WO2017057325A1 - 転写箔 - Google Patents
転写箔 Download PDFInfo
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- WO2017057325A1 WO2017057325A1 PCT/JP2016/078386 JP2016078386W WO2017057325A1 WO 2017057325 A1 WO2017057325 A1 WO 2017057325A1 JP 2016078386 W JP2016078386 W JP 2016078386W WO 2017057325 A1 WO2017057325 A1 WO 2017057325A1
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- WIPO (PCT)
- Prior art keywords
- layer
- transfer
- resin
- resins
- adhesion
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B41M5/5281—Polyurethanes or polyureas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/172—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
Definitions
- the present invention relates to a transfer foil.
- an ID card such as an ID card or an IC card such as a bank cash card (hereinafter collectively referred to as a card) has a base material
- An attempt has been made to transfer a transfer layer to the surface of a card using a transfer foil (sometimes referred to as a protective layer transfer sheet) including a transfer layer including a protective layer provided to be peelable from a base material. Yes.
- a transfer foil As a transfer foil, a transfer foil (intermediate transfer medium) provided with a transfer layer in which a protective layer and a receiving layer / adhesive layer are laminated in this order from the substrate side. Is also known). Such a transfer foil is required to have high transferability without causing transfer defects such as tailing and burrs when the transfer layer is transferred. According to the transfer foil proposed in Patent Document 1, by forming a protective layer using urethane-modified acrylate as an ionizing radiation curable resin, the film breakage during transfer and the durability of the protective layer are improved. Has been.
- Transfer of the transfer layer using the transfer foil is performed by applying thermal energy to the back side of the transfer foil and transferring the transfer layer corresponding to the area to which the energy is applied. Transferability is required. That is, there is a demand for a transfer foil that does not cause transfer defects in the transfer layer or does not easily cause transfer defects. Under such circumstances, a transfer foil or the like in which a release layer is provided between the substrate and the transfer layer for the purpose of improving the transferability (sometimes referred to as releasability) of the transfer layer has been proposed. ing.
- the release layer is a layer remaining on the substrate side when the transfer layer is transferred.
- the present invention has been made in view of such a situation, and provides a transfer foil that can improve the transferability of a transfer layer and can impart high durability to a printed material. This is the main issue.
- the present invention for solving the above problems is a transfer foil in which an adhesion layer, a release layer, and a transfer layer are provided in this order on a substrate, and the transfer layer is protected from the substrate side.
- Layer and an adhesive layer are laminated in this order, and the protective layer contains an actinic ray curable resin obtained by curing an actinic ray curable resin with an actinic ray, and the adhesion layer Is characterized by containing a cured binder resin which is a cured product of a binder resin and a curing agent.
- the adhesion layer as the cured binder resin, any one of a cured polyurethane resin obtained by curing a polyurethane resin with a curing agent, and a cured polyvinyl alcohol resin obtained by curing a polyvinyl alcohol resin with a curing agent, Or you may contain both.
- the adhesive layer may be an adhesive layer having a function of a receiving layer.
- the transfer property of the transfer layer can be improved, and extremely high durability can be imparted to the printed material to which the transfer layer has been transferred.
- a transfer foil 100 according to an embodiment of the present invention (hereinafter referred to as a transfer foil according to an embodiment) will be described with reference to the drawings.
- a transfer foil 100 according to an embodiment includes a base material 1, an adhesive layer 7, a release layer 2, and a transfer layer 10, and the adhesive layer 7 and the release layer 2 from the base material 1 side.
- the transfer layer 10 is laminated in this order.
- the transfer layer 10 has a laminated structure in which the protective layer 3 and the adhesive layer 5 are laminated in this order from the substrate 1 side (from the release layer 2 side).
- the transfer foil 100 is a transfer foil used for transferring a transfer layer 10 onto an arbitrary object (hereinafter, referred to as a transfer target) to obtain a printed material with high durability.
- the transfer target is not limited in any way, and examples thereof include a card substrate such as an IC card and an ID card, a thermal transfer image receiving sheet on which a thermal transfer image is formed, and the like. In addition, other materials can be used as the transfer target.
- the base material 1 is an essential configuration in the transfer foil 100 of one embodiment, and the adhesion layer 7, the release layer 2, the transfer layer 10 provided on one surface of the base material 1, and the other of the base material 1. Holds a back layer optionally provided on the surface.
- the material of the substrate 1 is not particularly limited, but has heat resistance that can withstand thermal energy (for example, heat of a thermal head) when the transfer layer 10 is transferred to a transfer target, and the release layer 2 or the transfer layer It preferably has mechanical strength and solvent resistance capable of supporting the layer 10.
- Examples of the material of the substrate 1 include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene.
- Polyester resins such as naphthalate co-extruded films, polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polyacrylates and polymethacrylates Acrylic resins such as acrylate and polymethyl methacrylate, imide resins such as polyimide and polyetherimide, polyarylate, polysulfone , Engineering resins such as polyethersulfone, polyphenylene ether, polyphenylene sulfide (PPS), polyaramid, polyetherketone, polyethernitrile, polyetheretherketone, polyethersulfite, polycarbonate, polystyrene, high impact polystyrene, acrylonitrile / styrene Examples thereof include styrene resins such as copolymers (AS resins) and acrylonitrile / butadiene / styrene copo
- the base material 1 may be a copolymer resin or a mixture (including an alloy) containing the resin exemplified above as a main component, or a laminate composed of a plurality of layers.
- a base film may be a stretched film or an unstretched film, it is preferable to use a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength.
- the substrate 1 is used as a film, sheet, or board formed of at least one layer of these resins.
- polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their excellent heat resistance and mechanical strength, and among these, polyethylene terephthalate films are more preferable.
- irregularities can be imparted to the surface of the substrate as necessary.
- means for forming irregularities on the substrate include a matting agent kneading process, a sandblasting process, a hairline process, a mat coating process, and a chemical etching process.
- the matting agent kneading process is a processing method of forming a base material with a resin kneaded with an inorganic substance or an organic substance.
- the mat coating process is a processing method in which a coating agent containing an organic substance or an inorganic substance is coated on the surface of a base material, and unevenness is imparted to the surface of the base material.
- the thickness of the base material 1 It is preferable that it is the range of 0.5 micrometer or more and 50 micrometers or less, and it is more preferable that it is the range of 4 micrometers or more and 20 micrometers or less.
- the thermal energy when transferring the transfer layer 10 from the transfer foil 100 can be sufficiently transmitted to the transfer layer side, and transferability when transferring the transfer layer can be improved. Further improvement can be achieved. Further, the mechanical strength of the substrate 1 can be increased, and the transfer layer 10 can be sufficiently supported.
- the surface of the substrate 1 on the side in contact with the adhesion layer 7 is previously subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) coating treatment, pre-heat treatment.
- corona discharge treatment plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) coating treatment, pre-heat treatment.
- primer also called an anchor coat, adhesion promoter, or easy adhesive coating treatment
- pre-heat treatment pre-heat treatment.
- easy adhesion treatment such as dust removal treatment, vapor deposition treatment, alkali treatment, and application of an antistatic layer may be performed.
- a release layer 2 is provided between the adhesion layer 7 and the transfer layer 10.
- the release layer 2 is an essential component in the transfer foil 100 of one embodiment, and is a layer for the purpose of improving transferability (sometimes referred to as release property) when the transfer layer 10 is transferred.
- the release layer 2 is a layer that does not constitute a transfer layer 10 to be described later, and the release layer 2 is a layer that remains on the substrate 1 side when the transfer layer 10 is transferred onto the transfer target. .
