly preferably in the range of 1 to 2 to 2 to 1, from the viewpoint of the balance between heat resistance and lubricity. The polyamideimide silicone resin is a copolymerized or modified product of a polyamideimide resin and a polyfunctional silicone compound having a molecular weight of 1000 to 6000, and the amount of copolymerization or modification is 0.01 to 0.00 with respect to the polyamideimide resin 1. 3 is preferred. In addition, the polyvalent metal salt of alkyl phosphate ester is preferably in a ratio of 1 to 100 parts by mass per 100 parts by mass of the binder, and further in the range of 5 to 20 parts by mass, the releasability and physical properties during heat application. From the point of balance of mechanical strength. Moreover, it is preferable that the said filler is mixed in the ratio of 2-20 mass parts per 100 mass parts of binders.
In this case, the heat resistant slipping layer is different from that in which an isocyanate compound is used to crosslink the resin, and without applying a crosslinking reaction, the coating liquid containing the above material is applied to the base sheet and dried. It has excellent heat resistance and slipperiness.

  The slipperiness imparting agent added to or overcoating the heat resistant slipping layer made of these resins includes phosphate ester, metal soap, silicone oil, graphite powder, silicone graft polymer, fluorine graft polymer, acrylic silicone graft polymer, acrylic. Examples thereof include silicone polymers such as siloxane and arylsiloxane. Preferably, it is a layer made of a polyol, for example, a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate ester compound, and a filler may be added. More preferred.

The heat-resistant slipping layer is prepared by dissolving or dispersing the above-described resin, slipperiness-imparting agent, and filler in an appropriate solvent on the base sheet to prepare a heat-resistant slipping layer coating solution. This can be formed by coating with a forming means such as gravure printing, screen printing, reverse roll coating using a gravure plate, and drying. The coating amount of the heat-resistant slip layer is in a dry ^{state, 0.1g / m 2 ~2.0g / m} 2 is preferred.

(Heat transferable color material layer)
In the present invention, the heat transferable color material layer can be formed in the surface order on the protective layer composed of two layers including the release layer and the adhesive layer, and the same substrate sheet. As a result, the thermal transfer colorant layer and the protective layer can be transferred with one head of the thermal transfer printer, and it is not necessary to provide a plurality of units for supplying and winding the thermal transfer sheet. And the printer transport system is not complicated.

  The heat transferable color material layer may be either a color material layer (heat meltable ink layer) made of heat meltable ink or a color material layer (dye layer) containing a sublimable dye. The hot-melt ink used in the present invention comprises a colorant and a vehicle, and various additives are added as necessary. As the colorant, among organic or inorganic pigments or dyes, those having a color density required as a recording material and not discolored by light, heat, temperature or the like are preferable. In addition, a substance that develops color when heated or a substance that develops color when in contact with a substance applied to the transfer target can also be used. In addition to cyan, magenta, yellow, black and the like, various colorants can be used as the colorant.

The vehicle is mainly composed of a wax, and in addition, a mixture of a wax and a drying oil, resin, mineral oil, cellulose, rubber derivatives, or the like is used. The heat transferable color material layer made of heat meltable ink may contain a heat conductive material in order to give good heat conductivity and melt transferability. Examples of such a heat conductive material include carbonaceous materials such as carbon black, aluminum, copper, tin oxide, and molybdenum disulfide. Examples of the method for forming the heat transferable color material layer on the base film using the above hot melt ink include known methods such as hot melt coating, hot lacquer coating, gravure coating, gravure reverse coating, and roll coating. It is done. The coating amount of the heat transferable color material layer made of a heat-meltable ink can be appropriately determined in consideration of the required printing density, heat sensitivity, etc., and is usually 0.1 g / m ^{2 to} 30 g at the time of drying. / M ² .

  The heat transferable color material layer (dye layer) containing a sublimable dye is obtained by dispersing or dissolving a heat transferable dye in a binder resin. As the binder resin, those having a moderate affinity with the dye, and those in which the dye in the binder resin is sublimated (heat transferred) by heating with a thermal head, and transferred to the transfer target are good. Use resin that does not transfer. Examples of the resin used as such a binder resin include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose nitrate, cellulose acetate, and acetic acid / butyric acid cellulose, polyvinyl alcohol, and polyacetic acid. Examples thereof include vinyl resins such as vinyl, polyvinyl butyral, polyacrylamide, and polyvinyl pyrrolidone, polyester, and polyamide.

