JP2007118563A - Transfer foil and image forming product using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer foil having a relief structure such as a hologram and a diffraction grating and hardly generating crazing or chipping in a thermal printer or the like, and an image forming product using it. <P>SOLUTION: Provided are a transfer foil exhibiting good shape imparting properties of a relief structure and good plate wear of a shape imparting stamper even in the case of a relief forming layer of high heat resistant materials, and exhibiting good transfer properties (printability) of a high resolution image even in the case of transfer by means of a thermal printer, etc., and an image forming product using it, characterized in that the transfer foil comprises a substrate 11, a release layer 13, a relief forming layer 15 and a reflective layer 17 being sequentially laminated, and the release layer contains at least a thermoplastic resin having a glass transition temperature of 120-200°C and the relief forming layer comprises a cured matter of an ionizing radiation-curing resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transfer foil. More specifically, the present invention relates to a transfer foil having a relief structure such as a hologram and / or a diffraction grating, and capable of high-precision transfer printing without cracking or chipping in a thermal printer or the like, and the use thereof Image forming product.

In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated.
In the present specification, the ionizing radiation curable resin is a precursor or composition before curing without irradiation with ionizing radiation, and a material cured by irradiation with ionizing radiation is referred to as ionizing radiation curable resin.

(Main use)
The use of the transfer foil of the present invention is to obtain an image formed product in which a relief structure such as a hologram and / or a diffraction grating is transferred and printed with high precision by a printing mold or a thermal printer. High-definition transfer printing is to reproduce a printing mold or printing information faithfully with very few defects such as cracks, chips, and burrs. Note that transfer printing is printing or printing as a result, and may be written as printing and / or printing depending on the situation.
The main application of the image-formed product using the transfer foil of the present invention is particularly limited as long as the application requires an image-formed product on which a relief structure such as a hologram and / or a diffraction grating is printed with high definition. It is not a thing. For example, credit cards, ID cards, prepaid cards and other cards, which cannot be reproduced with color copies, are transferred to paper certificates such as gift certificates, checks, bills, stock certificates, admission tickets, and various certificates. ing.
A transfer foil having a relief structure such as a hologram or a diffraction grating can express a unique decorative image or a three-dimensional image. Therefore, it is used for packaging materials, books, pamphlets, POPs, etc. Since it requires manufacturing technology and cannot be easily manufactured, it is used as a forgery prevention.

(Background technology)
As a means for transferring and bonding 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. In the heat transfer, a transfer foil is disposed between a metal engraved mark or roll and a transfer target, the transfer foil is pressed against the transfer target with the stamp or roll, and then the substrate is peeled off. However, in a transfer method using a hot stamp or a heating roll, an image having dots having a fine area of several mm square or less, adjacent dots, and fine non-transfer parts (called white parts in the same industry) is transferred. This is extremely difficult because burrs are easily generated, and is not suitable for high-definition printing.
In addition, transfer printing by a thermal printer has poor transferability (printability) such as cracking at the time of transfer, and thus heat resistance is required as a material for a relief forming layer for forming a relief in order to prevent cracking. However, in heat-resistant materials, in the manufacturing process for forming a relief, formability is poor, and the press stamper used for shaping is low in printing durability, and in particular functions such as computer graphic holograms and computer generated holograms (CGH) In the relief structure, formability and printing durability are remarkably lowered, and there is a possibility that the relief function cannot be sufficiently exhibited.
Conversely, a material with low heat resistance as the material of the relief forming layer has good printing durability, but the relief is not well shaped, and the relief is liable to deteriorate due to heat during transfer printing, resulting in burrs. There is a problem that it is easy to transfer and poor.
Therefore, the transfer foil having a relief structure such as a hologram and / or a diffraction grating has a good moldability of the relief structure even with a relief forming layer of a high heat resistant material, and a printing stamper has a good printing durability. High-definition images can be cracked, chipped and removed at high speed and with low energy while maintaining efficient design and / or optical function effects such as holograms and diffraction gratings even when transferred with a thermal printer, etc. There is a need for a transfer foil that is less susceptible to burrs, has good transferability (printability), and can be printed and / or printed accurately.

(Prior art)
2. Description of the Related Art Conventionally, a thermal printer using a thermal melting type or dye sublimation transfer type ink ribbon and transferring in a dot shape using a thermal head of the thermal printer is known (for example, see Patent Document 1). However, transfer foils with relief structures such as holograms and / or diffraction gratings with high design properties tend to cause cracks and chipping, making it impossible to accurately transfer (print) high-definition images, and conversely form reliefs. If a layer with a slightly low heat resistance is used for the layer, cracks and chipping will not occur, but the relief shape will change (deteriorate) due to heat during transfer, etc., and the design properties of holograms and / or diffraction gratings will deteriorate. There is a drawback.
The applicant has applied for a transfer foil that can be printed with a thermal printer with high definition (see, for example, Patent Documents 2 to 4). However, it is intended to accurately transfer (print) high-definition images. The heat resistance material of the relief forming layer, the moldability of the relief structure, the printing durability of the mold stamper, and the transfer suitability such as prevention of cracks There is no description or suggestion about coexistence of these.

JP-A-11-227368 JP 2004-98455 A Japanese Patent Application Laid-Open No. 2004-101834 JP 2004-361622 A

  Accordingly, the present invention has been made to solve such problems. Its purpose is to provide a relief-forming layer of a high heat-resistant material, so that the relief structure has a good moldability and the stamping stamper has a good printing durability. It is to provide a transfer foil with good printability and an image formed product using the same.