- the resin used for the release layer 2 is not particularly limited, and a conventionally known resin having releasability can be appropriately selected and used.
- releasable resins include waxes, silicone waxes, silicone resins, various silicone-modified resins such as silicone-modified acrylic resins, fluorine resins, fluorine-modified resins, polyvinyl alcohol, acrylic resins, and heat-crosslinkable epoxy-amino. Examples thereof include resins and thermally crosslinkable alkyd-amino resins, melamine resins, cellulose resins, urea resins, polyolefin resins, acrylic resins, and fiber resins.
- the release layer 2 may contain one kind of resin alone or may contain two or more kinds of resins.
- the release layer 2 may be formed by using a cross-linking agent such as an isocyanate compound, a catalyst such as a tin-based catalyst, and an aluminum-based catalyst in addition to a resin having releasability.
- the silicone-modified acrylic resin is a preferred resin in that the adhesion between the release layer 2 and the adhesion layer 7 described later can be further improved.
- the thickness of the mold release layer 2 It is preferable that it is the range of 0.1 micrometer or more and 5 micrometers or less, and it is more preferable that it exists in the range of 0.5 micrometer or more and 2 micrometers or less.
- the method for forming the release layer 2 is not particularly limited, and a release layer coating solution obtained by dispersing or dissolving the resin exemplified above in an appropriate solvent can be formed by a known coating method such as roll coating or gravure coating. It can be formed by applying and drying on the adhesion layer 7 and baking at a temperature of about 150 ° C. or higher and 200 ° C. or lower.
- a transfer layer 10 is provided on the release layer 2.
- the transfer layer 10 is provided so as to be peelable from the substrate 1 and is a layer that moves onto the transfer target during thermal transfer.
- the transfer layer 10 has a laminated structure in which the protective layer 3 and the adhesive layer 5 are laminated in this order from the substrate 1 side.
- the protective layer 3 and the adhesive layer 5 are essential components in the transfer foil 100 of one embodiment.
- the protective layer 3 included in the transfer layer 10 is a layer for imparting durability to a printed material obtained by transferring the transfer layer 10 onto a transfer target.
- the protective layer 3 is located closest to the substrate 1 among the layers constituting the transfer layer 10, and is on the outermost surface in the printed matter obtained by transferring the transfer layer 10 onto the transfer target. It becomes a layer to be located.
- the protective layer 3 for imparting durability to the printed material is obtained by irradiating an actinic ray curable resin with an actinic ray curable resin obtained by curing an actinic ray curable resin with an actinic ray, that is, actinic ray curable resin.
- Actinic ray curable resin in other words, actinic ray curable resin which is a reaction product of actinic ray curable resin and actinic ray (hereinafter, actinic ray curable resin obtained by curing actinic ray curable resin with actinic rays) This is referred to as an actinic ray curable resin).
- the actinic ray curable resin referred to in the present specification means a precursor or composition before irradiation with actinic rays.
- the actinic ray in the present specification means radiation that chemically acts on the actinic ray curable resin to promote polymerization, and specifically, visible light, ultraviolet ray, X-ray, electron beam. , ⁇ ray, ⁇ ray, ⁇ ray and the like.
- the protective layer 3 containing an actinic ray curable resin extremely high durability can be imparted to the printed matter obtained by transferring the transfer layer 10 onto the transfer target.
- the durability mentioned here includes not only physical durability such as scratch resistance but also chemical durability such as solvent resistance and plasticizer resistance. That is, according to the transfer foil 100 of one embodiment, a printed matter excellent in both physical durability and chemical durability can be obtained by transferring the transfer layer 10 onto the transfer target.
- An actinic ray curable resin as an example includes, as a polymerization component, a polymer, a prepolymer, an oligomer, and / or a polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group and a (meth) acryloyloxy group or an epoxy group in a molecule. Or the composition etc. which mixed the monomer suitably are included.
- an actinic ray curable resin as an example includes urethane (meth) acrylate as a polymerization component.
- urethane (meth) acrylate it is preferable to comprise polyfunctional urethane (meth) acrylate.
- the polyfunctional urethane (meth) acrylate is preferably a urethane (meth) acrylate having 5 to 15 functional groups, and more preferably a urethane (meth) acrylate having 6 to 15 functional groups.
- the protective layer 3 preferably contains a polyfunctional urethane (meth) acrylate in a range of 5% by mass to 80% by mass with respect to the total solid content of the protective layer 3, and is preferably 10% by mass to 50% by mass. It is more preferable to contain in the range below%.
- the protective layer 3 is composed of a urethane (meth) acrylate having 2 or more and 4 or less functional groups together with the polyfunctional urethane (meth) acrylate. It is preferable that either or both of (meth) acrylates having 2 to 5 bases are contained.
- the protective layer 3 has either a urethane (meth) acrylate having a functional group number of 2 or more and 4 or less, a (meth) acrylate having a functional group number of 2 or more and 5 or less, or both of the solid content of the protective layer 3. It is preferable to contain in the range of 5 mass% or more and 80 mass% or less with respect to the total amount, and it is more preferable to contain in the range of 10 mass% or more and 70 mass% or less.
- the mass average molecular weight (Mw) of the polyfunctional urethane (meth) acrylate and the urethane (meth) acrylate having 2 to 4 functional groups is preferably in the range of 400 to 20000, more preferably 500. It is the range of 10,000 or less.
- the mass average molecular weight (Mw) of the urethane (meth) acrylate is within the above numerical range, the wear resistance can be improved.
- the mass average molecular weight (Mw) of the (meth) acrylate having 2 to 5 functional groups is preferably in the range of 200 to 5000.
- Mw mass average molecular weight
- the protective layer 3 may also contain an unsaturated bond-containing (meth) acrylic copolymer as a polymerization component.
- unsaturated bond-containing (meth) acrylic copolymer include polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate.
- the acid value of the unsaturated bond-containing (meth) acrylic copolymer is preferably in the range of 5 mgKOH / g to 500 mgKOH / g, more preferably in the range of 10 mgKOH / g to 150 mgKOH / g.
- the transfer layer 10 having high surface strength can be obtained.
- “acid value” means the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of polymer, and conforms to JIS-K-2501 (2003). It can be measured by the method.
- the acid value of the polymer can be adjusted as appropriate by adjusting the ratio of monomer components constituting the polymer.
- the mass average molecular weight (Mw) of the unsaturated bond-containing (meth) acrylic copolymer is preferably in the range of 3000 to 100,000, more preferably in the range of 10,000 to 80,000.
- chemical durability such as heat resistance and chemical resistance, and physical durability such as scratch strength can be further improved.
- mass average molecular weight (Mw) within this range, it is possible to suppress the occurrence of a gelling reaction during the storage of the protective layer coating liquid for forming the protective layer. The storage stability of the coating liquid can be improved.
- the unsaturated bond-containing (meth) acrylic copolymer described above is preferably contained in the actinic ray curable resin in the range of 10% by mass to 80% by mass, and 20% by mass to 70% by mass. More preferably, it is contained in the range of 20 mass% or more and 50 mass% or less.
- actinic ray curable resin is not limited to (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta It may contain oligomers and / or monomers such as erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide and acrylonitrile. Moreover, the following prepolymers, oligomers and / or monomers may be included.
- prepolymer examples include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelin.
- Polybasic acids such as acid, sebacic acid, dodecanoic acid and tetrahydrophthalic acid, ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by the coupling of a polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol.
- a polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol.
- Ter (meth) acrylates for example, epoxy (meth) acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid
- an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid
- an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid
- an epoxy resin such as bisphenol A, epichlorohydrin, (meth) acrylic acid, phenol novolac, epichlorohydrin, (meth) acrylic acid
- Examples of the monomer or oligomer include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide.