  The proportion of the dye contained in the heat transferable color material layer varies depending on the dye sublimation (melting) temperature, dyeing property, etc., but is preferably 30 parts by mass or more, more preferably 100 parts by mass of the binder resin. Is 30 to 300 parts by weight. When the amount of the dye is less than 30 parts by mass, the printing density and the thermal sensitivity are low, and when it exceeds 300 parts by mass, the storage property and the adhesion of the heat transferable color material layer to the base film are deteriorated.

  The dye used in the heat transferable color material layer is a dye which melts, diffuses or sublimates by heat and moves to the transfer target, and a disperse dye is particularly preferably used. The dye is selected in consideration of sublimation (melting) property, hue, light resistance, solubility in a binder resin, and the like. Examples of these dyes include methine series such as diarylmethane series, triarylmethane series, thiazole series, and merocyanine, indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, and azomethine series represented by pyridone azomethine. , Xanthene series, oxazine series, dicyanostyrene, cyanomethylene series represented by tricyanostyrene, thiazine series, azine series, acridine series, benzeneazo series, pyridoneazo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, Azos such as thiadiazole azo, triazole azo, disazo, spiropyran, indolinospiropyran, fluoran, rhodamine lactam, naphthoquinone, anthraquino Systems include the quinophthalone like.

In order to provide the heat transferable color material layer, which is a dye layer, on the base film, a known method can be used. For example, a dye and binder resin are dissolved or dispersed together with a solvent to prepare an ink composition for a heat transferable color material layer, which is provided on a base film by a method appropriately selected from known printing methods or coating methods. It ’s fine. The coating amount of the dye layer, dry with ^{0.2g / m 2 ~5.0g / m 2} , and preferably from the thickness of ^{0.4g / m 2 ~2.0g / m 2} .

  The heat-transferable color material layer described above is required to form at least two heat-transferable color material layers having different hues in the surface order on the base sheet, but two or more heat-transferable color material layers The conditions of the above are two or more dye layers using a sublimable dye, a combination of a dye layer and a heat transferable color material layer of heat-meltable ink, or two heat-transferable color material layers of heat-meltable ink. There may be more than one. In the present invention, in particular, a yellow color material layer, a magenta color material layer, and a cyan color material layer are formed in the surface order as a heat transferable color material layer containing a sublimation dye in the base sheet, and a high color comparable to a full color photographic image. It is preferable to form a clear image in which a quality thermal transfer image is formed and a shift in print length is prevented between hues in a full color thermal transfer image. In the case of a black character or pattern thermal transfer image, it is possible to obtain black by overlaying the above three colors of the yellow color material layer, magenta color material layer, and cyan color material layer of the dye layer. It is preferable that a color material layer made of black heat-meltable ink using a black colorant is added to the base sheet. As a result, a clear image having a high black density can be obtained.

(Primer layer)
Further, a primer layer 7 is provided between the base sheet and the heat transferable color material layer, between the release layer and the adhesive layer, and / or between the base sheet and the heat resistant slipping layer. It can also be formed by coating. The primer layer can be formed from a resin as shown below. Polyester resin, Polyacrylate resin, Polyvinyl acetate resin, Polyurethane resin, Styrene acrylate resin, Polyacrylamide resin, Polyamide resin, Polyether resin, Polystyrene resin, Polyethylene resin, Polypropylene Examples thereof include vinyl resins such as resins, polyvinyl chloride resins, polyvinyl alcohol resins, and polyvinylidene chloride resins, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, and cellulose resins. The primer layer can be formed by a method appropriately selected from known printing methods or coating methods, and the coating amount of the primer layer is 0.2 to 5.0 g / m ² , preferably 0. A thickness of 4 to 2.0 g / m ² is suitable.