In order to solve the above problems, the transfer foil according to the invention of claim 1 is a transfer foil in which a base material, a release layer, a relief forming layer, and a reflective layer are sequentially laminated, and the release layer is at least a glass transition. It contains a thermoplastic resin at a temperature of 120 ° C. to 200 ° C., and the relief forming layer is made of a cured product of an ionizing radiation curable resin.
The transfer foil according to the invention of claim 2 is such that the thermoplastic resin is a cyclic olefin resin.
The transfer foil according to the invention of claim 3 is such that the cyclic olefin-based resin is a norbornene-based resin.
The transfer foil according to the invention of claim 4 is such that the relief forming layer is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer.
In the transfer foil according to the invention of claim 5, the urethane (meth) acrylate oligomer comprises (1) isocyanates having 3 or more isocyanate groups in the molecule, (2) at least one hydroxyl group in the molecule (meta It is a reaction product of polyfunctional (meth) acrylates having at least two acryloyloxy groups, and (3) polyhydric alcohols having at least two hydroxyl groups in the molecule.
The transfer foil according to the invention of claim 6 is such that the ionizing radiation curable resin is a mixture of urethane (meth) acrylate oligomer and methacrylic resin.
The transfer foil according to the invention of claim 7 is such that the mass-based ratio of the ionizing radiation curable resin is urethane (meth) acrylate oligomer: methacrylic resin = 1: 2 to 2: 1. is there.
The transfer foil according to the invention of claim 8 has a thickness of the release layer of 0.1 to 1.0 μm, a thickness of the relief forming layer of 0.3 to 2.5 μm, and a release layer and a relief forming layer. The thickness ratio is 1: 1 to 1:20.
The transfer foil according to the invention of claim 9 is such that the thickness of the substrate is 3.0 to 8.0 μm.
The transfer foil according to the invention of claim 10 is such that a heat-resistant protective layer is provided on the surface opposite to the relief forming layer of the substrate.
The transfer foil according to the invention of claim 11 is such that an adhesive layer is provided on the reflective layer surface.
The image-formed product according to the invention of claim 12 is formed by thermal transfer to a transfer medium using the transfer foil according to any one of claims 1-9.
The image formed product according to the invention of claim 13 is such that the thermal transfer means is a thermal printer.

  The present inventors pay attention to the fact that even a relief forming layer of a high heat resistant material achieves both the moldability of the relief structure, the printing durability of the mold stamper, and the transferability (printability). Then, by limiting the material, thickness, and thickness ratio of each layer constituting the transfer foil, (1) Even if it is a relief-forming layer of a high heat resistant material, (2) the formability of the relief structure is good The stamping stamper has good printing durability, can be manufactured efficiently, and (3) even with transfer by a thermal printer or the like, while maintaining the design and / or optical function effect of a hologram, diffraction grating, etc. It has been found that high-definition images with low energy are less susceptible to cracking, chipping, and burrs, and can be transferred and printed (printed and / or printed) with good transferability (printability).

According to the first to third aspects of the present invention, a high-definition image can be cracked at high speed and with low energy while maintaining the design and / or optical function effect of a hologram, a diffraction grating, etc. even in transfer by a thermal printer or the like. There is provided a transfer foil that is unlikely to be cracked, chipped, or burred, has good transferability (printability), and can be printed and / or printed accurately.
According to the fourth to fifth aspects of the present invention, in addition to the effect produced from the transfer foil of the first aspect, the relief forming layer of the high heat resistant material has a good relief structure and has a moldable stamper. A transfer foil having good printing durability and capable of being produced efficiently is provided.
According to this invention of Claims 6-7, the transfer foil which can increase the effect which arises from the transfer foil of Claim 4 more is provided.
According to the present invention of claims 8 to 9, even if it is a relief forming layer of a high heat resistance material, the moldability of the relief structure is good, the printing durability of the mold stamper is good, and it can be produced efficiently, In addition, even when transferring with a thermal printer or the like, while maintaining the design and / or optical function effect such as a hologram and diffraction grating, a high-definition image is not easily cracked, chipped, or flashed at high speed and low energy, A transfer foil having good transferability (printability) and capable of accurately printing and / or printing is provided.
According to the tenth aspect of the present invention, there is provided a transfer foil capable of performing a stable printing operation without causing the transfer ribbon to be in close contact with the receiving roll of the print head during transfer with a thermal printer.
According to the present invention of claim 11, there is provided a transfer foil that can be transferred without providing an adhesive layer on the transfer target.
According to the present invention of claims 12 to 13, even when transferring with a thermal printer or the like, the design and / or optical function effect such as a hologram and a diffraction grating is maintained, and cracks, chips and burrs are extremely small and high definition. An image formed product on which an image is formed is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of a transfer foil showing one embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of a transfer foil showing one embodiment of the present invention.

(Configuration of transfer foil)
As shown in FIG. 1, the transfer foil 1 of the present invention is provided with a release layer 13, a relief forming layer 15, a reflective layer 17, and an adhesive layer 19 on one surface of a base material 11. It is a layer structure of peeling layer 13 / relief forming layer 15 / reflective layer 17 / adhesive layer 19. The adhesive layer 19 is not essential because it may be provided on the transfer target, but it is usually provided on the transfer foil, so that the description will be made with the adhesive layer 19 provided. Further, as will be described later, as shown in FIG. 2, a heat-resistant protective layer 21 may be provided on the other surface of the substrate 11.
The relief forming layer 15 is a cured product of an ionizing radiation curable resin, preferably an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer, and more preferably, the urethane (meth) acrylate oligomer is (1) molecule. Isocyanates having three or more isocyanate groups in the interior, (2) polyfunctional (meth) acrylates having at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule, and (3) in the molecule It is a reaction product of polyhydric alcohols having at least two hydroxyl groups.
The release layer 13 is a cyclic olefin resin, preferably a norbornene resin.
The thickness of the release layer 13 is 0.1 to 1.0 μm, the thickness of the relief forming layer 15 is 0.3 to 2.5 μm, and the thickness ratio of the release layer 13 and the relief forming layer 15 is 1. : 1-1: 20.

(Transfer foil base material)
As the base material 11, various materials can be applied according to the use as long as the base material 11 has heat resistance, mechanical strength, mechanical strength, solvent resistance, etc. For example, 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 Polyamide resins such as nylon 6, nylon 66 and nylon 610, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polyacrylate, polymethacrylate and polymethyl methacrylate Acrylic resins, imide resins such as polyimide, polyamideimide, polyetherimide, polyarylate, polysulfone・ Engineering resins such as polyethersulfone, polyphenylene ether, polyphenylene sulfide (PPS), polyaramid, polyetherketone, polyethernitrile, polyetheretherketone, polyethersulfite, polycarbonate, polystyrene, high impact polystyrene, AS resin, ABS Examples include styrene resins such as resins, and cellulose films such as cellophane, cellulose triacetate, cellulose diacetate, and nitrocellulose.