- acrylate of ⁇ -caprolactone adduct of 1,3-dioxane alcohol monofunctional acrylic ester such as 1,3-dioxolane acrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diacrylate Triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypentylate neopentyl glycol diacrylate, neopentyl glycol Diacrylate of adipate, diacrylate of ⁇ -caprolactone adduct of neopentyl glycol hydroxypivalate, 2-
- content of actinic-light curable resin when higher durability is calculated
- the protective layer 3 may contain other resins together with the actinic ray curable resin.
- Other resins may be cured by a curing agent or the like, or may be uncured.
- the protective layer 3 may contain other components together with the actinic ray curable resin. Examples of other components include a filler. By including a filler in the protective layer 3, the foil breakability of the transfer layer 10 can be improved.
- fillers examples include organic fillers, inorganic fillers, and organic-inorganic hybrid fillers.
- the filler may be a powder or a sol, but since the selectivity of the solvent when preparing the protective layer coating solution is wide, a powder filler may be used. preferable.
- the filler contained in the protective layer 3 is preferably a filler having a volume average particle size of 1 nm to 200 nm, more preferably a filler having a volume average particle size of 1 nm to 50 nm, and a volume average particle size of More preferably, the filler is 7 nm or more and 25 nm or less.
- “Volume average particle diameter” means a volume average particle diameter measured in accordance with JIS-Z-8819-2 (2001). It can be measured by a known method using an apparatus, Nikkiso Co., Ltd.).
- Examples of the organic filler in powder include acrylic particles such as non-crosslinked acrylic particles and crosslinked acrylic particles, polyamide particles, fluorine particles, and polyethylene wax.
- Examples of the powdery inorganic filler include metal carbonate particles such as calcium carbonate particles, silica particles, and titanium oxide.
- Examples of the organic-inorganic hybrid filler include those obtained by hybridizing silica particles to an acrylic resin.
- examples of the sol filler include silica sol type and organosol type fillers. These fillers may be used alone or in combination of two or more.
- the filler is preferably contained in the protective layer 3 in a range of 3% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 45% by mass or less. More preferably, it is contained in the range of not less than 40% and not more than 40% by mass.
- the thickness of the protective layer 3 it is preferable that they are 1 micrometer or more and 8 micrometers or less, and it is preferable that they are 2 micrometers or more and 6 micrometers or less.
- the thickness of the protective layer 3 it is preferable that they are 1 micrometer or more and 8 micrometers or less, and it is preferable that they are 2 micrometers or more and 6 micrometers or less.
- a coating liquid for protective layers which consists of a composition containing actinic-light curable resin and arbitrary components is roll coat, reverse roll coat, gravure coat, reverse gravure coat
- a coating film is formed, and the polymerization components such as the above-mentioned polymerizable copolymer are crosslinked and cured by actinic rays. Can be formed.
- a conventionally known ultraviolet irradiation device can be used for the irradiation of ultraviolet rays, and various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED are used without limitation. be able to.
- the electron beam irradiation may be performed using either a high energy type electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV to 300 keV or a low energy type electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or less.
- the irradiation method may be either a scanning type or a curtain type irradiation device.
- an adhesive layer 5 is provided on the protective layer 3.
- the adhesive layer 5 constitutes the transfer layer 10 and is a layer for bringing the transfer target body and the transfer layer 10 into close contact when the transfer layer 10 is transferred onto the transfer target body. Therefore, in the transfer foil 100 of one embodiment, the adhesive layer 5 is a layer located on the outermost surface.
- the adhesive layer 5 may have a function as a receiving layer capable of receiving the dye of the dye layer.
- a thermal transfer image is formed by forming a thermal transfer image on the adhesive layer 5 located on the outermost surface of the transfer foil 100 of one embodiment by a thermal transfer sheet having a dye layer.
- the printed material can be obtained by transferring the transfer layer 10 including the adhesive layer 5 onto the transfer target.
- the material of the adhesive layer 5 is not particularly limited, and an adhesive material can be appropriately selected and used.
- the adhesive material include ionomer resins, acid-modified polyolefin resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, polyester resins, polyamide resins, 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, melamines -Alkyd resins, cellulose resins, polyurethane resins, polyvinyl ether resins, silicone resins, rubber resins and the like.
- the adhesive layer 5 may contain one kind of material alone, or may contain two or more kinds of materials.
- vinyl resins, acrylic resins, butyral resins, and polyester resins having high adhesion are preferable. More preferred are vinyl resins, acrylic resins, ethylene- (meth) ethyl acrylate copolymers, and acrylic ester copolymers.
- a conventionally known resin material that can easily receive a heat transferable coloring material such as a sublimable dye or a heat-meltable ink can be used.
- polyolefin resin such as polypropylene, halogenated resin such as polyvinyl chloride or polyvinylidene chloride, vinyl acetate, vinyl chloride-vinyl acetate polymer, ethylene-vinyl acetate copolymer or vinyl such as polyacrylate Resins, polyester resins such as polyethylene terephthalate or polybutylene terephthalate, polystyrene resins, polyamide resins, copolymers of olefins such as ethylene or propylene and other vinyl polymers, cellulose resins such as ionomers or cellulose diastases, Examples include polycarbonate, and among these, vinyl chloride-vinyl acetate polymer or polyvinyl chloride resin is preferable, and vinyl chloride-vinyl acetate polymer is particularly preferable. .
- the thickness of the adhesive layer is not particularly limited, but is preferably in the range of 0.1 ⁇ m to 10 ⁇ m, and more preferably in the range of 0.3 ⁇ m to 3 ⁇ m.
- the adhesive layer 5 is formed by dissolving or dispersing one or a plurality of materials selected from the above-mentioned materials and various additives added as necessary in an appropriate solvent such as water or an organic solvent. It can be formed by applying and drying on the protective layer 3 by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate.
- a receiving layer can be further provided between the adhesive layer 5 and the protective layer 3 (not shown).
- the thickness of the receiving layer is preferably in the range of 0.5 ⁇ m to 10 ⁇ m, and more preferably in the range of 1 ⁇ m to 3 ⁇ m.
- the transfer foil 100 has the protective layer 3 containing an actinic ray curable resin positioned closest to the release layer 2 side among the layers constituting the transfer layer 10.
- the durability of the protective layer 3 is improved, and the release property 2 is provided at a position in contact with the transfer layer 10 to improve the transferability when the transfer layer 10 is transferred.
- the coating solution for the protective layer containing the actinic ray curable resin is applied on the release layer 2 and dried to form a coating film, and then with actinic rays.
- the protective layer 3 is formed by crosslinking and curing the coating film.
- the release layer 2 and the coating film are crosslinked and cured at the time of crosslinking and curing of the coating film with actinic rays.
- the transfer layer 10 is transferred onto the transfer target, the release layer 2 that should remain on the substrate 1 side is the transfer layer. 10 is likely to cause abnormal transfer that moves to the transfer target side.
- an adhesion layer 7 is provided between the substrate 1 and the release layer 2 in order to suppress unintended transfer of the release layer.
- a cured binder resin that is a cured product of a binder resin and a curing agent in other words, a cured resin obtained by allowing a curing agent to act on the binder resin, that is, a cured resin obtained by curing the binder resin with a curing agent (
- a cured resin obtained by causing a curing agent to act on the binder resin is referred to as a cured binder resin).
- adherence layer 7 may contain 1 type of hardening binder resin independently, and may contain 2 or more types of hardening binder resin.
- the adhesion between the base material 1 and the adhesion layer 7 and the adhesion between the adhesion layer 7 and the release layer 2 can be improved, in other words.
