JP2005104043A - Thermal transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (hologram) thermal transfer sheet excelling in slipperiness in relation to an image receiving sheet on the occasion of thermal transfer and preventing conveyance troubles, so as to eliminate the conveyance trouble that the (hologram) thermal transfer sheet and the image receiving sheet stick to each other and cause a jam or the like and this wrinkles the (hologram) thermal transfer sheet, on the occasion when the (hologram) thermal transfer sheet is combined with the the image receiving sheet and a hologram or a metal vapor deposition layer is thermally transferred onto the image receiving sheet by a thermal head. <P>SOLUTION: In the (hologram) thermal transfer sheet 1 wherein a peeling layer 3, the metal vapor deposition layer 5 and an adhesive layer 6, or the peeling layer 3, a relief forming layer 4, the metal vapor deposition layer 5 and the adhesive layer 6, are formed in these sequences on a base sheet 2, the adhesive layer 6 contains a filler by 0.5-40% (on a mass basis) to the total solid content of the adhesive layer 6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermal transfer sheet that can thermally transfer characters, patterns, and the like having a metallic feeling such as metallic luster, and more particularly to a hologram thermal transfer sheet that can transfer a hologram having metallic luster.

  Conventionally, transfer foils having relief structures such as holograms and diffraction gratings can express unique decorative images and stereoscopic images, and these holograms and diffraction gratings require advanced manufacturing techniques and cannot be easily manufactured. It is used to prevent counterfeiting. For example, credit cards, ID cards, prepaid cards and other cards, which cannot be reproduced with color copies, can be transferred to gift certificates, checks, bills, stock certificates, admission tickets, paper certificates such as various certificates, etc. ing. Furthermore, due to its unique design, it is often used for packaging materials, books, pamphlets, POPs, and the like.

  As a means for attaching a relief structure such as a hologram or a diffraction grating to an article, a transfer printing method using a transfer foil is known. The transfer foil is formed by sequentially laminating a release layer, a relief forming layer in which a pattern such as a hologram or a diffraction grating is formed on a substrate, a reflective layer, and an adhesive layer. As a method for transfer printing of the transfer foil, a hot stamp (also called foil stamping) or a heat transfer using a heating roll is generally used.

  It is also known that a relief structure such as a hologram is formed by thermal transfer with a thermal head using a hologram thermal transfer sheet provided so as to be transferable from a substrate. For example, Patent Document 1 describes a structure in which a release layer, a resin layer on which a light diffraction structure is formed, and an adhesive layer are sequentially laminated on a base sheet. Since such a thermal head can be formed by thermally transferring a hologram in an arbitrary pattern, the hologram is thermally transferred and formed on a printed material on which a color image has been formed by a sublimation transfer method or a hot melt transfer method. .

  The thermal transfer sheet on which a hologram or a metal vapor deposition layer can be thermally transferred by the thermal head described above is used in an embossing (heating press) process to form an optical diffraction structure, and in the reflective layer formation, a vacuum vapor deposition method or a sputtering method is used. Manufactured using a special process of the thin film method. As described above, the thermal transfer sheet used in the sublimation transfer method and the thermal melt transfer method is manufactured in a different process. Therefore, the thermal transfer sheet used in the sublimation transfer method and the thermal melt transfer method, the hologram thermal transfer sheet and the transfer property. A thermal transfer sheet having a metal vapor deposition layer (hereinafter abbreviated as a hologram thermal transfer sheet) is used as a single thermal transfer sheet on the same substrate sheet, a colored transfer layer for sublimation transfer or thermal fusion transfer, a hologram transfer layer, transferability It is difficult to provide a metal vapor deposition layer.

Therefore, prepare a thermal transfer sheet for hologram transfer and a thermal transfer sheet for sublimation transfer or thermal melt transfer separately, and use a thermal transfer printer with two or more thermal heads to transfer thermal transfer images with one thermal head. Form and transfer the hologram or metal deposition layer with another thermal head to obtain an image formed product, or use two thermal transfer printers, sublimation transfer or thermal melt transfer with the first printer An image-formed product is obtained by forming a thermal transfer image and transferring a hologram or a metal vapor deposition layer with a second printer.
When a hologram thermal transfer sheet or the like is used by various methods as described above, a hologram or a metal vapor deposition layer is thermally transferred to the image receiving sheet by a thermal head. There is a problem that the image receiving sheet sticks and is transported without being peeled off, causing jamming or wrinkling on the hologram thermal transfer sheet or the like. As the cause of this, it is conceivable that the slidability of both the hologram thermal transfer sheet and the image receiving sheet is poor, and static electricity is generated in both. Various attempts have been made to improve the hologram thermal transfer sheet and the image receiving sheet in order to prevent this conveyance trouble, but there is no situation where a sufficient effect can be obtained.

  Therefore, in order to solve the above problems, the present invention combines a hologram thermal transfer sheet or the like and an image receiving sheet, and when transferring a hologram or a metal vapor deposition layer to the image receiving sheet by a thermal head, the hologram thermal transfer sheet or the like Hologram that has excellent slipperiness with respect to the image receiving sheet during thermal transfer and prevents conveyance troubles in order to eliminate problems such as jamming between the image receiving sheet and the image receiving sheet, and wrinkles on the hologram thermal transfer sheet. An object is to provide a thermal transfer sheet or the like.

  The invention according to claim 1 is a thermal transfer sheet in which a release layer, a metal vapor deposition layer, and an adhesive layer are formed in this order on a base sheet, and a filler is added to the adhesive layer with respect to the total solid content of the adhesive layer. It was set as the structure containing 0.5 to 40% (mass basis).

  The invention according to claim 2 is a hologram thermal transfer sheet in which a release layer, a relief forming layer, a metal vapor deposition layer, and an adhesive layer are formed in this order on a base material sheet. It was set as the structure containing 0.5 to 40% (mass basis) with respect to minutes.

  According to a third aspect of the present invention, a thermal transfer image is formed on an image receiving sheet from a thermal transfer sheet having a thermal transfer dye layer and / or a heat-fusible thermal transfer layer containing a sublimation dye by a first thermal head, and then the second thermal head. A thermal transfer recording comprising: using the thermal transfer sheet according to claim 1 or 2 to produce an image-formed product by thermally transferring a hologram or a metal vapor-deposited layer to an image-receiving sheet on which a thermal transfer image is formed. Is the method.

  According to a fourth aspect of the present invention, a serial thermal transfer printer is used to thermally transfer a hologram or a metal vapor-deposited layer on an image receiving sheet using the thermal transfer sheet according to the first or second aspect, thereby creating an image formed product. This is a thermal transfer recording method.