  The substrate may be a copolymer resin containing these resins as a main component, a mixture (including an alloy), or a laminate composed of a plurality of layers. The substrate 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 the strength. The substrate is used as a film, sheet or board formed of 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. The thickness of the substrate is usually about 2.5 to 50 μm, preferably 2.5 to 12 μm, and most preferably 3 to 8 μm in terms of transferability. If the thickness is greater than this, the heat transfer of the thermal head is poor, and if it is less than this, the mechanical strength is insufficient. In particular, when the substrate is thin, the heat of the thermal head is diffused and transmitted to the adhesive layer in the non-transfer area around the predetermined image, and the adhesive layer is activated. The adhesive layer is more closely attached to the transfer target and deteriorates the foil breakability. However, by using a cyclic polyolefin-based resin as the main component as the release layer 13, the release layer 13 is appropriately bonded to the base material 11 and the relief forming layer.

  Prior to application, the substrate 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 treatment. Alternatively, easy adhesion treatment such as vapor deposition treatment or 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. As the filler, extender pigments such as silica and calcium carbonate can be applied. As the colorant, a disperse dye is preferable, and disperse dyes such as monoazo, bisazo, anthraquinone, nitro, styryl, methine, alloyene, benzimidazole, aminonaphthylamide, naphthoquinoneimide, and coumarin derivatives can be applied. As the antistatic agent, nonionic surfactants, anionic surfactants, cationic surfactants, polyamides, acrylic acid derivatives, and the like can be applied.

(Peeling layer)
As a material for the release layer 13, a general thermoplastic resin having a glass transition temperature (Tg) of 120 to 200 ° C. can be applied. Usable resins include cyclic olefin resins, norbornene resins, polycarbonate resins, polyarylate resins, polyamideimide resins (Tg; 200 ° C. or lower), polyetherimide resins (Tg; 200 ° C. or lower), polysulfone resins, and the like. Can be mentioned. Cyclic olefin resins are preferred, and norbornene resins are more preferred. The material of the release layer may be a copolymer resin containing these resins as a main component, or a mixture (including an alloy). Examples of the cyclic olefin-based resin containing a cyclic structure include (a) a norbornene polymer, (b) a monocyclic olefin polymer, (c) a cyclic conjugated diene polymer, and (d) a vinyl alicyclic ring. And a hydride of (a) to (d). Among these, from the viewpoint of excellent heat resistance and mechanical strength, a norbornene polymer hydride, a vinyl alicyclic hydrocarbon polymer and a hydride thereof are preferable, and a hydride of a norbornene polymer is more preferable.
The glass transition temperature (Tg) described in the present invention is a glass transition point obtained from a DSC curve based on JIS K 7121-1987.

  The norbornene-based resin is, for example, (a-1) a ring-opening polymer of a norbornene-based monomer, or (a-2) a ring-opening copolymer of a norbornene-based monomer and another monomer copolymerizable therewith. A polymer, (a-3) an addition polymer of a norbornene monomer, (a-4) an addition polymer of a norbornene monomer and another monomer copolymerizable therewith, and (a- There are hydrides of 1) to (a-4).

As the norbornene-based monomer, bicyclo [2.2.1] hept-2-ene (common name:
Norbornene), tricyclo [4.3.12,5] deca-3,8-diene (common name:
Dicyclopentadiene), 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.12, 5.17. , 10] dodec-3-ene (common name: tetracyclododecene), derivatives of these compounds (having a substituent in the ring), and the like. Here, examples of the substituent include an alkyl group, an alkylene group, an alkoxycarbonyl group, and a carboxyl group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers may be used alone or in combination.

Examples of other monomers copolymerizable with norbornene monomers include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene and derivatives thereof; etc. Is mentioned.
These cyclic olefins can be used alone or in combination of two or more.
Among these cyclic olefins, norbornene, tricyclo [4.3.0.12.5] -3-decene, tricyclo [4.4.0.12.5] -3-undecene, tetracyclo [4.4. 0.12.5.17.10] -3-dodecene is preferred.

  To the cyclic olefin-based resin, other thermoplastic resins and additives such as fillers, plasticizers, lubricants, colorants, antistatic agents, etc. are added to control the adhesion to the substrate. May be.

The cyclic olefin-based resin used for the release layer 13 is a norbornene-based resin in terms of heat resistance, low birefringence, amorphousness, solvent solubility (applicability), adhesion to the substrate and the relief forming layer, or the like. What has a norbornene-type resin as a main component is preferable.
Moreover, the thermoplastic resin used for the peeling layer 13 has an appropriate glass transition temperature (Tg), and Tg is 120 degreeC-200 degreeC. If the Tg is higher than 200 ° C, the resolution of the transferred image cannot be obtained. If the Tg is lower than 120 ° C, the entire transfer layer has insufficient heat resistance, and cracks and the like occur due to heat during transfer. A high-definition hologram image formed product cannot be obtained.

(Relief forming layer)
As a material constituting the relief forming layer 15, for example, a cured product (ionizing radiation curable resin) of an ionizing radiation curable resin such as an epoxy-modified acrylate resin, a urethane-modified acrylate resin, or an acrylic-modified polyester can be applied. In addition, the ionizing radiation curable resin may be a copolymer resin containing these resins as a main component, or a mixture (including an alloy). The ionizing radiation curable resin is preferably one having excellent moldability and appropriate heat resistance.

That is, it is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer. Preferably, the urethane (meth) acrylate oligomer is (1) an isocyanate having three or more isocyanate groups in the molecule, (2) at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule. Reaction product of polyfunctional (meth) acrylates having, and (3) polyhydric alcohols having at least two hydroxyl groups in the molecule.
More preferably, the isocyanate having three or more isocyanate groups is at least one selected from a trimer of isophorone diisocyanate and a reaction product of isophorone diisocyanate and an active hydrogen-containing compound.

  Regarding the reaction of isocyanates, polyfunctional (meth) acrylates, and polyhydric alcohols, (1) first reacting isocyanates with polyhydric alcohols, ) Reacting acrylates, (2) reacting isocyanates with hydroxyl-containing polyfunctional (meth) acrylates first, and then reacting with polyhydric alcohols, (3) polyhydric alcohols and hydroxyl-containing polyfunctional ( Any method of reacting a mixture with (meth) acrylates with isocyanates can be used. When reaction is performed using at least one of at least one of isocyanates, hydroxyl group-containing polyfunctional (meth) acrylates, and polyhydric alcohols, two or more urethanes are used as reaction products. A mixture of (meth) acrylate oligomers is obtained.