- the adhesion between the substrate 1 and the release layer 2 can be improved.
- the adhesive layer 7 containing the cured binder resin between the base material 1 and the release layer 2 the adhesive force between the release layer 2 and the adhesive layer 7 is increased. 2 and the protective layer 3 can be made higher than the adhesive force, whereby unintended transfer of the release layer 2 can be suppressed.
- a layer containing a cured binder resin obtained by curing a binder resin with a curing agent is more than a layer containing an actinic ray curable resin obtained by crosslinking and curing an actinic ray curable resin using actinic rays. This is because the adhesion can be increased.
- the binder resin for obtaining the cured binder resin is not particularly limited, and may be a water-based binder resin or a solvent-based binder resin.
- water-based binder resins include polyvinyl pyrrolidone resin, polyvinyl alcohol resin, polyacrylic acid, polyhydroxyethyl acrylate, water-soluble (or water-dispersed) polyester resin, water-soluble (or water-dispersed) polyurethane resin, and water-dispersible chloride.
- Examples include vinyl resins, water-dispersible acrylic chloride resins, water-dispersible epoxy resins, gelatin, hydroxyethyl cellulose resins, hydroxypropyl cellulose resins, carboxymethyl cellulose, and the like.
- the aqueous binder resin means a water-soluble resin or a resin that is insoluble in an aqueous solvent but can be dispersed in an aqueous solvent, such as an emulsion or a dispersion.
- aqueous solvent include water and a mixed solvent of water and alcohol.
- Solvent-based binder resins include polyurethane resins, polyolefin resins, halogenated resins such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymer Examples include coalescence, polyvinyl butyral, polyester resin, polystyrene resin, polyamide resin, cellulose resin, polycarbonate, and acrylic resin.
- the solvent-based binder resin means a resin that can be dissolved or dispersed in an organic solvent.
- organic solvent for dissolving or dispersing the solvent-based binder resin examples include hydrocarbon solvents such as hexane and pentane, aromatic solvents such as xylene, toluene and benzene, ketone solvents such as methyl ethyl ketone and acetone, Examples thereof include alcohol solvents such as propanol, ethanol and methanol, or mixed solvents thereof.
- the resin contained in the release layer 2 is a solvent-based resin, in other words, on the adhesion layer 7, a release layer coating solution in which a solvent-based resin is dissolved or dispersed in an organic solvent is used.
- a release layer coating solution in which a solvent-based resin is dissolved or dispersed in an organic solvent is used.
- the release layer 2 it is more preferable to use an aqueous binder resin as the binder resin for obtaining the cured binder resin contained in the adhesion layer 7.
- the resin contained in the release layer 2 is a water-based resin
- the curing agent for obtaining the cured binder resin is not particularly limited, and may be appropriately selected according to the binder resin used.
- the curing agent include isocyanate curing agents, urethane curing agents, epoxy curing agents, melamine curing agents, urea resin curing agents, silane coupling agents, titanium chelating agents, zirconium chelating agents, aluminum chelating agents, and the like. And metal chelating agents.
- the adhesive layer 7 in a preferred form is either a cured polyvinyl alcohol resin that is a cured product of a polyvinyl alcohol resin and a curing agent, and a cured polyurethane resin that is a cured product of a polyurethane resin and a curing agent, or Contains both.
- it contains either or both of a cured polyvinyl alcohol resin obtained by curing a polyvinyl alcohol resin with a curing agent and a cured polyurethane resin obtained by curing a polyurethane resin with a curing agent.
- the adhesion layer 7 containing a cured polyvinyl alcohol resin and a cured polyurethane resin transfer stability can be improved, and unintended transfer of the release layer 2 due to the excellent adhesion. Can be sufficiently suppressed, and tailing that may occur when the transfer layer 10 is transferred can also be suppressed. Note that tailing refers to a transfer layer that starts from the boundary between the transfer region and the non-transfer region of the transfer layer 10 and protrudes from the boundary to the non-transfer region side when the transfer layer 10 is transferred onto the transfer target. This means a phenomenon in which 10 is transferred.
- the polyvinyl alcohol resin referred to in the present specification means a resin containing a vinyl alcohol polymer as a constituent element thereof, which may be a homopolymer of vinyl alcohol or a copolymer with other polymerization components. May be.
- the copolymer of vinyl alcohol and another polymerization component as a polyvinyl alcohol-type resin, it is preferable that the copolymerization ratio of the vinyl alcohol in the said copolymer is 50% or more.
- denatured polyvinyl alcohol partially can also be used as a polyvinyl alcohol-type resin.
- the polyurethane-type resin said by this-application specification means resin containing the polymer obtained by reacting a diisocyanate compound and a diol compound.
- curing agent for obtaining hardening binder resin It can set suitably according to the binder resin and hardening agent to be used.
- the binder resin and hardening agent for example, when a reactive resin having a functional group that reacts with the curing agent is used as the binder resin, the equivalent ratio of the total number of functional groups of the curing agent to the total number of functional groups of the reactive resin is 0. It is preferable to set the blending amount of the binder resin and the curing agent so as to be 5 or more and 5 or less.
- the reactive resin having a functional group that reacts with the curing material a polyurethane-based resin having a carboxy group is preferable.
- polyvinyl with respect to the total mass of a polyvinyl alcohol-type resin and a titanium chelating agent is used. It is preferable to set the blending amount of the binder resin and the curing agent so that the content of the alcohol resin is in the range of 40% to 90%. Further, when a polyurethane resin is used as the binder resin and a silane coupling agent is used as the curing agent, the total number of functional groups of the silane coupling agent relative to the total number of functional groups of the polyurethane resin, etc. It is preferable to set the blending amounts of the binder resin and the curing agent so that the quantitative ratio is about 0.5 or more and 5 or less.
- the content of the cured binder resin is not particularly limited, but the mass of the cured binder resin relative to the total mass of the adhesion layer 7 (the total mass when containing two or more cured binder resins) is 50% by mass or more. Is preferred. By setting the content of the cured binder resin to 50% by mass or more, the adhesion between the release layer 2 and the adhesion layer 7 can be further improved.
- the upper limit is not limited and is 100% by mass.
- adherence layer 7 it is preferable that it is the range of 0.02 micrometer or more and 3 micrometers or less. By making the thickness of the adhesion layer 7 within this range, the adhesion with the release layer 2 can be further improved. In addition, a stable adhesion layer can be formed.
- the adhesion layer 7 may contain an optional component together with the cured binder resin, if necessary.
- adhesion layer 7 forms by preparing coating liquid for adhesion layers containing binder resin and a hardening agent, and applying and drying this coating liquid for adhesion layers on substrate 1. be able to.
- a back layer (not shown) for the purpose of improving heat resistance, running property, etc. can be provided on the surface of the substrate 1 opposite to the surface on which the transfer layer 10 is provided.
- a back layer is the arbitrary structures in the transfer foil 100 of one Embodiment.
- the back layer can be formed by appropriately selecting a conventionally known thermoplastic resin or the like.
- thermoplastic resins include polyester resins, polyacrylic ester resins, polyvinyl acetate resins, styrene acrylate resins, polyurethane resins, polyethylene resins, polypropylene resins, and other polyolefin resins.
- Polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polyimide resin, polyamide imide resin, polycarbonate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin, polyvinyl acetoacetal resin examples thereof include thermoplastic resins such as polyvinyl acetal resin, and modified silicones thereof.