  In the thermal transfer sheet of the present invention, a release layer, a metal deposited layer, and an adhesive layer are formed on a base sheet in this order, or a release layer, a relief forming layer, a metal deposited layer, and an adhesive layer are formed in this order. Thus, the adhesive layer contains a filler in an amount of 0.5 to 40% (mass basis) with respect to the total solid content of the adhesive layer, so that the adhesive layer has an appropriate slip property with respect to the image receiving sheet. When the hologram or the metal vapor deposition layer was thermally transferred to the image receiving sheet by the head, it was possible to eliminate the conveyance trouble that the thermal transfer sheet and the image receiving sheet were stuck to each other or wrinkles were generated on the thermal transfer sheet.

  In the thermal transfer recording method of the present invention, a thermal transfer image is formed on an image receiving sheet from a thermal transfer sheet having a sublimation dye-containing thermal transfer dye layer and / or a heat-fusible thermal transfer layer by a first thermal head, and thereafter Using the thermal transfer sheet according to claim 1 or 2 with the thermal head of 2, the hologram or the metal vapor deposition layer was thermally transferred to the image receiving sheet on which the thermal transfer image was formed to produce an image formed product. As a result, an image is formed by transferring the colorant from the thermal transfer dye layer and / or the heat-meltable thermal transfer layer to the image receiving sheet with the first thermal head, and the image forming surface of the image receiving sheet is charged with a lot of static electricity. Even under the conditions, since the filler is contained in the adhesive layer in an amount of 0.5 to 40% (mass basis) with respect to the total solid content of the adhesive layer, the hologram or the metal deposition layer is thermally transferred to the image receiving sheet with the second thermal head. In this case, it was possible to prevent a conveyance trouble such as the thermal transfer sheet and the image receiving sheet sticking or wrinkles on the thermal transfer sheet. The thermal transfer recording method of the present invention uses a serial thermal transfer printer to produce an image formed product by thermally transferring a hologram or a metal vapor deposition layer to an image receiving sheet using the thermal transfer sheet according to claim 1 or 2. To do. As a result, the adhesive layer contains a filler of 0.5 to 40% (mass basis) with respect to the total solid content of the adhesive layer, so the hologram or metal vapor deposition layer is thermally transferred to the image receiving sheet with a serial type thermal head. In this case, it is possible to prevent a conveyance trouble that the thermal transfer sheet and the image receiving sheet are adhered to each other or the thermal transfer sheet is wrinkled.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic sectional view showing one embodiment which is a hologram thermal transfer sheet of the present invention. The illustrated hologram thermal transfer sheet 1 is obtained by sequentially laminating a release layer 3, a relief forming layer 4, a metal vapor deposition layer 5, and an adhesive layer 6 on one surface of a substrate sheet 2. FIG. 2 is a schematic sectional view showing another embodiment which is a hologram thermal transfer sheet of the present invention. In the illustrated hologram thermal transfer sheet 1, a release layer 3, a relief forming layer 4, a metal vapor deposition layer 5, and an adhesive layer 6 are sequentially laminated on one surface of a substrate sheet 2, and heat resistance is applied to the other surface of the substrate sheet 2. The protective layer 7 is provided. In addition, it is also possible to set it as the thermal transfer sheet | seat made into the structure of the base material sheet 2 / peeling layer 3 / metal vapor deposition layer 5 / adhesion layer 6 except the relief formation layer 4 in FIG.

Hereinafter, each layer constituting the thermal transfer sheet will be described in detail.
[Base material sheet]
The base sheet 2 of the present invention can be made of various materials depending on the use as long as it has heat resistance, mechanical strength, mechanical strength, solvent resistance, etc. that can withstand the heat of the thermal head. Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene naphthalate coextruded film And polyamide resins, vinyl resins such as polyvinyl chloride, acrylic resins, imide resins, engineering resins such as polyarylate, and cellulose films such as polycarbonate and cellophane.

  The base sheet may be a copolymer resin containing these resins as a main component, a mixture (including alloy), or a laminate composed of a plurality of layers. The base sheet may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable for the purpose of improving strength. The thickness of the base sheet is usually about 2.5 to 50 μm, preferably 2.5 to 12 μm, and most preferably 4 to 6 μm. If the thickness is larger than this, the heat transfer of the thermal head becomes worse. Below this, the mechanical strength is insufficient.

The base sheet is used as a film, sheet or board comprising at least one layer of these resins. Usually, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their good heat resistance and mechanical strength, and polyethylene terephthalate is most suitable. Prior to application, the base sheet is subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) application treatment, pre-heat treatment, dust removal. Easy adhesion treatment such as treatment, vapor deposition treatment, and alkali treatment may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, as needed.
[Peeling layer]
In the thermal transfer sheet of the present invention, a relief forming layer, a metal vapor deposition layer, and an adhesive layer are sequentially laminated on a base sheet via a release layer 3. The release layer 3 is appropriately bonded to the base sheet by adding a thermoplastic resin to the ionizing radiation curable resin as necessary, and cured with ionizing radiation, and from the base sheet when the thermal head is thermally loaded. It is easily peeled off and transferred to a transfer medium (image receiving sheet). Also, as the release layer material, use a combination of thermoplastic resins such as acrylic, polyester, urethane, epoxy, norbornene, etc. that have appropriate adhesiveness to the base sheet and release properties, and thermoplastic resins with different characteristics. Also good.

  That is, the release layer does not drop off due to vibration or impact during transportation, handling, or mounting operation of the thermal transfer sheet, and the base sheet is easily removed during thermal transfer of the hologram (relief formation layer) or metal deposition layer. It functions so that it can be peeled off and transferred. When the adhesive strength to the base material sheet is insufficient, the relief forming layer or the metal vapor deposition layer falls off due to vibration and impact during transportation and handling of the thermal transfer sheet and mounting operation on the printer. Alternatively, when the thermal transfer is performed by the thermal head, an unnecessary transfer portion remains in a portion adjacent to the heating portion, and so-called burrs are generated. In addition, when the content of the thermoplastic resin is too large, the adhesive force to the base sheet is too good, so that it cannot be transferred without peeling from the base sheet at the time of thermal transfer.

  As the ionizing radiation curable resin constituting the release layer, the same resin as the ionizing radiation curable resin constituting the relief forming layer described later is used, and as a thermoplastic resin to be added as necessary, polyolefin such as polypropylene is used. Resin, vinyl halide resins such as polyvinyl chloride and polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins and polyamide resins Examples thereof include resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, cellulose resins such as ionomers and cellulose diacetate.