The total hydroxyl group equivalent of polyhydric alcohols and hydroxyl group-containing polyfunctional (meth) acrylates with respect to 1 equivalent of isocyanate groups in the isocyanate is preferably 0.9 to 1.8 equivalents. When the total hydroxyl group equivalent is less than 0.9 equivalent, the stability of the resin composition after the reaction is lowered, and when it exceeds 1.8 equivalent, sufficient cured properties cannot be obtained.
The molar ratio of the polyfunctional (meth) acrylates used is preferably 5 to 15 moles per mole of polyhydric alcohols. When there are few polyfunctional (meth) acrylates outside this range, sufficient curability is not obtained by gelation. Moreover, when it exceeds this range and sufficient hardened | cured material property is not obtained.

  Moreover, the mixture of the said urethane (meth) acrylate oligomer and other resin can be used as an ionizing radiation curable resin, and a mixture with a methacryl resin is optimal. As a mixture of a urethane (meth) acrylate oligomer and a methacrylic resin, a mass-based ratio is preferably urethane (meth) acrylate oligomer: methacrylic resin = 1: 2 to 2: 1. When there are many urethane (meth) acrylate oligomers exceeding this range, there is a drawback that sufficient formability cannot be obtained, and when there are few urethane (meth) acrylate oligomers outside this range, sufficient There is a drawback that heat resistance cannot be obtained.

  In addition, it is preferable that it is not sticky in a coating state before being cured with ionizing radiation and can be cured with ionizing radiation after the relief structure is easily formed, and an isocyanate compound having a melting point of 40 ° C. or higher and a (meth) acryloyl group. It is preferable to use an ionizing radiation curable resin containing a reaction product of a (meth) acrylic compound which has an isocyanate group and has a softening point of 40 ° C. or higher. Furthermore, the heat resistance of the ionizing radiation curable resin constituting the relief forming layer 15 has an appropriate glass transition temperature (Tg), preferably 120 to 300 ° C. Excessive heat resistance exceeding this range reduces the moldability due to the layer being hard, and if the heat resistance is lower than this range, the bent-shaped relief structure is deformed and deteriorated by heat during transfer. As a result, performance decreases.

  Further, when a relief is formed (replicated) on the relief forming layer 15, a stamper (metal plate or resin plate) having an uneven relief formed on the surface thereof is pressure-bonded to the surface of the relief forming layer 15. The relief is formed (replicated) on the relief forming layer 15. At this time, a release agent may be added to the relief forming layer 15 in advance so that the stamper can be easily peeled off from the relief forming layer 15. As the release agent, known release agents can be applied, for example, solid waxes such as polyethylene wax, amide wax and Teflon (registered trademark), fluorine-based and phosphate-based surfactants, silicone, and the like. Particularly preferably, the release agent is a modified silicone. Specifically, modified silicone side chain type, modified silicone both end type, modified silicone one end type, modified silicone side chain both end type, methylpolysiloxane containing trimethylsiloxysilicic acid (referred to as silicone resin) , Silicone graft acrylic resin, and methylphenyl silicone.

Modified silicone includes reactive silicone and non-reactive silicone. As the reactive silicone oil, amino modification, epoxy modification, carboxyl group modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-terminal reactivity, heterogeneous functional group modification, and the like can be used. As the non-reactive silicone oil, polyether modification, methyl styryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, fluorine modification and the like can be used.
As modified silicone, what does not inhibit the adhesiveness of the relief forming layer 15 in which the relief unevenness | corrugation was formed, and the reflective layer 17 provided in the relief surface is good, and reactive silicone and silicone resin are preferable.

  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 exceeds the above range, repellency occurs during coating of the composition, the surface of the coating film becomes rough, the adhesion with the substrate or the reflective layer is deteriorated, or transfer Since the relief forming layer 15 film sometimes breaks (film strength becomes too weak), it is not preferable.

(Ionizing radiation)
The ionizing radiation curable resin becomes an ionizing radiation curable resin (relief forming layer 15) when cured (reacted) by irradiation with 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.

(Photopolymerization initiator)
As the photopolymerization initiator, 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 photosensitizer and photopolymerization accelerator may be known photosensitizers, such as benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, and α-phenylbenzoin. Compounds: anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl; diacetyl; phenyl ketone compounds such as acetophenone and benzophenone; sulfide compounds such as diphenyl disulfide and tetramethylthiuram sulfide; α-chloromethylnaphthalene; anthracene and hexachlorobutadiene, penta There are halogenated hydrocarbons such as chlorobutadiene, n-butylamine, triethylamine, and tri-n-butylphosphine. 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 the ionizing radiation curable resin composition, in addition to the above components, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazine and the like: coppers and the like When the polymerization inhibitor is added, the storage stability is improved. Furthermore, you may mix | blend various adjuvants, such as an accelerator, a viscosity regulator, surfactant, and an antifoamer, as needed. Moreover, you may mix | blend polymer bodies, such as a styrene-butadiene rubber.

  The relief forming layer 15 is an ionizing radiation cured product obtained by curing an ionizing radiation curable resin with ionizing radiation, and the thickness of the relief forming layer 15 is usually about 0.2 to 10.0 μm, preferably 0.3. ~ 2.5 μm.

(Thickness and thickness ratio)
Transferability can be improved by the thickness and thickness ratio of the release layer 13 and the relief forming layer 15, that is, the thickness of the release layer 13 is 0.1 to 1.0 μm and the thickness of the relief forming layer 15 is 0.3 to 2 μm. By setting the thickness ratio of the release layer 13 and the relief forming layer 15 to 1: 1 to 1:20, the release characteristics of the transfer layer including the release layer and the relief forming layer and the moldability of the transfer foil are set. Etc. can be optimized, and transferability (printability), moldability and heat resistance by a thermal printer or the like can be improved.
When the thickness of the release layer 13 is less than 0.1 μm, the transferability and moldability are lowered, and when it is thicker than 1.0 μm, the transferability is lowered. Further, when the thickness of the relief forming layer 15 is less than 0.3 μm, the moldability and heat resistance are lowered, and when it is thicker than 2.5 μm, the transferability is lowered. When the thickness ratio between the release layer 13 and the relief forming layer 15 is outside the range of 1: 1 to 1:20, the release layer 13 is thin, and the relief forming layer 15 is thick, the transfer layer base material is used. Therefore, the formability and transferability are lowered. Further, when the release layer 13 is thick and the relief forming layer 15 is thin, the proportion of the relief forming layer in the transfer layer is relatively low, so that the moldability is lowered.
When transferability is low, printability by a thermal printer or the like may be reduced. In addition, when the heat resistance is low, cracks after printing tend to occur, and there is a possibility that the image quality after printing of a high-definition image having a precise and complicated relief structure may be lowered.
When the moldability is low, the relief structure cannot be molded sufficiently, and the optical function may be deteriorated. In particular, the computer graphic hologram or the computer generated hologram (CGH) to which the relief structure has added optical functionality may be used. ) And the like have a precise and complicated relief structure, and there is a possibility that the relief cannot be sufficiently molded due to a decrease in moldability.