- the back layer is made of wax, higher fatty acid amide, phosphate ester compound, metal soap, silicone oil, release agent such as surfactant, organic powder such as fluororesin, silica, clay for the purpose of improving the slip property. It is preferable that various additives such as inorganic particles such as talc and calcium carbonate are contained, and it is particularly preferable that at least one of phosphate ester or metal soap is contained.
- the back layer is formed, for example, by applying a coating solution for the back layer, in which the above thermoplastic resin and various additives added as necessary are dispersed or dissolved in an appropriate solvent, onto the substrate 1, gravure printing, screen It can be formed by coating and drying by a known means such as a printing method or a reverse roll coating printing method using a gravure plate.
- the thickness of the back layer is preferably in the range of 0.1 ⁇ m to 5 ⁇ m, more preferably in the range of 0.3 ⁇ m to 2.0 ⁇ m, from the viewpoint of improving heat resistance and the like.
- a known transfer method may be used, for example, hot stamping by hot stamping (foil stamping), entire surface by a hot roll or A known method such as stripe transfer or a thermal printer (also referred to as a thermal transfer printer) using a thermal head (thermal printing head) can be applied.
- the material to be transferred is not particularly limited as long as the application requires durability such as wear resistance and plasticizer resistance.
- natural fiber paper, coated paper, tracing paper, and heat at the time of transfer Any material such as plastic film, glass, metal, ceramics, wood, cloth or dye-receptive medium that does not deform may be used.
- the transfer foil 100 of one embodiment does not include a receiving layer, the surface to which the transfer layer 10 of the transfer object is transferred is Generally, a print layer, a hologram layer, or the like is provided.
- the part is the blending amount
- the component in which the solid content is described is obtained by multiplying the blending amount (part) by the solid content (%) in the coating liquid. It becomes the mass (solid content) of the component.
- Tg means the glass transition temperature.
- Example 1 On a 12 ⁇ m-thick polyethylene terephthalate (PET) film, an adhesion layer coating solution 1 having the following composition was applied so that the thickness upon drying was 0.2 ⁇ m to form an adhesion layer. Subsequently, a release layer was formed on the adhesion layer by applying a release layer coating solution having the following composition to a thickness of 1 ⁇ m when dried. Next, a protective layer coating liquid having the following composition is applied onto the release layer by gravure coating and dried to a thickness of 6 ⁇ m, and then dried, and then exposed to a UV exposure device (Fusion UV, F600V, LH10).
- a UV exposure device Fusion UV, F600V, LH10
- a protective layer was formed by irradiating with ultraviolet rays using a lamp, H bulb, and reflector (cold type).
- a coating solution for receiving layer and adhesive layer having the following composition by gravure coating, the thickness after drying is 2 ⁇ m, and drying to form a receiving layer and adhesive layer,
- a transfer foil of Example 1 in which an adhesion layer, a release layer, and a transfer layer were laminated in this order on a substrate was obtained.
- the transfer layer which comprises the transfer foil of an Example and a comparative example means the laminated body of a protective layer and a receiving layer and adhesion layer.
- ⁇ Coating fluid for receiving layer and adhesive layer > ⁇ 95 parts of vinyl chloride-vinyl acetate copolymer (Solvain (registered trademark) CNL Nissin Chemical Industry Co., Ltd.) ⁇ Epoxy-modified silicone oil 5 parts (KP-1800U Shin-Etsu Chemical Co., Ltd.) ⁇ Toluene 200 parts ⁇ Methyl ethyl ketone 200 parts
- Example 2 In place of the adhesive layer coating solution 1, the adhesive layer coating solution in which the amount of the epoxysilane compound (WSA950 DIC Corporation) in the adhesive layer coating solution 1 is changed from 0.2 part to 0.1 part. Except that the adhesion layer was formed using the liquid 2, the transfer foil of Example 2 in which the adhesion layer, the release layer, and the transfer layer were laminated in this order on the substrate in the same manner as in Example 1. Got.
- Example 3 In place of the adhesive layer coating solution 1, the adhesive layer coating solution in which the amount of the epoxysilane compound (WSA950 DIC Corporation) in the adhesive layer coating solution 1 is changed from 0.2 part to 0.4 part. Except that the adhesion layer was formed using the liquid 3, the transfer foil of Example 3 in which the adhesion layer, the release layer, and the transfer layer were laminated in this order on the substrate in the same manner as in Example 1. Got.
- Example 4 Except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution 4 having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order on the substrate in the same manner as in Example 1. A laminated transfer foil of Example 4 was obtained.
- Example 5 In place of the adhesive layer coating solution 1, a titanium chelating agent (as a curing agent) of the adhesive layer coating solution 4 (solid content: 42%) (Orgax (registered trademark) TC-300 Matsumoto Fine Chemical Co., Ltd.) Except that the adhesion layer was formed using the adhesion layer coating liquid 5 in which the blending amount was changed from 2.55 parts to 5 parts, the adhesion layer and the mold release were formed on the substrate in the same manner as in Example 1. A transfer foil of Example 5 in which the layers and the transfer layer were laminated in this order was obtained.
- Example 6 Except for changing the adhesive layer coating solution 1 to the adhesive layer coating solution 6 having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order on the substrate in the same manner as in Example 1. A laminated transfer foil of Example 6 was obtained.
- ⁇ Coating liquid 6 for adhesion layer Polyvinyl alcohol resin (degree of polymerization 1700) 1.81 parts (Kuraray Poval (registered trademark) PVA-117 Kuraray Co., Ltd.) ⁇ Titanium chelating agent (as curing agent) (solid content 42%) 4.7 parts (Orgatechs (registered trademark) TC-300 Matsumoto Fine Chemical Co., Ltd.) Water-based polyurethane (solid content 22.5%) 1.94 parts (Hydran (registered trademark) AP-40 DIC Corporation) ⁇ Antistatic agent (solid content: 30.4%) 2.55 parts (Chemist (registered trademark) 6120 Sanyo Chemical Industries, Ltd.) ⁇ Water 44.5 parts ⁇ Denatured ethanol 44.5 parts
- Example 7 Except for changing the adhesive layer coating solution 1 to the adhesive layer coating solution 7 having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order on the substrate in the same manner as in Example 1. A laminated transfer foil of Example 7 was obtained.
- Comparative Example 1 A transfer foil of Comparative Example 1 was obtained in which a release layer and a transfer layer were laminated in this order on a substrate in the same manner as Example 1 except that the adhesion layer was not formed.
- Comparative Example 2 Except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution A having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order in the same manner as in Example 1. A laminated transfer foil of Comparative Example 2 was obtained.
- Comparative Example 3 Except for changing the adhesive layer coating solution 1 to the adhesive layer coating solution B having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order in the same manner as in Example 1. A laminated transfer foil of Comparative Example 3 was obtained.
- Comparative Example 4 Except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution C having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order on the substrate in the same manner as in Example 1. A laminated transfer foil of Comparative Example 4 was obtained.
- Polyester resin number average molecular weight: 3000, Tg: 53 ° C.
- Byron registered trademark 220 Toyobo Co., Ltd.
- Methyl ethyl ketone 100 parts
- Toluene 100 parts
- Comparative Example 5 Except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution D having the following composition, the adhesive layer, the release layer and the transfer layer were formed in this order in the same manner as in Example 1. A laminated transfer foil of Comparative Example 5 was obtained.
- Polyester resin number average molecular weight: 3000, Tg: 90 ° C. 15 parts (Byron (registered trademark) 700 Toyobo Co., Ltd.) ⁇ Methyl ethyl ketone 100 parts ⁇ Toluene 100 parts
- Comparative Example 6 Except that the adhesive layer coating solution 1 was changed to the adhesive layer coating solution E having the following composition, the adhesive layer, the release layer, and the transfer layer were formed in this order on the substrate in the same manner as in Example 1. A laminated transfer foil of Comparative Example 6 was obtained.