As described above, the release layer is prepared by dissolving or dispersing an ionizing radiation curable resin and, if necessary, a material added with a thermoplastic resin, a release agent, a coupling agent, a photopolymerization initiator, etc. in an appropriate solvent. Thus, a coating solution is prepared, and this coating solution is applied and dried by a conventional coating means such as a gravure coater, a roll coater, or a wire bar. The thickness of the release layer is usually about 0.1 to 10 g / m ² , preferably 0.2 to 5 g / m ² in a dry state.
[Relief forming layer]
The relief forming layer 4 is mainly composed of an ionizing radiation curable resin. As the ionizing radiation curable resin, for example, epoxy-modified acrylate resin, urethane-modified acrylate resin, acrylic-modified polyester and the like can be applied, preferably urethane-modified acrylate resin, particularly urethane-modified acrylic resin represented by the following general formula Is preferred.

ここで、６個のＲ₁は夫々互いに独立して水素原子またはメチル基を表わし、Ｒ₂は炭素数が１〜１６個の炭化水素基を表わし、ＸおよびＹは直鎖状または分岐鎖状のアルキレン基を表わす。ｌ、ｍ、ｎ、ｏ及びｐの合計を１００とした場合に、ｌは２０〜９０、ｍは０〜８０、ｎは０〜５０、ｏ＋ｐは１０〜８０、ｐは０〜４０の整数である。

Here, six R _{1 s} each independently represent a hydrogen atom or a methyl group, R ₂ represents a hydrocarbon group having 1 to 16 carbon atoms, and X and Y are linear or branched. Represents an alkylene group. When the total of l, m, n, o and p is 100, l is an integer from 20 to 90, m is from 0 to 80, n is from 0 to 50, o + p is from 10 to 80, and p is an integer from 0 to 40. is there.

  The urethane-modified acrylic resin represented by the above formula includes, for example, methyl methacrylate 20-90 mol, methacrylic acid 0-50 mol, 2-hydroxyethyl methacrylate 10-80 mol, and Z as isobornyl methacrylate. A resin obtained by copolymerizing 0 to 80 mol, and obtained by reacting a hydroxyl group present in the copolymer with methacryloyloxyethyl isocyanate (2-isocyanate ethyl methacrylate) It is.

  Therefore, the methacryloyloxyethyl isocyanate need not react with all the hydroxyl groups present in the copolymer, preferably at least 10 mol% or more of the hydroxyl groups of 2-hydroxyethyl methacrylate units in the copolymer. It is sufficient that 50 mol% or more is reacted with methacryloyloxyethyl isocyanate. Instead of or in combination with the above 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Monomers having a hydroxyl group such as 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate can also be used.

  As described above, by using a hydroxyl group present in a hydroxyl group-containing acrylic resin, a resin composition mainly composed of a urethane-modified acrylic resin in which a number of methacryloyl groups are introduced into the molecule, for example, diffraction. When forming a lattice or the like, ionizing radiation such as ultraviolet rays or electron beams can be used as a curing means, and a diffraction lattice or the like excellent in flexibility and heat resistance can be formed while having a high crosslinking density.

The urethane-modified acrylic resin represented by the above formula is dissolved in a solvent capable of dissolving the copolymer, for example, a solvent such as toluene, ketone, cellosolve acetate, dimethyl sulfoxide, and the like while stirring. By dropping and reacting methacryloyloxyethyl isocyanate, the isocyanate group reacts with the hydroxyl group of the acrylic resin to form a urethane bond, and the methacryloyl group can be introduced into the resin through the urethane bond. The amount of methacryloyloxyethyl isocyanate used in this case is in the range of 0.1 to 5 moles, preferably 0.5 to 3 moles of isocyanate groups per mole of hydroxyl groups based on the ratio of hydroxyl groups to isocyanate groups of the acrylic resin. Amount. When methacryloyloxyethyl isocyanate having an equivalent amount or more than the hydroxyl group in the resin is used, the methacryloyloxyethyl isocyanate also reacts with a carboxyl group in the resin to form a —CONH—CH ₂ CH ₂ — linkage. It can happen.

  Z in the above formula can be introduced to modify the above urethane-modified acrylic resin. For example, a monomer having an aromatic ring such as phenyl group or naphthyl group or a heteroaromatic ring such as pyridine, ) Silicone oil (resin) having polymerizable double bond groups such as acryloyl modified silicone oil (resin), vinyl modified silicone oil (resin), long chain alkyl groups such as lauryl (meth) acrylate, stearyl (meth) acrylate Monomer having silicon-containing group such as γ- (meth) alkoxypropyltrimethoxysilane, fluorine-containing group such as 2- (perfluoro-7-methyloctyl) ethyl acrylate, heptadecafluorodecyl (meth) acrylate Monoborn imparting releasability, such as a monomer having Monomers having a bulky structure such as (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, EO-modified dicyclopentenyl (meth) acrylate, acryloylmorpholine, Any monomer having a cyclic hydrophilic group such as vinyl pyrrolidone or vinyl caprolactone can be used.

The above examples are cases where, in the above general formula, all R ₁ and R ₂ are methyl groups, and X and Y are ethylene groups, but the present invention is not limited to these, and 6 R ₁ may independently be a hydrogen atom or a methyl group, and specific examples of R ₂ include, for example, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert- Examples thereof include a butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and specific examples of X and Y include an ethylene group, a propylene group, a diethylene group, and a dipropylene group. As the total molecular weight of the urethane-modified acrylic resin used in the present invention thus obtained, the average molecular weight in terms of standard polystyrene measured by GPC is 10,000 to 200,000, and more preferably 2 to 40,000. preferable.

  Furthermore, in order to adjust the flexibility and viscosity of the ionizing radiation curable resin layer (relief-forming layer) after curing, in the present invention, the ionizing radiation curable resin may be replaced with a normal thermoplastic resin, acrylic or other simple substance. Functional or polyfunctional monomers, oligomers and the like can be included. For example, monofunctional (mono) methacrylates such as tetrahydrofurfuryl (meth) acrylate are monofunctional, and bifunctional and higher functional polyols such as epoxy-modified polyol (meth) acrylate and lactone-modified polyol (meth) acrylate are ) Acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, other polybutadiene, isocyanuric acid, hydantoin, melamine, phosphoric acid, imide, phosphazene, etc. Various monomers, oligomers, and polymers that are poly (meth) acrylates that are ultraviolet and electron beam curable can be used.

  The number of functional groups is not particularly limited, but if the number of functional groups is less than 3, the heat resistance tends to decrease, and a part of the relief forming layer is scratched or the relief surface becomes cloudy. Since there exists a tendency for a softness | flexibility to fall in the above, a 3-20 functional thing is especially preferable.

  A plurality of the monomers or oligomers may be used in combination. The amount used is in the range of 5 to 90 parts by mass, preferably 10 to 70 parts by mass, per 100 parts by mass of the urethane-modified acrylic resin. If the amount of the monomer or oligomer used is less than the above range, it cannot be said that the strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to the base sheet of the ionizing radiation curable resin layer obtained are sufficient, On the other hand, when the amount of the monomer or oligomer used exceeds the above range, the surface tack becomes high, causing blocking, or a part of the material remains on the plate (press stamper) during relief replication such as a relief hologram or diffraction grating ( This phenomenon is not preferable in that the phenomenon that a person skilled in the art calls plate printing), the repeated relief replication (embossing), and the like are lowered.