(Reflective layer)
By providing the reflection layer 17 on the relief of the relief forming layer 15 provided with a relief structure such as a hologram or a diffraction grating, the reproduced image of the hologram and / or the diffraction grating can be clearly seen. When a metal that reflects light is used as the reflection layer 17, it becomes an opaque type, and when a transparent metal compound having a refractive index different from that of the relief forming layer 15 surface is used, it becomes a transparent type. As the reflective layer 17, 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 are used. , 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.

(Transparent reflective layer)
Further, as the transparent type reflection layer 17, a transparent metal compound having a difference in refractive index from the surface of the relief forming layer 15 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 reflective layer 17, the larger the difference in refractive index from the surface of the relief forming layer 15, the more effective, and the difference in refractive index is 0.3 or more, preferably 0.5 or more, more preferably 1. 0 or more. For example, ZnS, TiO2, Al2O3, Sb2O3, SiO, TiO, SiO2, ITO, etc. can be applied, preferably ITO or tin oxide, both having a refractive index of 2.0, and a sufficient difference in refractive index. have. In addition, examples of low refractive index include LiF, MgF2, and AlF2. 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 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 that the thickness of each of the metal or transparent metal compound is about 10 to 2000 nm, preferably 20 to 500 nm. . If the thickness of the reflective layer 17 is not less than this range, cracking tends to occur during transfer, and if it is less than this range, the reflection effect is low.

(Adhesive layer)
The adhesive layer 19 can be applied with a heat-bonding adhesive that is melted or softened by heat, for example, ionomer resin, acid-modified polyolefin resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic. Acid ester copolymer, polyester resin, polyamide resin, vinyl resin, acrylic / methacrylic (meth) acrylic resin, acrylic ester resin, maleic resin, butyral resin, alkyd resin, polyethylene Oxide resin, phenolic resin, urea resin, melamine resin, melamine-alkyd resin, cellulose resin, polyurethane resin, polyvinyl ether resin, silicone resin, rubber resin, etc. can be applied. Use in combination.

  The resin of the adhesive layer 19 is preferably a vinyl resin, an acrylic resin, a butyral resin, or a polyester resin in terms of adhesive strength. More preferable is a maleic acid-vinyl chloride-vinyl acetate copolymer in terms of adhesiveness.

  The thickness of the adhesive layer 17 is usually about 0.05 to 5.0 μm, preferably 0.10 to 0.25 μm. If the thickness of the adhesive layer 19 is less than this range, the adhesive strength with the transfer medium is insufficient and drops off, and if the thickness is higher than this range, the adhesive effect is sufficient and the effect remains unchanged, which is wasteful in cost. Furthermore, the heat of the thermal head is wasted. Furthermore, additives such as a filler, a plasticizer, a colorant, and an antistatic agent may be appropriately added to the adhesive layer 19 as necessary. As the filler, extender pigments such as silica and calcium carbonate can be applied. In particular, addition of extender pigments improves foil breakage. As the antistatic agent, nonionic surfactants, anionic surfactants, cationic surfactants, polyamides, acrylic acid derivatives, and the like can be applied.

(Heat-resistant protective layer)
Furthermore, the heat-resistant protective layer 21 may be provided on the surface of the substrate opposite to the release layer or the relief forming layer. The heat-resistant protective layer 21 includes a heat-resistant thermoplastic resin binder and a substance that functions as a heat release agent or a lubricant as basic constituent 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 forming the heat-resistant protective layer 21 is formed by blending 10 to 100 parts by mass of the above-mentioned lubricant or thermal release agent with respect to 100 parts by mass of the thermoplastic resin binder. For application to a substrate, an ink is kneaded with an appropriate solvent, and the coating method such as roll coating method, gravure coating method, screen coating method, fountain coating method, etc. is applied in the same manner as the general coating agent coating method. What is necessary is just to apply | coat and dry to the surface which is not a relief formation layer of material. The thickness of the heat-resistant protective layer 21 is about 0.01 to 1.0 μm, preferably 0.1 to 0.2 μm.

  In order to ensure adhesion between the base material sheet and the heat-resistant protective layer 21, a primer layer may be provided on the substrate 11 in advance. The primer layer is selected according to the material of the substrate 11 and the type of the thermoplastic resin binder of the heat-resistant protective layer 21, 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 forming the primer layer, it is preferable to form a layer having a thickness of about 0.05 to 0.5 μm. If the layer is too thin, the adhesiveness is insufficient. On the other hand, if the layer is too thick, the sensitivity and heat resistance of the thermal head are reduced. This is not preferable because the adhesiveness is reduced due to cohesive failure. The primer layer may be applied by an arbitrary method using an appropriate solvent in the form of an ink, as in the application of the composition of the heat-resistant protective layer 21.

  Thus, by using the transfer foil having the heat-resistant protective layer 21, the surface of the object to be transferred is enlarged, or the surface of the heat-resistant protective layer 21 of the transfer foil is increased as the transfer (printing, printing) speed is increased. When performing thermal printing from a thermal head to a thermal head, so-called sticking occurs in which the substrate and the thermal head are thermally fused even if this operation is performed under the high energy required to obtain sufficient transfer efficiency. It does not occur.

(Layer structure, material, thickness and thickness ratio)
The layer structure of the transfer foil of the present invention is the layer structure of heat-resistant protective layer 21 (if necessary) / base material 11 / peeling layer 13 / relief forming layer 15 / reflective layer 17 / adhesive layer 19 (if necessary). The preferred thickness of each layer is as follows: heat-resistant protective layer 21 (0.1 to 0.2 μm) / base material 11 (3 to 8 μm) / peeling layer 13 (0.1 to 1.0 μm) / relief forming layer 15 (0.3 to 2.5 μm) / reflective layer 17 (30 to 1000 nm) / adhesive layer 19 (0.15 to 0.25 μm), and the thickness ratio of the release layer 13 and the relief forming layer 15 is 1: 1. ~ 1: 20. Thus, in addition to the combination of the layer structure, the relief forming layer 15 made of ionizing radiation curable resin, and the release layer 13 mainly composed of a cyclic olefin-based resin, by limiting the thickness and thickness ratio of the layers, high heat resistance Even if a relief forming layer of a conductive material is used, the moldability of the relief structure is good, the press life of the mold stamper is good, it can be produced efficiently, and it can be transferred with high precision by a thermal printer or the like.