  Among them, the primer layer provided between the release layer and the adhesive layer preferably contains ultrafine particles of a colloidal inorganic pigment. Examples of the ultrafine particles of colloidal inorganic pigment include, for example, metal silicates such as aluminum silicate and magnesium silicate; alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate thereof, Suspicious boehmite etc.), silica or silica sol, metal oxides such as magnesium oxide and titanium oxide; carbonates such as magnesium carbonate; and the like can be used. In the present invention, metal oxides and carbonates are preferable, metal oxides are more preferable, alumina or alumina hydrate is more preferable, and alumina sol is particularly preferable because of its high effect of imparting heat resistance and toughness. The primer layer may be composed of only one kind as the above-mentioned colloidal inorganic pigment ultrafine particles, or may be composed of two or more kinds as the above-mentioned colloidal inorganic pigment ultrafine particles. In any case, the colloidal inorganic pigment ultrafine particles used may be any material that does not have a phase transition temperature up to the instantaneous maximum heating temperature from the thermal head during printing.

  The average particle size of the colloidal inorganic pigment ultrafine particles is usually 100 nm or less, preferably 50 nm or less, particularly preferably 3 to 30 nm. The colloidal inorganic pigment ultrafine particles may be processed into an acidic type by adding a dispersion stabilizer such as hydrochloric acid or acetic acid for the purpose of facilitating dispersion in a sol form in an aqueous solvent. It may be one that has been subjected to surface treatment. The colloidal inorganic pigment ultrafine particles may be commercially available products such as alumina sol 100 (manufactured by Nissan Chemical Industries, Ltd.) and alumina sol 200 (manufactured by Nissan Chemical Industries, Ltd.).

The primer layer can be generally formed by applying an aqueous primer layer coating liquid containing colloidal inorganic pigment ultrafine particles onto a release layer of a substrate sheet and drying. The primer layer is more preferably formed using a sol-gel method. Since the primer layer forms a film without using a binder resin, the heat resistance and toughness of the protective layer can be imparted, and the adhesion to adjacent layers (peeling layer, adhesive layer) is good. It is. In addition, the formation method of said sol-gel method performs drying by exposing to 90-130 degreeC hot air etc. in a coating so that it may become a dry gel form from the sol state of a colloidal inorganic pigment ultrafine particle. The primer layer coating liquid can be prepared by dispersing colloidal inorganic pigment ultrafine particles in an aqueous medium. That is, examples of the aqueous medium in the primer layer coating liquid include water, a water-soluble alcohol such as isopropyl alcohol, a mixed liquid of water and a water-soluble alcohol, and the like. In the primer layer coating liquid, the colloidal inorganic pigment ultrafine particles are aqueous medium 1
It is preferable to contain 1-100 mass parts with respect to 00 mass parts.

Moreover, the primer layer containing the colloidal inorganic pigment ultrafine particles can be composed not only of the above-mentioned colloidal inorganic pigment ultrafine particles but also a water-soluble resin or an emulsifiable hydrophilic resin. . Specific examples of water-soluble resins include polyvinyl pyrrolidone resins, polyvinyl alcohol resins, hydrophilic urethane resins, hydroxylalkyl-substituted derivatives of cellulose, polyacrylamide, poly (meth) acrylic acid and metal salts thereof. The addition amount of the hydrophilic resin is preferably 0 to 50% by mass of the total solid content of the primer layer. In this case, the primer layer is formed by adjusting the above coating liquid and applying it by a known means such as a gravure printing method, a screen printing method, a reverse roll coating method using a gravure plate, and the like. can do. The primer layer in this case can be applied in an amount such that the coating amount after drying is 0.01 to 10 g / m ² , but it is applied after drying in terms of imparting excellent heat resistance, toughness and the like. it is preferred that the amount is applied in an amount of ^{0.05g / m 2 ~1.0g / m 2} .

  The protective layer is required to improve “rainbow unevenness” (a phenomenon in which rainbow-colored stripes appear in the flow direction of printing) in addition to the required performance for stabilization of peeling. By using the colloidal inorganic pigment ultrafine particles as described above for the primer layer between the release layer and the adhesive layer, there is an effect of further preventing the above-mentioned rainbow unevenness printing failure.