  Further, when a relief is formed (replicated) on the ionizing radiation curable resin layer (relief forming layer), a stamper (metal plate or resin plate) having an uneven relief formed on the surface is formed on the relief forming layer. The unevenness relief is formed (replicated) on the relief forming layer by pressure bonding. At this time, a release agent may be added to the relief forming layer in advance so that the stamper can be easily peeled off from the relief forming layer. As the release agent, known release agents can be applied, for example, solid waxes such as polyethylene wax, amide wax, Teflon (registered trademark) powder, fluorine-based, phosphate-based surfactant, silicone, and the like. Particularly preferably, the release agent is a modified silicone. Specifically, modified silicone oil side chain type, modified silicone oil both end type, modified silicone oil one end type, modified silicone oil side chain both end type, methylpolysiloxane containing trimethylsiloxysilicate (referred to as silicone resin) ), Silicone graft acrylic resin, and methylphenyl silicone oil.

  Among the above silicone oils, the reactive silicone oil reacts with the resin when it is cured with ionizing radiation, and is combined and integrated. Therefore, it does not bleed out on the surface of the relief forming layer on which relief irregularities are formed later. This characteristic performance can remarkably improve the adhesion between the relief forming layer and the metal vapor deposition layer provided on the relief surface. The amount of the release agent used is in the range of about 0.1 to 50 parts by mass, preferably in the range of about 0.5 to 10 parts by mass, per 100 parts by mass of the ionizing radiation curable resin. If the usage-amount of a mold release agent is less than the said range, peeling with a press stamper and an ionizing radiation cured resin layer is inadequate, and it is difficult to prevent the contamination of a press stamper. On the other hand, if the amount of the release agent used exceeds the above range, the coating surface is roughened during coating of the composition, the coating surface becomes rough, the adhesion with the substrate sheet or the metal deposition layer deteriorates, or thermal transfer Since the film of the relief forming layer sometimes causes destruction (film strength becomes too weak), it is not preferable.

  Furthermore, in order to improve the heat resistance, the film strength, and the adhesion with the metal vapor deposition layer of the ionizing radiation curable resin layer (relief forming layer) after curing, the ionizing radiation curable resin is previously provided with an organic metal cup. A ring agent may be included. Examples of the organometallic coupling agent include known silane coupling agents, titanium coupling agents, zirconium coupling agents, and aluminum coupling agents. Such an organometallic coupling agent is preferably used in the range of 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation curable resin.

  The ionizing radiation curable resin becomes an ionizing radiation curable resin layer (relief forming layer) when it is cured (reacted) by irradiating ionizing radiation after the relief is formed. As the ionizing radiation, ultraviolet rays (UV), visible rays, gamma rays, X-rays, electron beams (EB), or the like can be applied, and ultraviolet rays (UV) are preferable. An ionizing radiation curable resin that is cured by ionizing radiation may contain a photopolymerization initiator and / or a photopolymerization accelerator in the case of ultraviolet curing, and may not be added in the case of high energy electron beam curing. Can be cured even with thermal energy.

  As the photopolymerization initiator in the relief forming layer, for example, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylmeurum monosulfide, thioxanthones and the like can be applied. Moreover, a photosensitizer and a photopolymerization accelerator are added as necessary. The content of such a photopolymerization initiator and photosensitizer is preferably used in the range of about 0.5 to 10 parts by mass per 100 parts by mass of the urethane-modified acrylic resin.

  In addition to the above-mentioned components, the ionizing radiation curable resin composition is improved in storage stability by adding a polymerization inhibitor such as phenols such as hydroquinone, quinones such as benzoquinone, phenothiazine, etc. . Furthermore, you may mix | blend various adjuvants, such as an accelerator, a viscosity regulator, surfactant, and an antifoamer, as needed. It is also possible to blend a polymer such as styrene / butadiene rubber.

As described above, the relief forming layer is made of an ionizing radiation curable resin and, if necessary, a material added with a thermoplastic resin, a release agent, an organic metal coupling agent, a photopolymerization initiator, etc. in an appropriate solvent. A coating solution is prepared by dissolving or dispersing, and this coating solution is applied and dried by a conventional coating means such as a gravure coater, a roll coater, or a wire bar. The thickness of the relief forming layer is usually about 0.2 to 30 g / m ² , preferably 0.5 to 10 g / m ² in a dry state.
[Metal deposition layer]
The metal vapor-deposited layer 5 is provided with a metal vapor-deposited layer on the relief forming layer surface provided with a relief structure such as a hologram or a diffraction grating, so that the reproduced image of the hologram and / or the diffraction grating can be clearly recognized. When a metal that reflects light is used as the metal vapor deposition layer, it becomes an opaque type, and when a transparent metal compound having a difference in refractive index from the relief forming layer surface is used, it becomes a transparent type. Metal deposition layers include metals such as Cr, Ti, Fe, Co, Ni, Cu, Ag, Au, Ge, Al, Mg, Sb, Pb, Pd, Cd, Bi, Sn, Se, In, Ga, and Rb. , And thin films such as oxides, sulfides and nitrides thereof may be used singly or in combination. Preferred metals are aluminum, chromium, nickel, gold and silver.

Moreover, as a transparent type metal vapor deposition layer, a transparent metal compound having a difference in refractive index from the relief forming layer surface is used. Since the optical refractive index is different from that of the relief forming layer, a relief such as a hologram can be visually recognized with a substantially colorless and transparent hue and no metallic luster. As the refractive index of the metal vapor-deposited layer, the larger the difference in the refractive index from the relief forming layer surface, the more effective the refractive index difference is 0.3 or more, preferably 0.5 or more, more preferably 1.0 or more. It is. For example, ZnS, TiO ₂ , Al ₂ O ₃ , Sb ₂ O ₃ , SiO, TiO, SiO ₂ , ITO, etc. can be applied, preferably ITO or tin oxide, each having a refractive index of 2.0. There is a sufficient difference in refractive index. In addition, examples with a small refractive index include LiF, MgF ₂ , and AlF ₂ . In addition, this transparent should just permeate | transmit visible light enough, and a colorless or colored and transparent thing is also contained.