  Transferability by a thermal printer or the like can be transferred with high definition by keeping the thickness of the release layer and the relief forming layer at a constant ratio. Further, since the relief forming layer 15 has high heat resistance, the transferred relief forming layer 15 is not cracked, and therefore the reflective layer 17 formed on the surface of the relief forming layer 15 is very unlikely to crack. High-definition images can be transferred. Details about the thickness and thickness ratio are described in the examples. Furthermore, since a relief forming layer of a high heat resistant material is used, high-definition images can be generated at high speed, low energy, and without cracking while maintaining design and / or optical function effects such as holograms and diffraction gratings. In addition, chipping and burrs are hardly generated, transferability (printability) is good, and transfer printing (printing and / or printing) can be performed.

(Production method)
In the method for producing a transfer foil of the present invention, (a) a base layer 11 is provided with a release layer 13 containing a cyclic polyolefin resin, (b) a relief forming layer 15 is provided on the surface of the release layer 13, and (c) the Relief is formed on the relief forming layer 15, (d) ionizing radiation is applied to the relief forming layer 15, (e) the reflective layer 17 is provided on the relief surface, and (f) the adhesive layer 19 is provided on the reflective layer 17 surface. A known manufacturing process can be applied. The formation of the release layer 13, the relief forming layer 15, the reflective layer 17, and the adhesive layer 19 is well known to those skilled in the art and is omitted. (C) Relief shaping to the relief forming layer 15 and (d) Irradiation irradiation Only will be described.

(C: Step of shaping a relief on the relief forming layer 15)
A relief is formed on the surface of the relief forming layer 15 coated on the substrate. The relief is an uneven relief structure which is a surface uneven pattern capable of reproducing a two-dimensional and / or three-dimensional image, or an optical diffraction pattern having various optical functions. As this surface unevenness relief structure, a hologram or diffraction grating in which the light intensity distribution of the interference fringes due to the interference between the object light and the reference light is recorded in an uneven pattern can be applied. Holograms include Fresnel holograms, Fraunhofer holograms, lensless Fourier transform holograms, laser reproduction holograms such as image holograms, and white light reproduction holograms such as rainbow holograms, as well as color holograms, computer holograms, holograms using these principles There are displays, multiplex holograms, holographic stereograms, holographic diffraction gratings, computer graphic holograms designed with special optical functions, and so on. These holograms and / or diffraction gratings may be recorded in a single or multiple manner or in combination. Examples of the diffraction grating include a holographic diffraction grating using a hologram recording means. In addition, an arbitrary diffraction light can be obtained based on a calculation by mechanically creating a diffraction grating using an electron beam drawing apparatus or the like. A diffraction grating can also be mentioned.

Also, computer graphic holograms designed with special optical functions have a complex relief structure and a high-definition relief structure, so there is a high possibility that the relief cannot be faithfully formed if the formability is lowered. It is important to shape.
The computer graphic hologram and the computer generated hologram (CGH) are not particularly limited, and examples thereof include a relief structure such as a Fourier transform hologram, a holographic stereogram, a 3D hologram, and a hologram optical element.

  Usually, shaping is performed by pressing (so-called embossing) a stamper (metal plate or resin plate) on which a relief is formed on the surface of the relief forming layer 15 to form the relief on the relief forming layer 15 (replication). ) And then removing the stamper. The stamper that replicates the relief can be used as the master itself, but it may be worn out or damaged. As in analog records, etc., apply metal plating or UV curable resin to the master, and then cure it by irradiating with UV light. By using a method such as peeling (referred to as a 2P method by those skilled in the art), replication is performed with metal or resin, and commercial replication is performed using a replicated mold (stamper).

  The method of commercial duplication is to irradiate the surface of the relief forming layer 15 with a mold or resin type stamper and irradiate ionizing radiation after replicating the relief, or irradiate ionizing radiation during embossing. After that, the relief is duplicated by peeling off the stamper. This commercial duplication can be carried out in a long form, allowing continuous duplication work.

  In the present invention, as described above, the material, thickness, and thickness ratio of the release layer 13 and the relief forming layer 15 are optimized, for example, to emboss-mold a computer graphic hologram computer generated hologram or the like. Even when the stamper is not contaminated, the stamper has good peelability from the relief forming layer 15 and the stamper can be used continuously for a long period of time (repetitive embossing), so that the printing durability is excellent.

(D: Step of irradiating the relief and release layer with ionizing radiation)
The surface of the relief forming layer 15 is irradiated with ionizing radiation during embossing with a stamper, after embossing, or during embossing and after embossing, thereby curing the ionizing radiation curable resin. The ionizing radiation may be classified according to the quantum energy of the electromagnetic wave, but in this specification, all ultraviolet rays (UV-A, UV-B, UV-C), visible light, gamma rays, X-rays, electrons It is defined as including a line. Therefore, ultraviolet rays (UV), visible rays, gamma rays, X-rays, electron beams, etc. can be applied as ionizing radiation, but ultraviolet rays (UV) are suitable from the standpoint of stable technology that can be used with existing equipment. .

(Printer)
A thermal printer (also referred to as a thermal transfer printer) that can preferably use the transfer foil of the present invention will be described, but it goes without saying that it can also be used for conventional hot stamping (foil stamping) by thermal stamping. As the transfer foil of the present invention, a thermal printer for heat transfer that is conventionally used can be used. In the thermal printer, a thermal printing head (also referred to as a thermal head or a printer head) and a platen roller are opposed to each other, and a transfer foil (also referred to as a holo transfer ribbon) of the present invention is interposed between them. Is sandwiched between the transfer target and the transfer target. These are pressed against the thermal head by a rotating platen roller, and travel according to the rotation. The adhesive layer of the transfer foil is opposed to the transfer target.

(Thermal head)
Then, the heating element corresponding to the image of the thermal head generates heat and is selectively heated, and the relief forming layer 15 / reflective layer 17 / adhesive layer 19 is transferred to the transfer target, and a predetermined image is recorded by thermal transfer recording. (Printed). The printing method includes 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 hologram ribbon and the transfer medium are traveling), only a predetermined heating element is heated, and an image is printed on the entire width direction. Note that the predetermined image by thermal transfer is not particularly limited, and examples thereof include letters, numbers, images, illustrations, and photographs.