- Polyester resin number average molecular weight: 20000, Tg: 61 ° C.
- solid content 30% 15.21 parts
- Vinyl (registered trademark) MD-1245 Toyobo Co., Ltd.) ⁇ Water 42.4 parts ⁇ 2-propanol 42.39 parts
- Comparative Example 7 Except for changing the adhesion layer coating solution 1 to the adhesion layer coating solution F having the following composition, the adhesion layer, the release layer, and the transfer layer were formed in this order in the same manner as in Example 1. A laminated transfer foil of Comparative Example 7 was obtained.
- ⁇ Coating fluid F for adhesion layer > ⁇ Carboxyl group-containing urethane resin (solid content: 35%) 6 parts (Hydran (registered trademark) AP40N DIC Corporation) ⁇ 10 parts of water ⁇ 50 parts of denatured ethanol
- Comparative Example 8 Except for changing the adhesion layer coating solution 1 to the adhesion layer coating solution G having the following composition, the adhesion layer, the release layer, and the transfer layer were formed in this order in the same manner as in Example 1. A laminated transfer foil of Comparative Example 8 was obtained.
- the transfer foils of the examples and comparative examples were molded to a width of 65 mm, and the molded transfer foils of the examples and comparative examples were heated on a hot stage (HP2000 Shinto Kagaku Co., Ltd.) adjusted to 70 ° C.
- the surfaces of the hot stage and the transfer layers of the transfer foils of Examples and Comparative Examples were bonded using a transparent double-sided tape (Nystack NW-15 15 mm Nichiban Co., Ltd.).
- the transfer layer of the thermal transfer sheet is peeled off at a peeling angle of 90 ° and a peeling speed of 5 mm / sec, and peeling is started.
- the peel force from the starting point to a position 15 mm away (peel length 10 mm) from a position 5 mm away in the peel direction was measured using a round spring tension gauge, and the peel force within this peel length range The average value of was calculated.
- the average value of the peeling force was calculated three times for each of the transfer foils of Examples and Comparative Examples. In the calculation of the average value of the three peeling forces, the peeling force A is the average value of the peeling force having the largest value, the peeling force C is the average value of the peeling force having the smallest value, and the peeling value is intermediate.
- Evaluation criteria A: The fluctuation value of the peeling force is 1 or more and less than 1.75, and the average values of the peeling force A, the peeling force B, and the peeling force C are 20 g or more and less than 100 g.
- NG The variation value of the peeling force is 1.75 or more, or the average value of the peeling force A, the peeling force B, and the peeling force C is 200 g or more.
- Tailing evaluation The printed matter of each Example and Comparative Example was visually confirmed, and tailing evaluation was performed based on the following evaluation criteria. The evaluation results are shown in Table 1.
- B Trailing occurs (greater than 1 mm and 2 mm or less).
- NG There is considerable tailing (greater than 2 mm).
- Evaluation criteria A: The surface state after 3000 cycles is good. B: The surface state after 2000 cycles was good, but the surface state after 3000 cycles was not good. C: Although the surface state after 1000 cycles is not good, it is at a level where there is no practical problem. NG: The surface state after 100 cycles is not good.
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Abstract
Description
以下、本発明の一実施形態の転写箔100(以下、一実施形態の転写箔と言う)について図面を参照して説明する。図1に示すように、一実施形態の転写箔100は、基材1、密着層7、離型層2、及び転写層10を備え、基材1側から、密着層7、離型層2、転写層10がこの順で積層されてなる。また、転写層10は、基材1側から(離型層2側から)保護層3、接着層5がこの順で積層されてなる積層構成を呈している。
基材1は、一実施形態の転写箔100における必須の構成であり、基材1の一方の面上に設けられる密着層7、離型層2、転写層10や、基材1の他方の面上に任意に設けられる背面層を保持する。
図1に示すように密着層7と転写層10との間には、離型層2が設けられている。離型層2は、一実施形態の転写箔100における必須の構成であり、転写層10を転写するときの転写性(離型性と言う場合もある)の向上を目的とする層である。なお、離型層2は、後述する転写層10を構成しない層であり、離型層2は、被転写体上に転写層10を転写したときに、基材1側に残存する層である。
図1に示すように、離型層2上には、転写層10が設けられている。転写層10は、基材1から剥離可能に設けられており、熱転写時において、被転写体上に移行する層である。転写層10は、基材1側から、保護層3、接着層5がこの順で積層されてなる積層構成を呈している。保護層3、接着層5は、一実施形態の転写箔100における必須の構成である。
転写層10に含まれる保護層3は、被転写体上に転写層10を転写することで得られる印画物に耐久性を付与するための層である。なお、保護層3は、転写層10を構成する層のうち、基材1から最も近くに位置しており、被転写体上に転写層10を転写することで得られる印画物において最表面に位置する層となる。
図1に示すように、保護層3上には、接着層5が設けられている。接着層5は、転写層10を構成し、被転写体上に転写層10を転写するときに、被転写体と転写層10とを密着させるための層である。したがって、一実施形態の転写箔100において、接着層5は、最表面に位置する層となっている。
上記で説明したように、一実施形態の転写箔100は、転写層10を構成する層のうち離型層2側から最も近くに、活性光線硬化樹脂を含有する保護層3を位置させることで、保護層3の耐久性を向上させており、また、転写層10と接する位置に、離型層2を設けることで、転写層10を転写するときの転写性を向上させている。