The formation of the above metal or transparent metal compound can be obtained by a vacuum thin film method such as a vacuum deposition method, a sputtering method, or an ion plating method so as to have a thickness of about 10 to 2000 nm, preferably 20 to 1000 nm. . If the thickness of the metal vapor deposition layer is less than this range, light is transmitted to some extent and the effect is reduced, and if it is more than that, the reflection effect is not changed, which is wasteful in cost.
[Adhesive layer]
The adhesive layer 6 of the present invention is mainly composed of a heat-bonding adhesive and a filler that are bonded by melting or softening with heat. % (Mass basis). Preferably, it contains 2 to 10% (mass basis). When the amount added is too small, the slipperiness is not improved. If the amount added is too large, blurring of the hologram image, reduction of metallic gloss, and sagging of the image occur. It adjusts suitably in the said range according to the kind and particle size of a filler to be used. The above-mentioned heat-bonding adhesive is, for example, an ionomer resin, an acid-modified polyolefin resin, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester copolymer, a polyester resin, or a polyamide resin. , Vinyl resins, acrylic / methacrylic (meth) acrylic resins, acrylic ester resins, maleic resins, butyral resins, alkyd resins, polyethylene oxide resins, phenolic resins, urea resins, melamine resins, Melamine-alkyd resin, cellulose resin, polyurethane resin, polyvinyl ether resin, silicone resin, rubber resin, etc. can be applied, and these resins are used alone or in combination. The resin of these adhesive layers is preferably an acrylic resin, a butyral resin, or a polyester resin in terms of adhesive strength.

  Examples of the filler contained in the adhesive layer include organic fillers such as an acrylic resin filler, a silicone resin filler, a fluorine resin filler, a benzoguanamine / formaldehyde condensate filler, and a melamine / formaldehyde condensate filler. Also, oxide fillers such as titanium oxide, silica, zinc oxide, tin oxide, magnesium oxide, hydroxide fillers such as aluminum hydroxide and magnesium hydroxide, carbonate fillers such as calcium carbonate and magnesium carbonate, magnesium sulfate, etc. Examples include inorganic fillers such as sulfate fillers, talc, clay, and silicate fillers such as calcium silicate. In particular, the use of spherical particles of a benzoguanamine / formaldehyde condensate or a melamine / formaldehyde condensate is preferable because it improves slipperiness with the image receiving sheet. Examples of the fillers of the benzoguanamine / formaldehyde condensate and melamine / formaldehyde condensate include Ester MS, Eposter M30, Eposter S12, Eposter S6, Eposter S and the like manufactured by Nippon Shokubai Co., Ltd.

  In addition, the average particle diameter of these fillers is 0.01-20 micrometers, Preferably it is 0.05-5 micrometers, More preferably, it is about 0.1-3 micrometers, The coating-film surface of an adhesive layer is contained by containing the said filler. In addition, the friction coefficient can be reduced by reducing the contact point with the image receiving sheet, the sliding property can be imparted, and the sliding property of the thermal transfer image receiving sheet can be enhanced. Furthermore, processing suitability such as reduction of wrinkles during winding can be improved by roughening the surface of the coating film.

For the adhesive layer, as described above, a heat-adhesive adhesive and a filler and, if necessary, additives such as a plasticizer, a colorant and an antistatic agent are appropriately added, and dissolved or dispersed in an appropriate solvent. Then, a coating solution is prepared, and this coating solution is applied and dried by a conventional coating means such as a gravure coater, a roll coater, or a wire bar. The thickness of the adhesive layer is usually about 0.05 to 10 g / m ² , preferably 0.1 to 5 g / m ² in a dry state. If the thickness of the adhesive layer is less than this range, the adhesive force with the transfer medium is insufficient and drops off, and if it is more than that, the adhesive effect is sufficient and the effect does not change, so it is wasteful in cost. Furthermore, the heat of the thermal head is wasted. Furthermore, additives such as a plasticizer, a colorant, and an antistatic agent may be appropriately added to the adhesive layer as needed. Examples of the antistatic agent include nonionic surfactants and anionic surfactants. Surfactants, cationic surfactants, polyamides, acrylic acid derivatives, and the like can be applied.
(Heat-resistant protective layer)
Furthermore, the heat-resistant protective layer 7 can be provided on the opposite surface of the substrate sheet where the release layer, (relief forming layer), metal deposition layer, and adhesive layer are provided. The heat-resistant protective layer includes a heat-resistant thermoplastic resin binder and a substance that functions as a heat release agent or a lubricant as basic components. The thermoplastic resin binder having heat resistance can be selected from a wide range, but preferable examples include acrylic resin, polyester resin, styrene-maleic acid copolymer, polyimide resin, polyamide resin, and polyamideimide resin. , Cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate, vinylidene fluoride resin, nylon, polyvinyl carbazole, chlorinated rubber, cyclized rubber and polyvinyl alcohol. These resins have a glass transition point of 60 ° C. or higher, or a compound having two or more amino groups or a diisocyanate or triisocyanate added to a thermoplastic resin having an OH group or a COOH group to cause a slight cross-linking cure. It is empirically known that these are preferred.

  Thermal release agents or lubricants to be blended with the above thermoplastic resins include waxes such as polyethylene wax and paraffin wax, higher fatty acid amides, esters or salts, higher alcohols and phosphate esters such as lecithin. There are those that melt by heating to act, and those that are useful as solids, such as fluororesin or inorganic powder. In addition to these lubricants or thermal release agents, other release agents such as fluorine-containing resin powder, guanamine resin powder and wood powder can be used in combination. High effect is obtained.

The composition for forming the heat-resistant protective layer is formed by blending 10 to 100 parts by mass of the above-described lubricant or thermal release agent with respect to 100 parts by mass of the thermoplastic resin binder. Application to the base sheet is kneaded with an appropriate solvent to make an ink, and in the same manner as a general coating agent application method, for example, by a coating method such as a roll coating method, a gravure coating method, a screen coating method, a fountain coating method, It can form by apply | coating to the surface which is not a relief formation layer of a base material sheet so that it may become about 0.1-4 g / m < ² > in a dry state, and drying.

In order to ensure adhesion between the base sheet and the heat-resistant protective layer, a primer layer may be provided on the base sheet in advance. The primer layer is selected according to the material of the base sheet and the kind of the thermoplastic resin binder of the heat-resistant protective layer, and is an acrylic resin, polyester resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer or polyol / isocyanate, Materials such as epoxy / isocyanate and polyol / melamine combinations can be applied. When the primer layer is formed, it is preferably formed so as to have a thickness of about 0.05 to 0.5 g / m ² in a dry state. If it is too thin, the adhesiveness is insufficient. This is not preferable because the sensitivity, heat resistance, and adhesiveness due to cohesive failure are reduced. The application method of the primer layer may be carried out by an arbitrary method in the form of an ink using an appropriate solvent, as in the application of the composition of the heat-resistant protective layer.