  As the thermal head, a laser heat mode thermal head, a photothermal recording head, a thermal head, or the like can be applied. The thermal head is the most general thermal head that prints an image by causing a dot-like heating element to generate heat in accordance with an image signal and transferring a transfer layer of a hologram ribbon to a transfer target. In the present invention, any thermal head may be used, and a preferable resolution of the thermal head is a high-definition thermal head having a resolution of 300 dpi or more, and more preferably 600 dpi or more.

  EXAMPLES Hereinafter, although an Example and a reference example demonstrate this invention further in detail, it is not limited to this.

<Creation of urethane (meth) acrylate oligomer>
The urethane (meth) acrylate oligomer used in the composition for relief forming layers of the following examples was prepared under the following conditions.
A reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 206.0 g of ethyl acetate and 133.0 g of a trimer of isophorone diisocyanate (HULS product, VESTANAT T1890, melting point 110 ° C.), 80 The temperature was raised to 0 ° C. to prepare a solution in which the chemical was dissolved. After blowing air into the solution, 0.38 g of hydroquinone monomethyl ether, 249.0 g of pentaerythritol triacrylate (product of Osaka Organic Chemical Industry Co., Ltd., Viscoat 300) and 0.38 g of dibutyltin dilaurate were charged and reacted at 80 ° C. for 5 hours. Then, 689.0 g of ethyl acetate was added and cooled. It was confirmed by infrared absorption spectrum analysis that the absorption of isocyanate groups in the obtained reaction product solution was extinguished. The softening temperature of the solvent distilled from the reaction product solution was 43 ° C.

Example 1
・ <Composition for heat-resistant protective layer>
Silicone-modified acrylic resin (solid content 26%) 10.0 parts (trade name: Polyalloy NSA-X55, manufactured by NATCO)
Toluene / methyl ethyl ketone (mass ratio 1/1) 40.0 parts <Composition for release layer>
40.0 parts of norbornene resin (trade name Arton G, manufactured by JSR) (Tg; 171 ° C.)
Acrylic polyol resin 10.0 parts (trade name Thermolac SU-100A, manufactured by Soken Chemical Co., Ltd.)
Toluene / methyl ethyl ketone (mass ratio 7/3) 50.0 parts <Composition for relief forming layer>
Methacrylic resin 50.0 parts (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
Urethane (meth) acrylate oligomer 50.0 parts (urethane (meth) acrylate oligomer created under the conditions described above)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
Photopolymerization initiator 5.0 parts (Brand name Irgacure 907, manufactured by Ciba Specialty Chemicals)
100 parts of methyl ethyl ketone A polyester terephthalate film (F-53, manufactured by Toray Industries, Inc.) having a thickness of 6 μm was used as a base material. The above composition for a heat-resistant protective layer was applied to one surface of the substrate by a gravure coating method and dried to form a heat-resistant protective layer having a thickness of 0.15 μm. The release layer composition was applied to the base material surface opposite to the heat-resistant protective layer surface with a roll coater so that the thickness after drying was 0.2 μm and dried at 80 ° C. Formed. A relief forming layer composition is applied to the surface of the release layer 13 at a film speed of 50 m / min with a gravure reverse coater so that the thickness after drying is 1.5 μm and dried at 100 ° C. to form a relief. The film 15 obtained by forming the layer 15 is not sticky at room temperature, and can be stored and processed in a wound state. A stamper is pressed (embossed) on the surface of the relief forming layer 15 to form a relief. Separately, a resin stamper duplicated by the 2P method from CGH is attached to the embossing roller of the duplicating machine, and heated and pressed (embossed) between the rollers facing each other at 150 ° C. to give a relief consisting of a fine uneven pattern. Let it shape. Immediately after shaping, the film was cured by irradiating with ultraviolet light with a high-pressure mercury lamp. Aluminum was deposited to a thickness of 40 nm on the relief surface by vacuum deposition to form a reflective relief hologram. Example 1 A maleic acid-vinyl chloride-vinyl acetate copolymer adhesive was applied to the relief surface with a gravure coat and dried at 100 ° C. to form an adhesive layer having a thickness of 0.2 μm. A transfer foil was obtained.

(Examples 2 to 6)
Transfer foils of Examples 2 to 6 were obtained in the same manner as in Example 1 except that the layer thickness of the transfer foil was as shown in Table 1.

(Example 7)
A transfer foil of Example 7 was obtained in the same manner as in Example 1 except that the composition of the relief forming layer composition was as follows.
・ <Composition for relief forming layer>
Methacrylic resin 30.0 parts (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
Urethane (meth) acrylate oligomer 60.0 parts (urethane (meth) acrylate oligomer prepared under the conditions described above.)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
Photopolymerization initiator 5.0 parts (Brand name Irgacure 907, manufactured by Ciba Specialty Chemicals)
100 parts of methyl ethyl ketone

(Example 8)
A transfer foil of Example 8 was obtained in the same manner as in Example 1 except that the composition of the relief forming layer composition was as follows.
・ <Composition for relief forming layer>
Methacrylic resin 60.0 parts (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
Urethane (meth) acrylate oligomer 30.0 parts (urethane (meth) acrylate oligomer prepared under the conditions described above)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
Photopolymerization initiator 5.0 parts (Brand name Irgacure 907, manufactured by Ciba Specialty Chemicals)
100 parts of methyl ethyl ketone

Example 9
A transfer foil of Example 9 was obtained in the same manner as in Example 1 except that the heat-resistant protective layer was not provided.

(Examples 10 to 15)
Transfer foils of Examples 10 to 15 were obtained in the same manner as in Example 1 except that the layer thickness of the transfer foil was as shown in Table 2.

(Example 16)
A transfer foil of Example 16 was obtained in the same manner as in Example 1 except that the thickness of the substrate was 2.5 μm.

(Example 17)
A transfer foil of Example 17 was obtained in the same manner as Example 1 except that the thickness of the substrate was 9.0 μm.