硬化バインダー樹脂を得るためのバインダー樹脂について特に限定はなく、水系のバインダー樹脂であってもよく、溶剤系のバインダー樹脂であってもよい。水系のバインダー樹脂としては、ポリビニルピロリドン樹脂、ポリビニルアルコール系樹脂、ポリアクリル酸、ポリヒドロキシエチルアクリレート、水溶性(或いは水分散)ポリエステル樹脂、水溶性(或いは水分散)ポリウレタン系樹脂、水分散性塩化ビニル樹脂、水分散性塩化アクリル系樹脂、水分散性エポキシ樹脂、ゼラチン、ヒドロキシエチルセルロース樹脂、ヒドロキシプロピルセルロース樹脂、カルボキシメチルセルロース等を挙げることができる。水系のバインダー樹脂とは、水溶性樹脂、或いは水系溶媒に不溶性であるが、エマルジョンやディスパージョンのように、水系溶媒に分散可能な樹脂を意味する。水系溶媒としては、水や、水とアルコールとの混合溶媒等を挙げることができる。
また、基材1の転写層10が設けられている面とは反対側の面に、耐熱性や、走行性等の向上を目的とする背面層(図示しない)を設けることもできる。なお、背面層は、一実施形態の転写箔100における任意の構成である。
一実施形態の転写箔100を用いて、被転写体上に転写層10を転写する方法としては、公知の転写法でよく、例えば、熱刻印によるホットスタンプ(箔押)、熱ロールによる全面又はストライプ転写、サーマルヘッド(感熱印画ヘッド)によるサーマルプリンタ(熱転写プリンタともいう)などの公知の方法が適用できる。
厚さ12μmのポリエチレンテレフタレート(PET)フィルム上に、下記組成の密着層用塗工液1を乾燥時の厚みが0.2μmとなるように塗工し密着層を形成した。次いで、この密着層上に、下記組成の離型層用塗工液を乾燥時の厚みが1μmとなるように塗工し離型層を形成した。次いで、この離型層上に、下記組成の保護層用塗工液をグラビアコーティングにより、乾燥後の厚みが6μmになるように塗布、乾燥させた後に、UV露光器(Fusion UV、F600V、LH10ランプ、Hバルブ、反射鏡はコールドタイプ)を用いて紫外線を照射し、保護層を形成した。次いで、保護層上に、下記組成の受容層兼接着層用塗工液をグラビアコーティングにより、乾燥後の厚みが2μmになるように塗布、乾燥して受容層兼接着層を形成することで、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例1の転写箔を得た。なお、実施例、及び比較例の転写箔を構成する転写層は、保護層と受容層兼接着層との積層体を意味する。
・カルボキシ基を有するウレタン樹脂(固形分:35%) 6部
(ハイドラン(登録商標)AP40N DIC(株))
・エポキシシラン化合物(硬化剤として) 0.2部
(WSA950 DIC(株))
・水 10部
・変性エタノール 50部
・エポキシ基含有シリコーン変性アクリル樹脂 16部
(セルトップ(登録商標)226 (株)ダイセル)
・アルミニウム触媒(固形分10%) 3部
(セルトップ(登録商標)CAT-A (株)ダイセル)
・トルエン 20部
・メチルエチルケトン 20部
・多官能アクリレート 40部
(NKエステルA-9300 新中村化学工業(株))
・ウレタンアクリレート 25部
(NKオリゴマーUA122-P 2官能 新中村化学工業(株))
・ウレタンアクリレート 30部
(NKエステルU-15HA 15官能 新中村化学工業(株))
・光重合開始剤 5部
(イルガキュア(登録商標)907 BASFジャパン)
・フィラー 5部
(MEK-AC2140 体積平均粒子径12nm 日産化学工業(株))
・トルエン 200部
・メチルエチルケトン 200部
・塩化ビニル-酢酸ビニル共重合体 95部
(ソルバイン(登録商標)CNL 日信化学工業(株))
・エポキシ変性シリコーンオイル 5部
(KP-1800U 信越化学工業(株))
・トルエン 200部
・メチルエチルケトン 200部
密着層用塗工液1にかえて、密着層用塗工液1のエポキシシラン化合物(WSA950 DIC(株))の配合量を0.2部から0.1部に変更した密着層用塗工液2を用いて密着層を形成した以外は、全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例2の転写箔を得た。
密着層用塗工液1にかえて、密着層用塗工液1のエポキシシラン化合物(WSA950 DIC(株))の配合量を0.2部から0.4部に変更した密着層用塗工液3を用いて密着層を形成した以外は、全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例3の転写箔を得た。
密着層用塗工液1を下記組成の密着層用塗工液4に変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例4の転写箔を得た。
・ポリビニルアルコール(固形分100%、重合度1700)2.67部
(クラレポバール(登録商標)PVA―117 (株)クラレ)
・チタンキレート剤(硬化剤として)(固形分42%) 2.55部
(オルガチックス(登録商標)TC-300 マツモトファインケミカル(株))
・水 45.89部
・変性エタノール 45.89部
密着層用塗工液1にかえて、密着層用塗工液4のチタンキレート剤(硬化剤として)(固形分42%)(オルガチックス(登録商標)TC-300 マツモトファインケミカル(株))の配合量を2.55部から5部に変更した密着層用塗工液5を用いて密着層を形成した以外は、全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例5の転写箔を得た。
密着層用塗工液1を下記組成の密着層用塗工液6に変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例6の転写箔を得た。
・ポリビニルアルコール樹脂(重合度1700) 1.81部
(クラレポバール(登録商標)PVA―117 (株)クラレ)
・チタンキレート剤(硬化剤として)(固形分42%) 4.7部
(オルガチックス(登録商標)TC-300 マツモトファインケミカル(株))
・水系ポリウレタン(固形分22.5%) 1.94部
(ハイドラン(登録商標)AP-40 DIC(株))
・帯電防止剤(固形分30.4%) 2.55部
(ケミスタット(登録商標)6120 三洋化成工業(株))
・水 44.5部
・変性エタノール 44.5部
密着層用塗工液1を下記組成の密着層用塗工液7に変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる実施例7の転写箔を得た。
・ポリエステル樹脂 3.3部
(バイロン(登録商標)200 東洋紡(株))
・塩化ビニル-酢酸ビニル共重合体 2.7部
(ソルバイン(登録商標)CNL 日信化学工業(株))
・イソシアネート硬化剤 3部
(XEL硬化剤 DICグラフィックス(株))
・メチルエチルケトン 6.7部
・トルエン 3.3部
密着層を形成しなかった以外は全て実施例1と同様にして、基材上に、離型層、転写層がこの順で積層されてなる比較例1の転写箔を得た。
密着層用塗工液1を下記組成の密着層用塗工液Aに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例2の転写箔を得た。
・アクリル樹脂 15部
(BR-87 三菱レイヨン(株))
・メチルエチルケトン 100部
・トルエン 100部
密着層用塗工液1を下記組成の密着層用塗工液Bに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例3の転写箔を得た。
・酢酸セルロース樹脂 15部
(L-20 (株)ダイセル)
・メチルエチルケトン 100部
・トルエン 100部
密着層用塗工液1を下記組成の密着層用塗工液Cに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例4の転写箔を得た。
・ポリエステル樹脂(数平均分子量:3000、Tg:53℃) 15部
(バイロン(登録商標)220 東洋紡(株))
・メチルエチルケトン 100部
・トルエン 100部
密着層用塗工液1を下記組成の密着層用塗工液Dに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例5の転写箔を得た。
・ポリエステル樹脂(数平均分子量:3000、Tg:90℃) 15部
(バイロン(登録商標)700 東洋紡(株))
・メチルエチルケトン 100部
・トルエン 100部
密着層用塗工液1を下記組成の密着層用塗工液Eに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例6の転写箔を得た。
・ポリエステル樹脂(数平均分子量:20000、Tg:61℃)(固形分30%) 15.21部
(バイロナール(登録商標)MD-1245 東洋紡(株))
・水 42.4部
・2-プロパノール 42.39部
密着層用塗工液1を下記組成の密着層用塗工液Fに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例7の転写箔を得た。
・カルボキシ基を有するウレタン樹脂(固形分:35%) 6部
(ハイドラン(登録商標)AP40N DIC(株))
・水 10部
・変性エタノール 50部
密着層用塗工液1を下記組成の密着層用塗工液Gに変更した以外は全て実施例1と同様にして、基材上に、密着層、離型層、転写層がこの順で積層されてなる比較例8の転写箔を得た。
・ポリビニルアルコール樹脂(固形分100%、重合度1700)
2.67部
(クラレポバール(登録商標)PVA―117 (株)クラレ)
・水 45.89部
・変性エタノール 45.89部
各実施例、及び比較例の転写箔と、下記組成のカード基材とを組み合わせ、
FARGO HDP-5000プリンタ(HID Global(株))により、カード基材上に、各実施例、及び比較例の転写箔の転写層を転写して、各実施例、及び比較例の印画物を得た。
・ポリ塩化ビニルコンパウンド(重合度800) 100部
(安定化剤などの添加剤を10%含有)
・白色顔料(酸化チタン) 10部
・可塑剤(フタル酸ジオクチル) 0.5部