(Transfer material)
The protective layer transfer sheet of the present invention can transfer the protective layer to any transfer target as long as it is a transfer target capable of forming a thermal transfer image.
Examples of the material to be transferred include a structure in which a conventionally known (dye) receiving layer is provided on a base of various papers and plastic sheets, and dyeing of a dye such as a soft polyvinyl chloride resin. In the case of a material composed of a substrate having a property, the substrate alone can be used as a transfer target without providing a receiving layer. Examples of the above various papers include, for example, condenser paper, glassine paper, sulfuric acid paper, or high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality paper, art paper, coated paper, cast-coated paper, wallpaper, Examples thereof include backing paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin-added paper, paperboard, cellulose fiber paper, and the like.

  Examples of the various plastic sheets include polyester, polyacrylate, 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, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene , Polychlorotrifluoroethylene, polyvinylidene fluoride, etc., and their synthesis White opaque sheet was formed by adding white pigments and fillers to fat (film) or a porous sheet (film) having minute voids (microvoids) inside the substrate can be used is not particularly limited.

  Moreover, the laminated body by arbitrary combinations of the base material of said paper or a plastic sheet can also be used. Examples of typical laminates include a laminate of cellulose fiber paper and synthetic paper or cellulose fiber paper and a plastic sheet. The thickness of the transferred material can be arbitrarily selected, and is usually about 10 to 300 μm.

Next, an Example and a comparative example are given and this invention is further explained in full detail. In the text, “part” or “%” is based on mass unless otherwise specified. The mass average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).
Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, parts or% is based on mass.

<Synthesis Example 1: Synthesis of Dispersant 1>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate were added and stirred, and the polymerization apparatus While the inside was replaced with nitrogen, the temperature was raised to a polymerization temperature of 50 ° C., 0.02 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the polymerization temperature was further raised to 60 ° C. The temperature rose. Simultaneously with the addition of the polymerization initiator, methyl methacrylate was continuously added dropwise at a rate of 0.24 parts / minute for 75 minutes using a dropping pump, maintained at a polymerization temperature of 60 ° C. for 6 hours, and then cooled to room temperature. Thus, a dispersant 1 having a solid content of 10%, which is a transparent polymer aqueous solution, was obtained.

<Production Example 1: Production of acrylic copolymer resin 1 for release layer>
In a polymerization apparatus equipped with a stirrer, a condenser tube, and a thermometer, 145 parts of deionized water, 0.5 part of sodium sulfate, and 0.2 part of dispersant 1 (solid content 10%) were added and stirred. An aqueous solution was obtained. Next, 99.5 parts of methyl methacrylate, 0.5 part of methacrylic acid, 1.4 parts of 2-ethylhexyl thioglycolate, 0.3 part of 2,2′-azobis (2-methylbutyronitrile) are added, and aqueous A suspension was obtained. Next, the inside of the polymerization apparatus was replaced with nitrogen, the polymerization temperature was raised to 75 ° C., and the reaction was carried out for about 1.5 hours. In order to further increase the polymerization rate, the post-treatment temperature was raised to 95 ° C. and held for 30 minutes. Then, it cooled to 40 degreeC and obtained the aqueous suspension containing a granular polymer. The aqueous suspension was filtered through a nylon filter cloth having an opening of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain an acrylic copolymer resin 1. The acrylic copolymer resin 1 had a mass average molecular weight (Mw) of 24,800.

<Production Examples 2 to 6: Production of acrylic copolymer resins 2 to 6 for release layer>
Acrylic copolymer resins 2 to 6 were obtained in the same manner as the acrylic copolymer resin 1 except that the monomers shown in Table 1 were used in the proportions shown in Table 1. The obtained mass average molecular weight results are shown in Table 1.