(Example 18)
A transfer foil of Example 18 was obtained in the same manner as in Example 1 except that the composition of the relief forming layer composition was as follows.
・ <Composition for relief forming layer>
Methacrylic resin 25.0 parts (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
Urethane (meth) acrylate oligomer 75.0 parts (a urethane (meth) acrylate oligomer prepared under the conditions described above)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
Photopolymerization initiator 5.0 parts (Brand name Irgacure 907, manufactured by Ciba Specialty Chemicals)
100 parts of methyl ethyl ketone

Example 19
A transfer foil of Example 19 was obtained in the same manner as in Example 1 except that the composition of the relief forming layer composition was as follows.
・ <Composition for relief forming layer>
Methacrylic resin 75.0 parts (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
Urethane (meth) acrylate oligomer 25.0 parts (a urethane (meth) acrylate oligomer prepared under the conditions described above)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
Photopolymerization initiator 5.0 parts (Brand name Irgacure 907, manufactured by Ciba Specialty Chemicals)
100 parts of methyl ethyl ketone

(Comparative Example 1)
A transfer foil of Comparative Example 1 was obtained in the same manner as in Example 1 except that the composition of the release layer composition was as follows.
<Composition for release layer>
Methyl methacrylate resin (Tg; 105 ° C)
(Brand name BR-80, manufactured by Mitsubishi Rayon Co., Ltd.) 6.0 parts Toluene / 2-butanol (mass ratio 1/1) 30.0 parts

(Comparative Example 2)
A transfer foil of Comparative Example 2 was obtained in the same manner as in Example 1 except that the composition of the release layer composition was as follows.
<Composition for release layer>
Polyamideimide resin (Tg; 250 ° C.) 19.0 parts Dimethylacetimide 45.0 parts Toluene 35.0 parts

(Comparative Example 3)
A transfer foil of Comparative Example 3 was obtained in the same manner as in Example 1 except that the composition of the relief forming layer composition was as follows, and after shaping, the step of irradiating and curing with ultraviolet light with a high-pressure mercury lamp was omitted. It was.
・ <Composition for relief forming layer>
100 parts of methacrylic resin (trade name Parapet GF, manufactured by Kuraray Co., Ltd.)
1.0 parts of silicone (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.)
100 parts of methyl ethyl ketone

(Evaluation and evaluation method)
The moldability is obtained by sticking a resin stamper duplicated by the 2P method to the embossing roller of the duplicating machine and running between the opposing rollers at a roll temperature of 150 ° C. and a speed of 10 m / min. It was cured by irradiating ultraviolet rays with a mercury lamp, and a relief composed of a fine uneven pattern was formed. The molding is performed continuously for 1000 m, and the molding at the start and 1000 m is compared. If there is no difference, “pass = ◎” is set, and if there is a slight difference, “pass = ○” is set, The remarkable thing was made into "failure = x". In addition, “failed = x” was defined as a copy of the embossing roller that could not be copied sufficiently under the above-mentioned duplication conditions.
Using a thermal printer with a thermal head (300 dpi, 4500 Ω), the transferability is transferred (printed) to a vinyl chloride card with a pattern of 0.5 mm wide stripes arranged in parallel at intervals of 0.5 mm. evaluated. “Pass = ◎” means that the stripes are clear and the white areas between the stripes are clear, and the stripe has a slight gap, but there is no practical problem and the white areas between the stripes are clear Was “accepted = ◯”, and those in which the stripes were missing or the white portions between the stripes were buried were regarded as “failed = ×”.
The heat resistance was observed in the above transferability evaluation with a 100 × optical microscope, and when the reflection layer was not cracked, “Pass = ◎” was given, but although there was a slight crack, there was no practical problem. The thing was set as "pass = ○", and the thing in which an obvious crack is recognized was set as "failure = x".

(Evaluation results)
The evaluation results are shown in Table 1, Table 2, and Table 3.
In Examples 1 to 8, it was “pass = ◎” in all of formability, transferability, and heat resistance.
In Examples 9 to 19, “accept = ◯” was included in any item of the evaluation items, but the level was practically acceptable.
In Comparative Examples 1 to 3, any of the evaluation items was unacceptable.

It is typical sectional drawing of the transfer foil which shows one Example of this invention. It is typical sectional drawing of the transfer foil which shows one Example of this invention.

Explanation of symbols

1: Transfer foil 11: Base material 13: Release layer 15: Relief forming layer 17: Reflective layer 19: Adhesive layer 21: Heat-resistant protective layer

Claims (13)

  In the transfer foil in which the substrate, the release layer, the relief forming layer, and the reflective layer are laminated in this order, the release layer contains a thermoplastic resin having at least a glass transition temperature of 120 ° C. to 200 ° C., and the relief A transfer foil comprising a cured product of an ionizing radiation curable resin.   The transfer foil according to claim 1, wherein the thermoplastic resin is a cyclic olefin resin.   The transfer foil according to claim 1, wherein the cyclic olefin-based resin is a norbornene-based resin.   The transfer foil according to any one of claims 1 to 3, wherein the relief forming layer is a cured product of an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer.   The urethane (meth) acrylate oligomer is (1) an isocyanate having three or more isocyanate groups in the molecule, (2) a polyfunctional having at least one hydroxyl group and at least two (meth) acryloyloxy groups in the molecule. The transfer foil according to any one of claims 1 to 4, which is a reaction product of (meth) acrylates and (3) polyhydric alcohols having at least two hydroxyl groups in the molecule.   The transfer foil according to claim 4 or 5, wherein the ionizing radiation curable resin is a mixture of a urethane (meth) acrylate oligomer and a methacrylic resin.   The transfer foil according to claim 6, wherein the mass-based ratio of the ionizing radiation curable resin is urethane (meth) acrylate oligomer: methacrylic resin = 1: 2 to 2: 1. The release layer has a thickness of 0.1 to 1.0 μm, and the relief forming layer has a thickness of 0.3 to 2.
The transfer foil according to any one of claims 1 to 7, wherein the transfer foil has a thickness ratio of 5 µm and a release layer to a relief forming layer of 1: 1 to 1:20.   The transfer foil according to any one of claims 1 to 8, wherein the substrate has a thickness of 3.0 to 8.0 µm.   The transfer foil according to claim 1, wherein a heat-resistant protective layer is provided on a surface opposite to the relief forming layer of the base material.   The transfer foil according to claim 1, wherein an adhesive layer is provided on the reflective layer surface.   An image-formed product obtained by thermal transfer to a transfer medium using the transfer foil according to any one of claims 1 to 11.   13. The image formed product according to claim 12, wherein the thermal transfer means is a thermal printer.

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