  The primer layer can be antistatic treated with an antistatic agent. Antistatic agents include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts and fatty acid ethylene oxide adducts, polyhydric alcohol type nonionic surfactants such as polyethylene oxide and fatty acid esters of glycerin, higher fatty acids Amino acid types such as carboxylates such as alkali metal salts, anionic surfactants such as higher alcohol sulfates, cationic surfactants such as quaternary ammonium salts such as alkyltrimethylammonium salts, and higher alkylaminopropionates Examples thereof include amphoteric surfactants and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines, and one or more of these can be used. Moreover, a metal oxide fine powder can also be used, for example, a tin oxide with a particle size of 5-50 micrometers can be used.

  Furthermore, the primer layer is applied as an ink form using an appropriate solvent, but the resin of the primer layer can be made water-dispersible or water-soluble. The solvent of the primer layer ink is applied and dried to be removed from the primer layer, but often remains as a so-called residual solvent without being completely removed. This residual solvent has the disadvantage that it softens the heat-resistant protective layer and the adhesive layer and makes the rolled-up thermal transfer sheet in an intimate contact state, making it difficult to pay out, but this is not the case if the solvent is water. Further, the solvent is discharged as a gas by drying, but if it is water, it does not pollute the atmospheric environment. In general, water-dispersed resins are less likely to be re-dissolved once formed into a film, and are less likely to be exposed to the solvent when forming a heat-resistant protective layer in contact with this layer. Can do.

In this way, by using a thermal transfer sheet having a heat-resistant protective layer, the target of the transfer target is enlarged, or as the transfer (printing, printing) speed is increased, the thermal head is changed from the heat-resistant protective layer surface of the thermal transfer sheet. Even when this operation is performed under the high energy required to obtain sufficient transfer efficiency when performing heat printing by the so-called sticking, so-called sticking occurs in which the base sheet and the thermal head are thermally fused. There is nothing.
(Thermal transfer recording method)
In the thermal transfer recording method of the present invention, a thermal transfer image is formed on an image receiving sheet from a thermal transfer sheet having a sublimation dye-containing thermal transfer dye layer and / or a heat-meltable thermal transfer layer by a first thermal head, and then a second transfer head is formed. Using the thermal transfer sheet according to claim 1 or 2 by a thermal head, it is preferable to thermally transfer a hologram or a metal vapor deposition layer to an image receiving sheet on which a thermal transfer image is formed to produce an image formed product. In addition, a peeling layer, a (relief forming layer), a metal vapor deposition layer, and an adhesive layer are formed in this order on the base sheet, and a filler is added to the adhesive layer with respect to the total solid content of the adhesive layer. % (Mass basis) containing a thermal transfer sheet can be applied by using a thermal transfer printer equipped with only one thermal head and applying a simple method of thermally transferring a hologram or a metal vapor deposition layer to the image receiving sheet. .

  Since the thermal transfer sheet of the present invention is configured to contain 0.5 to 40% (mass basis) of the filler in the adhesive layer based on the total solid content of the adhesive layer as described above, the thermal transfer dye is used in the first thermal head. The image is formed by transferring the colorant from the heat transfer layer and / or the heat-meltable heat transfer layer to the image receiving sheet, and the image is received on the image forming surface of the image receiving sheet by the second thermal head even under severe conditions. When the hologram or the metal vapor deposition layer is thermally transferred to the sheet, it is possible to prevent a conveyance trouble such that the thermal transfer sheet and the image receiving sheet are stuck, or wrinkles are generated on the thermal transfer sheet. In other words, by using the thermal transfer sheet of the present invention under conditions that are likely to cause thermal transfer recording conveyance troubles, the functions of the thermal transfer sheet can be fully exhibited.

  FIG. 3 is a schematic diagram showing one embodiment of the thermal transfer recording method of the present invention. In this embodiment, a thermal transfer printer including a first thermal transfer recording unit having a first thermal head 13 and a platen roller 15 and a second thermal transfer recording unit having a second thermal head 14 and a platen roller 16 as main components is used. . In the first thermal transfer recording unit, a thermal transfer sheet 8 provided with a thermal transfer dye layer and / or a heat-meltable thermal transfer layer containing a sublimation dye on a base sheet is used, and from a supply roll 9 around which the thermal transfer sheet is wound, It is comprised so that it may wind up on the winding roll 10. FIG. Then, an image receiving sheet 17 that is a transfer target is supplied from the paper feeding unit, and the thermal transfer sheet 8 and the image receiving sheet 17 are pressed against each other between the first thermal head 13 and the first platen roller 15, By applying energy according to image information from the thermal head 13, the dye and pigment of the thermal transfer sheet 8 are transferred to the image receiving surface of the image receiving sheet 17 to form a thermal transfer image. During this thermal transfer, the thermal transfer sheet 8 and the image receiving sheet 17 are controlled and conveyed by the respective conveying means.

  For example, when the thermal transfer sheet 8 is formed by repeatedly forming each of the yellow, magenta, and cyan dye layers and the thermal transferable protective layer on the base sheet in the surface order, the tip of the yellow dye layer is the thermal head 13. It is conveyed so as to reach the position, and conveyed so that the leading end of the image receiving sheet 17 reaches the position of the thermal head 13. Then, the thermal transfer sheet 8 and the image receiving sheet 17 are transported between the thermal head 13 and the platen roller 15 while being pressurized and heated by the thermal head, and the yellow dye is transferred to the image receiving sheet 17 in an image form. Then, it moves to the image formation start position in the direction in which the image receiving sheet 17 is returned, and the thermal transfer sheet 8 is conveyed so that the tip of the magenta dye layer reaches the position of the thermal head 13. The thermal transfer sheet 8 and the image receiving sheet 17 are heated between the thermal head 13 and the platen roller 15 while being heated by the pressure and the thermal head, and the magenta dye is transferred to the image receiving sheet 17 in an image form. The thermal transfer of the cyan dye layer and the heat transferable protective layer is also transported and thermally transferred in the same manner as described above. The thermal transfer sheet and the image receiving sheet may be conveyed in the paper discharge direction or the paper feed direction when the thermal head is heated.

  Next, the image receiving sheet 17 on which the thermal transfer image is formed and the (hologram) thermal transfer sheet 1 are pressed against each other between the second thermal head 14 and the second platen roller 16 and heated by the second thermal head 14. Thus, the hologram or the metal vapor deposition layer is transferred in a pattern onto the image receiving surface on which the image on the image receiving sheet 17 is formed. (Hologram) The first thermal transfer recording is performed so that the leading end of the relief forming layer of the thermal transfer sheet 1 is conveyed so as to reach the position of the thermal head 14 and the leading end of the image receiving sheet 17 reaches the position of the thermal head 14. Transported from the unit. The (hologram) thermal transfer sheet 1 and the image receiving sheet 17 are conveyed between the thermal head 14 and the platen roller 16 while being pressurized and heated by the thermal head, and the hologram or metal deposition layer is transferred to the image receiving sheet 17. The image is transferred. Then, the image receiving sheet 17 is conveyed to the paper discharge unit. In this case as well, the conveyance direction of the hologram or the (hologram) thermal transfer sheet and the image receiving sheet at the time of heating the thermal head of the metal vapor deposition layer may be the paper discharge direction or the paper feed direction. .