各実施例、及び比較例の転写箔を65mm幅に成型し、成型した各実施例、及び比較例の転写箔を、70℃に温調したホットステージ(HP2000 新東科学(株))上に、ホットステージの表面と各実施例、及び比較例の転写箔の転写層とが対向するように、透明両面テープ(ナイスタックNW-15 15mm ニチバン(株))を用いて貼り合わせた。次いで、各実施例、及び比較例の転写箔を70℃に保った状態で、この熱転写シートの転写層を、剥離角度90°、剥離速度5mm/secの条件で剥離し、剥離が開始される起点から、剥離方向に向かって5mm離れた位置から15mm離れた位置(剥離長さ10mm)までの剥離力を、丸型バネ式テンションゲージを用いて測定し、この剥離長さの範囲における剥離力の平均値を算出した。この剥離力の平均値の算出は、各実施例、及び比較例の転写箔について、それぞれ3回ずつ行った。この3回の剥離力の平均値の算出の中で、値が最も大きい剥離力の平均値を剥離力A、値が最も小さい剥離力の平均値を剥離力Cとし、値が中間となる剥離力の平均値を剥離力Bとし、下式(1)に基づいて剥離力の変動値を算出し、以下の評価基準に基づいて剥離安定性の評価を行った。評価結果を表1に示す。
剥離力の変動値=剥離力A/剥離力C・・・式(1)
A:剥離力の変動値が1以上1.75未満であり、且つ剥離力A、剥離力B、剥離力Cの平均値が20g以上100g未満である。
B:剥離力の変動値が1以上1.75未満であり、且つ剥離力A、剥離力B、剥離力Cの平均値が20g未満または100g以上200g未満である。
NG:剥離力の変動値が1.75以上であるか、又は剥離力A、剥離力B、剥離力Cの平均値が200g以上である。
各実施例、及び比較例の印画物を目視で確認し、以下の評価基準に基づいて尾引き評価を行った。評価結果を表1に示す。
A:尾引きが殆ど生じない(1mm以下)。
B:尾引きが生じる(1mmより大きく2mm以下)。
NG:尾引きがかなり生じる(2mmより大きい)。
各実施例、及び比較例の印画物を目視で確認し、以下の評価基準に基づいて転写性評価を行った。評価結果を表1に示す。
A:転写層のみが正確に転写されている。
B:カード基材側に転写層のみが転写されている。
NG:転写層とともに、離型層や、密着層がカード基材側に全面転写されている。
上記転写層の転写によって得られた、各実施例、及び比較例の印画物の耐摩耗試験(Taber試験)を、ANSI-INCITS322-2002、5.9 Surface Abrasionに準拠して、3000サイクル実施した。100サイクル毎に、各実施例、及び比較例の印画物の表面の状態を目視で確認し、以下の評価基準に基づいて、表面強度評価を行った。評価結果を表1に示す。また、表面強度評価を行うにあたり、300サイクル毎に摩耗輪(摩耗輪:CS-10F 荷重:500gf)を研磨した。
A:3000サイクル実施後の表面状態が良好である。
B:2000サイクル実施後の表面状態は良好であったが、3000サイクル実施後の表面状態が良好ではない。
C:1000サイクル実施後の表面状態が良好ではないが実用上問題ないレベルである。
NG:100サイクル実施後の表面状態が良好ではない。
1 基材
2 離型層
3 保護層
5 接着層
7 密着層
10 転写層
Claims (3)
- 基材上に、密着層、離型層、転写層がこの順で設けられた転写箔であって、
前記転写層は、前記基材側から、保護層、接着層がこの順で積層されてなる積層構成を呈しており、
前記保護層が、活性光線により活性光線硬化性樹脂を硬化してなる活性光線硬化樹脂を含有しており、
前記密着層が、バインダー樹脂と硬化剤との硬化物である硬化バインダー樹脂を含有していることを特徴とする転写箔。 - 前記密着層は、前記硬化バインダー樹脂として、ポリウレタン系樹脂と硬化剤との硬化物である硬化ポリウレタン系樹脂、及びポリビニルアルコール系樹脂と硬化剤との硬化物である硬化ポリビニルアルコール系樹脂の何れか一方、又は双方を含有していることを特徴とする請求項1に記載の転写箔。
- 前記接着層が、受容層の機能を有する接着層であることを特徴とする請求項1又は2に記載の転写箔。
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JP2016574194A JP6187714B1 (ja) | 2015-09-28 | 2016-09-27 | 転写箔 |
US15/762,193 US10538119B2 (en) | 2015-09-28 | 2016-09-27 | Transfer film |
KR1020187001804A KR102468525B1 (ko) | 2015-09-28 | 2016-09-27 | 전사박 |
CN201680051269.XA CN107949487B (zh) | 2015-09-28 | 2016-09-27 | 转印箔 |
EP16851496.6A EP3342603A4 (en) | 2015-09-28 | 2016-09-27 | Transfer foil |
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EP (1) | EP3342603A4 (ja) |
JP (1) | JP6187714B1 (ja) |
KR (1) | KR102468525B1 (ja) |
CN (1) | CN107949487B (ja) |
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CN110171220A (zh) * | 2019-05-27 | 2019-08-27 | 青艺(福建)烫画科技有限公司 | 烫画印载体冷撕哑光热转印底片及其制备方法和应用 |
DE102019132787A1 (de) * | 2019-12-03 | 2021-06-10 | Leonhard Kurz Stiftung & Co. Kg | Dekorfolie, Verfahren zur Herstellung einer Dekorfolie und Verfahren zur Dekoration eines Zielsubstrats |
CN115674924A (zh) * | 2021-07-29 | 2023-02-03 | 苏州苏大维格科技集团股份有限公司 | 一种深纹路图案转移膜、转移材料及其制备方法 |
CN114261222B (zh) * | 2021-12-21 | 2024-01-19 | 湖南鼎一致远科技发展有限公司 | 一种用于增加热升华色带适用基材的碳带及其制备方法 |
DE102022104164A1 (de) * | 2022-02-22 | 2023-08-24 | Forever Gmbh | Transferfolie, Beschichtungssystem und Verfahren zum Übertragen von Abbildungen auf Substrate |
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US5344808A (en) * | 1992-09-09 | 1994-09-06 | Toppan Printing Co., Ltd. | Intermediate transfer medium and process for producing image-recorded article making use of the same |
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- 2016-09-27 KR KR1020187001804A patent/KR102468525B1/ko active IP Right Grant
- 2016-09-27 MY MYPI2018701198A patent/MY170682A/en unknown
- 2016-09-27 WO PCT/JP2016/078386 patent/WO2017057325A1/ja active Application Filing
- 2016-09-27 CN CN201680051269.XA patent/CN107949487B/zh active Active
- 2016-09-27 EP EP16851496.6A patent/EP3342603A4/en active Pending
- 2016-09-27 JP JP2016574194A patent/JP6187714B1/ja active Active
- 2016-09-29 TW TW105131371A patent/TWI773650B/zh active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2021200948A1 (ja) * | 2020-03-31 | 2021-10-07 | ||
WO2021200948A1 (ja) * | 2020-03-31 | 2021-10-07 | 大日本印刷株式会社 | 加飾シートおよび加飾樹脂成形品 |
JP7127755B2 (ja) | 2020-03-31 | 2022-08-30 | 大日本印刷株式会社 | 加飾シートおよび加飾樹脂成形品 |
Also Published As
Publication number | Publication date |
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CN107949487A (zh) | 2018-04-20 |
KR20180063037A (ko) | 2018-06-11 |
TWI773650B (zh) | 2022-08-11 |
US10538119B2 (en) | 2020-01-21 |
TW201726417A (zh) | 2017-08-01 |
CN107949487B (zh) | 2020-12-11 |
JPWO2017057325A1 (ja) | 2017-10-05 |
EP3342603A4 (en) | 2018-10-03 |
JP6187714B1 (ja) | 2017-08-30 |
US20180272779A1 (en) | 2018-09-27 |
KR102468525B1 (ko) | 2022-11-17 |
MY170682A (en) | 2019-08-26 |
EP3342603A1 (en) | 2018-07-04 |
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