( Reference Example 1)
The following heat-resistant slipping layer coating solution is applied to one surface of a 6 μm-thick polyethylene terephthalate long film (Lumirror, manufactured by Toray Industries, Inc.) using a gravure coater as a solid content 1 A heat resistant slipping layer was formed by applying and drying at a rate of 0.0 g / m ² .
<Coating fluid for heat resistant slipping layer>
13.6 parts of polyvinyl butyral resin (manufactured by SREC BX-1 by Sekisui Chemical Co., Ltd.)
0.6 parts of polyisocyanate curing agent (Takenate D218, manufactured by Mitsui Chemicals Polyurethanes)
Phosphate 0.8 parts (Pricesurf A208N, Daiichi Kogyo Seiyaku Co., Ltd.)
Methyl ethyl ketone 42.5 parts Toluene 42.5 parts

Next, an ink having the following composition is applied on the surface opposite to the surface on which the heat-resistant slip layer of the substrate sheet is formed, and a dye layer is formed with three colors as one set. A heat transferable color material layer was formed. The coating amount of the dye layer is 1.0 g / m ² when all three colors are dried.

<Composition of ink for yellow dye layer>
5.5 parts of dye (FORON BRILLIANT YELLOW S-6GL)
Polyvinyl acetal resin 4.5 parts (trade name KS-5: manufactured by Sekisui Chemical Co., Ltd.)
Polyethylene wax 0.1 part Solvent (toluene: methyl ethyl ketone = 1: 1 mass ratio) 89 parts

<Composition of magenta dye layer ink>
Dye 1 1.5 parts (MS RED-G)
Dye 2 2.0 parts (MACROLEX RED VIORET R)
Polyvinyl acetal resin 4.5 parts (trade name KS-5: manufactured by Sekisui Chemical Co., Ltd.)
Polyethylene wax 0.1 part Solvent (toluene: methyl ethyl ketone = 1: 1 mass ratio) 89 parts

<Composition of cyan dye layer ink>
Dye 1.5 parts (Kaya Set Blue 714)
Polyvinyl acetal resin 4.5 parts (trade name KS-5: manufactured by Sekisui Chemical Co., Ltd.)
Polyethylene wax 0.1 part Solvent (toluene: methyl ethyl ketone = 1: 1 mass ratio) 89 parts

Next, between each set of the above dye layers, the following release layer coating liquid is applied with a gravure coater so that the coating amount after drying is 1.0 g / m ^2. Formed.
<Coating liquid for release layer>
The release layer coating solution for release layer is obtained by dissolving the acrylic copolymer resin 1 for release layer obtained in the above production example in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content is 20% by mass. Was made.

On said release layer by coating with a gravure coater adhesive layer coating solution having the following, as coating amount after drying is 1.0 g / m ^2, to form an adhesive layer, reference The protective layer transfer sheet of Example 1 was produced. (The arrangement of the protective layer and the heat transferable color material layer is the same as that shown in FIG. 1.)
<Coating liquid for adhesive layer>
50 parts of vinyl chloride-vinyl acetate copolymer (Solvine CNL, manufactured by Nissin Chemical Industry Co., Ltd.)
Toluene 50 parts Methyl ethyl ketone 50 parts

( Reference Example 2)
A protective layer transfer sheet of Reference Example 2 was prepared in the same manner as Reference Example 1, except that the coating liquid for the release layer of the protective layer transfer sheet of Reference Example 1 was changed to the following coating liquid.
<Coating liquid for release layer>
The release layer coating solution was prepared by dissolving the release layer acrylic copolymer resin 2 in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content was 20% by mass.

(Example 3)
A protective layer transfer sheet of Example 3 was produced in the same manner as Reference Example 1, except that the coating liquid for the release layer of the protective layer transfer sheet of Reference Example 1 was changed to the following coating liquid.
<Coating liquid for release layer>
The release layer coating solution was prepared by dissolving the release layer acrylic copolymer resin 3 in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content was 20% by mass.

(Comparative Example 1)
A protective layer transfer sheet of Comparative Example 1 was produced in the same manner as Reference Example 1 except that the release layer of the protective layer transfer sheet of Reference Example 1 was changed to the following coating solution.
<Coating liquid for release layer>
The release layer coating solution was prepared by dissolving the release layer acrylic copolymer resin 4 in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content was 20% by mass.