  If the (hologram) thermal transfer sheet of the present invention is used, the (hologram) thermal transfer sheet 1 and the image receiving sheet 17 are located between the thermal head 14 and the platen roller 16 in the second thermal transfer recording unit in the thermal transfer recording method as described above. Then, while being pressurized and heated by a thermal head, both are transported and the (hologram) thermal transfer sheet 1 is attached to the image receiving sheet 17 while the hologram or metal deposition layer is transferred to the image receiving sheet 17 in an image form. There are no conveyance troubles such as sticking jams or wrinkles on the (hologram) thermal transfer sheet.

In the present invention, in the conveyance trouble as described above, in the (hologram) thermal transfer sheet in which a release layer, a relief forming layer, a metal vapor deposition layer, and an adhesive layer are formed in this order on the base sheet, the relief forming layer is ionizing radiation. Those composed mainly of a curable resin such as a curable resin, in particular, the (hologram) thermal transfer sheet tends to stick to the image receiving sheet and cause jamming, etc., and the (hologram) thermal transfer sheet tends to wrinkle. Therefore, an effect can be demonstrated as a countermeasure to the conveyance trouble by the structure which contains a filler for 0.5 to 40% (mass basis) with respect to the total solid of an adhesive layer in an adhesive layer. Even in a thermal transfer sheet in which an uneven pattern such as a hologram is not formed on the surface of the relief forming layer, a sheet mainly composed of a curable resin such as an ionizing radiation curable resin may cause a conveyance trouble or wrinkle. Therefore, with the configuration in which the filler contains 0.5 to 40% (mass basis) of the filler in the total solid content of the adhesive layer, the effect can be exhibited as a countermeasure for the conveyance trouble.
(Thermal head)
There are two types of thermal transfer recording methods: a serial method and a line method. In the serial method, the thermal head is scanned in a direction perpendicular to the traveling direction of the transfer object, and printing is performed line by line. In the line method, a line-type thermal head having a plurality of heating element groups arranged in a row in a direction perpendicular to the running direction is fixed along the running direction of the transfer target, and a printing operation ( While the ink ribbon and the transfer medium are traveling), only a predetermined heating element is heated, and an image is printed on the entire width direction. Since the line system is more likely to cause a conveyance trouble during thermal transfer, the present invention is preferably applicable to the line system thermal transfer recording. In the present invention, a thermal transfer printer equipped with a serial thermal head is used to form an image by thermally transferring a hologram or a metal vapor deposition layer to the image receiving sheet using the thermal transfer sheet according to claim 1 or 2. It is also possible to make a product, and since the filler contains 0.5 to 40% (mass basis) of filler in the total solid content of the adhesive layer, a hologram is formed on the image receiving sheet with a serial type thermal head. Alternatively, when the metal vapor deposition layer is thermally transferred, it is possible to prevent a conveyance trouble that the thermal transfer sheet and the image receiving sheet are stuck together or wrinkles are generated on the thermal transfer sheet. The serial thermal head scans in a direction perpendicular to the traveling direction of the transfer target and reciprocates.

  Thermal heads include laser heat mode thermal heads, photothermal recording heads, thermal heads, and the like. The laser heat mode thermal head irradiates an ink ribbon with laser light corresponding to an image signal from a laser light source through a transparent support, and the ink ribbon that absorbs the laser generates heat, and the ink (dye of the ink ribbon) Alternatively, a heat-meltable ink) is transferred and transferred to a transfer medium, whereby an image is printed. The photothermal recording head has a two-layer structure of a photoconductive layer and a heat generating layer that are made conductive by light irradiation and generate heat, or a photoconductive heat generating layer composed of one layer of a photoconductive heat generating layer and a photoconductive heat generating layer sandwiched between them. The head is basically composed of a pair of electrode layers to which a predetermined voltage is applied. The head irradiates a laser beam or the like in accordance with an image signal from the light source, and the photoconductivity of the irradiated portion. The heat generation layer or the photoconductive heat generation layer in the heat generation layer generates heat, and the ink (dye or heat-meltable ink) of the ink ribbon is transferred to the transfer target, thereby printing an image.

  The thermal head prints an image by causing a dot-like heating element to generate heat in accordance with an image signal and transferring the ink ribbon ink (dye or heat-meltable ink) to a transfer medium. It is a thermal head. In the present invention, any thermal head may be used.

  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.

  Next, the manufacture example of the composition for relief forming layers (ink) is shown below.

(Production Example Production of relief forming layer composition (ink))
A composition having the following blending ratio was diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%, and a relief forming layer composition (ink) was obtained.
Ionizing radiation curable resin A 100 parts In general formula (1), dicyclopentenyloxyethyl methacrylate is introduced into Z, —CH ₃ is introduced into R 1 and R ₂ , —C ₂ H ₄ — is introduced into X and Y, and n is 0 It is a certain resin.
Silicone (trimethylsiloxysilicic acid-containing methylpolysiloxane, KF-7312, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 1 part polyfunctional urethane acrylate (purple UV1700B, manufactured by Nippon Gosei Chemical Co., Ltd., trade name) 25 parts photopolymerization started Agent (Irgacure 907, manufactured by Ciba Specialty Chemicals, Inc., trade name) 5 parts A composition having the following blending ratio is diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%, and a release layer composition ( Ink).