(Comparative Example 2)
A protective layer transfer sheet of Comparative Example 2 was produced in the same manner as Reference Example 1, except that the release layer of the protective layer transfer sheet of Reference Example 1 was changed to the following coating solution.
<Coating liquid for release layer>
The release layer coating solution was prepared by dissolving the release layer acrylic copolymer resin 5 in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content was 20% by mass.

(Comparative Example 3)
A protective layer transfer sheet of Comparative Example 3 was produced in the same manner as Reference Example 1, except that the release layer of the protective layer transfer sheet of Reference Example 1 was changed to the following coating solution.
<Coating liquid for release layer>
The release layer coating solution was prepared by dissolving the release layer acrylic copolymer resin 6 in a solvent (toluene: methyl ethyl ketone = 1: 1) so that the solid content was 20% by mass.

[Evaluation]
The following evaluation was performed about the protective layer transfer sheet produced in the said Example and comparative example.
(Peeling power)
Receiving a protective layer composed of a release layer and an adhesive layer of the protective layer transfer sheet prepared in the above examples and comparative examples, an image receiving sheet for thermal transfer (an image receiving sheet for Canon compact photo printer CP710 cut into an arbitrary size) On the layer, using a test printer, a “sample with both adhered” was prepared by transferring under the following conditions, and the peeling force was measured under the following conditions.
The evaluation criteria were as follows.
○: Peeling force of less than 30 Δ: Peeling force of 30 or more ×: Measurement impossible (caused by ribbon sticking / cohesive failure)

<Printing conditions>
-Heating element average resistance: 4858Ω
Print density in the main scanning direction: 300 dpi, printing density in the sub-scanning direction: 300 dpi
・ Printing voltage: 18.5V
・ One line cycle; 2msec / line
・ Printing start temperature: 27 ℃
・ Print width: 3cm
-Applied pulse (gradation control method); using a multi-pulse test printer that can vary the number of divided pulses from 0 to 255 in one line period and having a pulse length obtained by equally dividing one line period into 256, The duty ratio of each divided pulse was fixed to 90%, and the protective layer was heated under the condition of 220 pulses ((gradation)) to form a protective layer on the transferred body, provided that the transferred body and the protective layer The transfer sheet is a sample in a state of being overlapped and bonded and integrated, that is, a sample in which the protective layer transfer sheet is not peeled off from the transfer target.

<Peeling conditions>
Using the sample to which the transferred body and the protective layer transfer sheet were bonded, the peeling force when peeling the protective layer transfer sheet from the transferred body was measured with the following apparatus. .
・ Peeling device: Instron's universal material testing machine 5565
・ Peeling speed: 300 mm / min

(Adhesion evaluation)
90 ° direction after tape (Post It (trademark), 3M) is bonded to the protective layer consisting of the release layer and adhesive layer of the protective layer transfer sheet prepared in the above examples and comparative examples and rubbed several times with fingers. Was peeled at a speed of 0.6 m / min. The adhesion of the protective layer was confirmed visually, and the evaluation criteria were as follows.
◎: No peeling ○: There is no peeling trace, but there is a deposit on the tape ×: The peeling trace is clear

(Plasticizer resistance)
Using the protective layer transfer sheets of Examples and Comparative Examples, the protective layer was transferred to the transfer material on which the thermal transfer image was formed under the following conditions, and the image surface of the printed material transferred with the protective layer and the plasticizer A soft vinyl chloride sheet (Mitsubishi Chemical Co., Ltd., Altron # 480, thickness 400 μm) was placed on top of each other, applied to a load of 40 g / cm ² and stored in a 50 ° C. environment for 48 hours. Thereafter, the deterioration of the image by the plasticizer was visually evaluated according to the following evaluation criteria.
○: No image transfer to the vinyl chloride sheet was observed.
Δ: Partial transfer of the image to the vinyl chloride sheet was observed.
X: Transfer of the image to the vinyl chloride sheet was observed throughout.

<Printing conditions>
-Heating element average resistance: 4858Ω
Print density in the main scanning direction: 300 dpi, printing density in the sub-scanning direction: 300 dpi
・ Printing voltage: 18.5V
・ One line cycle; 2msec / line
・ Printing start temperature: 27 ℃
・ Print width: 3cm
-Applied pulse (gradation control method); using a multi-pulse test printer that can vary the number of divided pulses from 0 to 255 in one line period and having a pulse length obtained by equally dividing one line period into 256, The duty ratio of each divided pulse is fixed to 90%, and each color of yellow, magenta, and cyan is transferred in this order to the receiving surface of the transfer target to form a black image. The protective layer was transferred and formed by printing with 255 pieces. In addition, the black image by yellow, magenta, and cyan and the protective layer transfer were performed using the protective layer transfer sheet produced in each Example and the comparative example.

(Abrasion resistance)
The printing conditions were the same as in the evaluation of plasticizer resistance, and the protective layer was transferred to the transfer target on which the thermal transfer image was formed, using the protective layer transfer sheets of Examples and Comparative Examples. The abrasion resistance test on the image surface of the printed material transferred with the protective layer was performed under the following conditions.
Thereafter, the deterioration of the image by the plasticizer was visually evaluated according to the following evaluation criteria.
○: Image destruction is not observed.
Δ: Some image destruction was observed.
X: Image destruction was observed throughout.

<Abrasion resistance test conditions>
Using the sample on which the black image and the protective layer were transferred, an abrasion resistance test was performed under the following conditions.
・ Evaluation equipment: Gakshin (Gakushin) tester ・ Evaluation conditions: Cotton cloth, load 200 g, repeated 100 times (30 times / min)

The protective layer transfer sheets of Reference Examples 1, 2 and Example 3 can suppress the peeling force even when the energy applied during the transfer of the protective layer is increased, and there is no defective transfer of the protective layer. Indicates that it is possible. In addition, by using the protective layer transfer sheets of Reference Examples 1 and 2 and Example 3, it is possible to obtain an image-formed product with improved wear resistance and suppression of deterioration due to the plasticizer, especially compared to the conventional case. Show. Further, the adhesiveness of the protective layer transfer sheet of Example 3 was particularly good.
On the other hand, in the protective layer transfer sheets of Comparative Examples 1 and 2, when the energy applied during the transfer of the protective layer is increased, the peeling failure of the protective layer transfer due to an increase in the peeling force between the base sheet and the peeling layer occurs. Show. Furthermore, it was also shown that when the protective layer transfer sheets of Comparative Examples 1 and 2 were used, the abrasion resistance was insufficient and the image of the printed matter was deteriorated by the plasticizer. Further, it was found that the protective layer transfer sheet of Comparative Example 3 had a problem in adhesion.

It is a schematic sectional drawing which shows one Embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment of the protective layer transfer sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Protective layer transfer sheet 2 Base material sheet 3 Peeling layer 4 Adhesive layer 5 Heat resistant slipping layer 6 Protective layer 7 Primer layer Y Yellow dye layer M Magenta dye layer C Cyan dye layer BK Black hot melt ink layer

Claims (2)

One side of the base sheet has a heat resistant slipping layer, and a protective layer capable of thermal transfer is provided on at least a part of the base sheet opposite to the side where the heat resistant slipping layer is provided. and the protective layer transfer sheet, the protective layer is peeled off layer from the substrate sheet side, includes an adhesive layer sequentially, the release layer, main methacrylic acid ester (a) (meth) acrylic acid ester acrylic acid (b) copolymerizing an acrylic copolymer resins comprising the (c) containing as a main component,
Prior Symbol methacrylate (a) and (meth) acrylic copolymer resin obtained by copolymerizing an acrylic acid (b) acrylic acid ester (c), the (meth) acrylic acid (b) is 0.1 A protective layer transfer sheet comprising ˜1% by mass and the acrylic ester (c) in a range of 0.1 to 8% by mass.   In the acrylic copolymer resin obtained by copolymerizing the methacrylic acid ester (a), the (meth) acrylic acid (b), and the acrylic acid ester (c), the methacrylic acid ester (a) is 91 to 99% by mass, The said (meth) acrylic acid (b) is 0.1-1 mass%, and the said acrylic acid ester (c) is contained in the range of 0.1-8 mass%, It is characterized by the above-mentioned. Protective layer transfer sheet.