Ionizing radiation curable resin A 100 parts Silicone (methylpolysiloxane containing trimethylsiloxysilicate)
(KF-7312, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 1 part polyfunctional urethane acrylate (purple light UV1700B, manufactured by Nissei Synthetic Chemical Industry Co., Ltd., trade name) 25 parts Photopolymerization initiator (Irgacure 907)
(Product name, manufactured by Ciba Specialty Chemicals) 5 parts Thermoplastic resin (Polyester, Byron 29SS)
(Product name, manufactured by Toyobo Co., Ltd.) 2 parts Thickness in which a heat-resistant protective layer was previously provided using a heat-resistant protective layer coating solution shown below so that the thickness after drying was 1 g / m ^2. On the surface opposite to the heat-resistant protective layer of a polyester terephthalate film (F-53, manufactured by Toray Industries, Inc.) having a thickness of 6 μm, the release layer composition (ink) was dried at a film speed of 50 m / min and the thickness after drying was 0.00. It was coated with a roll coater so as to be 5 g / m ² and dried at 80 ° C. to form a release layer. The relief layer composition (ink) is applied to the release layer surface with a gravure reverse coater at a film speed of 50 m / min so that the thickness after drying is 0.5 g / m ² and dried at 100 ° C. Thus, the relief forming layer is formed, and the obtained film is not sticky at room temperature, and can be stored and post-processed in a wound state.
(Heat-resistant protective layer coating solution)
Styrene-acrylonitrile copolymer 8.5 parts (Cebian AD, manufactured by Daicel Chemical Industries, Ltd.)
0.5 part of linear saturated polyester resin (Eliether UE3200, manufactured by Unitika Ltd.)
Melamine-aldehyde resin crosslinked powder 2.5 parts (Eposter S, particle size 0.30 μm, manufactured by Nippon Shokubai Chemical Co., Ltd.)
Metal soap; Product name 5.0 parts Methyl ethyl ketone 83.0 parts Toluene 0.5 parts A relief is formed by pressurizing (embossing) a stamper on the surface of the relief forming layer. A stamper duplicated by the 2P method is affixed to an empos roller of a duplicating device from a master hologram made separately using laser light, and heated and pressed (embossed) with an opposing roller at 150 ° C. A relief consisting of a concavo-convex pattern was shaped. Immediately after shaping, the UV output window was pyrex (registered trademark) glass (wavelength selective filter, hereinafter referred to as a wavelength cut filter), and cured by irradiating with an ultraviolet ray that was almost cut in a wavelength region of 300 nm or less. . Aluminum was deposited to a thickness of 30 nm on the relief surface by vacuum deposition to form a reflective relief hologram. The relief surface was coated with a gravure coat using the adhesive layer coating solution 1 having the following composition, dried at 100 ° C., and an adhesive layer having a dry thickness of 0.2 g / m ² was formed. The hologram thermal transfer sheet of Example 1 was obtained.
(Adhesive layer coating solution 1)
20 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: DENKARAC)
0.2 parts of melamine / formaldehyde condensate filler (Eposter S, particle size 0.30 μm, manufactured by Nippon Shokubai Chemical Co., Ltd.)
Toluene 40 parts Methyl ethyl ketone 40 parts [Comparative Example 1]
The adhesive layer coating solution 1 for the hologram thermal transfer sheet in Example 1 above was changed to the following coating solution 2, coated with a gravure coat, dried at 100 ° C., and the dry thickness was 0.2 g. An adhesive layer of / m ² was formed. Otherwise, the hologram thermal transfer sheet of Comparative Example 1 was obtained in the same manner as the hologram thermal transfer sheet of Example 1.
(Adhesive layer coating solution 2)
20 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: DENKARAC)
Toluene 40 parts Methyl ethyl ketone 40 parts Using the hologram thermal transfer sheets obtained in the above examples and comparative examples, the suitability of a thermal transfer printer such as the transportability of a hologram thermal transfer sheet during hologram thermal transfer was examined under the following conditions.
(Thermal transfer printer conditions and transportability evaluation method)
Shinko Electric Co., Ltd. uses a line-type thermal head (300 dpi) as the first thermal head 13 and a line-type thermal head (300 dpi) as the second thermal head 14 in the thermal transfer printer as shown in FIG. A S8045 printer manufactured by S8045 printer manufactured by SHINKO ELECTRIC CO., LTD. The yellow, magenta, and cyan dye layers and the thermal transfer protective layer dedicated to the S8045 printer manufactured by Shinko Electric Co., Ltd. are repeated in the surface order to provide a thermal transfer sheet provided on the substrate. In addition, as the image receiving sheet 17, an image receiving sheet dedicated to S8045 printer manufactured by Shinko Electric Co., Ltd. is prepared, and a thermal transfer image of a test pattern with each dye is formed by the first thermal head. The protective layer was transferred in a solid shape so as to cover the entire thermal transfer image. Next, the second thermal head 14 uses the hologram thermal transfer sheets of Examples and Comparative Examples to transfer the hologram on the thermal transfer image (protective layer) in a pattern different from the test pattern. Create an image formation. At this time, the hologram thermal transfer sheet 1 and the image receiving sheet 17 in the second thermal transfer recording unit using the second thermal head are conveyed between the thermal head 14 and the platen roller 16 while being pressurized and heated by the thermal head. During the transfer of the hologram onto the image receiving sheet 17 in the form of an image, the hologram thermal transfer sheet 1 will not stick to the image receiving sheet 17 and cause wrinkles or wrinkles on the hologram thermal transfer sheet. The transportability was examined.
(Evaluation results)
When the hologram thermal transfer sheet of Example 1 was used, in the above transportability, ten image receiving sheets were continuously thermally transferred and recorded, and no transport trouble occurred. On the other hand, when the hologram thermal transfer sheet of Comparative Example 1 was used, in the transportability described above, when 10 image receiving sheets were continuously subjected to thermal transfer recording, the third hologram thermal transfer sheet 1 was the image receiving sheet 17. Sticking to the surface, jamming occurred, thermal transfer recording stopped, and a normal printed matter could not be obtained.

It is a schematic sectional drawing which shows one embodiment which is the hologram thermal transfer sheet of this invention. It is a schematic sectional drawing which shows other embodiment which is a hologram thermal transfer sheet of this invention. It is the schematic which shows one embodiment which is the thermal transfer recording method in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 (Hologram) Thermal transfer sheet 2 Base material sheet 3 Release layer 4 Relief formation layer 5 Metal vapor deposition layer 6 Adhesive layer 7 Heat-resistant protective layer 8 Thermal transfer sheet 9 Supply roll 10 Hoist roll 11 Supply roll 12 Hoist roll 13 First thermal head 14 First 2 Thermal head 15 Platen roller (first)
16 Platen roller (second)
17 Image receiving sheet

Claims (4)

  In the thermal transfer sheet in which the release layer, the metal vapor deposition layer, and the adhesive layer are formed in this order on the base sheet, the filler is added to the adhesive layer in an amount of 0.5 to 40% (mass basis) with respect to the total solid content of the adhesive layer. And a thermal transfer sheet.   In the hologram thermal transfer sheet in which the release layer, the relief forming layer, the metal vapor deposition layer, and the adhesive layer are formed in this order on the base material sheet, the filler is added to the adhesive layer with respect to the total solid content of the adhesive layer. A hologram thermal transfer sheet containing 40% (by mass).   3. A thermal transfer image is formed on an image receiving sheet from a thermal transfer sheet having a thermal transfer dye layer and / or a heat-fusible thermal transfer layer containing a sublimation dye by a first thermal head, and thereafter a second thermal head is used to form a thermal transfer image. A thermal transfer recording method comprising producing an image-formed product by thermally transferring a hologram or a metal deposition layer to an image receiving sheet on which a thermal transfer image is formed, using the thermal transfer sheet described in 1. A thermal transfer recording method, wherein a serial thermal transfer printer is used to produce an image formed product by thermally transferring a hologram or a metal vapor deposition layer to an image receiving sheet using the thermal transfer sheet according to claim 1.

Images