JP6651770B2 - Transfer foil - Google Patents

Description

  The present invention relates to a transfer foil, and more particularly, to a transfer foil having good transferability and capable of imparting sufficient hard coat performance and plasticizer resistance performance to the surface of an object to be transferred.

  ID cards such as identification cards and IC cards such as cash cards such as banks have individual information such as face photo, address, and name recorded on the surface, and security processing is applied to prevent the contents from being forged or altered. Have been. For example, a hologram provided on the surface of an IC card is widely distributed. On the surface of such an IC card, a transfer layer is provided using a transfer foil in order to protect recorded information and holograms.

  The transfer foil has a configuration in which a transfer layer including a transferable protective layer and the like is provided on a base material. The transfer foil is transferred to the surface of a transfer target such as an IC card by transferring the transfer layer. The hard coat performance can be imparted to the surface of the transfer body. The transfer layer is preferably adhered to the base material with a minimum necessary adhesive force, since the transfer efficiency is improved as the transfer layer is more easily peeled from the base material. If the adhesive strength between the substrate and the base material is too weak, a problem of so-called tailing or burrs occurs in that a transfer layer in a portion not intended to be transferred is also transferred to a transfer target. In order to solve such a problem, for example, by adding a melamine resin or the like to a release layer provided between the base material and the transfer layer, the adhesive strength of the transfer layer is appropriately maintained on the base material. Application to a transfer foil has been performed (for example, see Patent Document 1).

  By the way, the protective layer provided by using the transfer foil serves to protect the surface of the transfer-receiving body such as an IC card, so that the protective layer is required to have high surface strength. Therefore, the protective layer is formed using an actinic ray-curable resin that is cured by ultraviolet rays or the like. However, when these resins are used to increase the surface hardness of the protective layer, a release layer containing a melamine resin is used. Even if it is provided, the breakage of the foil is deteriorated, or depending on the actinic ray-curable resin used, the adhesive strength between the transfer layer and the base material is excessively reduced, or the surface strength of the protective layer is reduced. There was a problem.

JP 2009-67013 A

  The present inventors have now found that the above-described poor transfer is due to some interaction between components in the resin used for the protective layer and the melamine resin in the release layer. Based on these findings, the transfer foil is provided with a release layer containing an actinic ray-curable resin and a thermosetting resin, and a protective layer containing an actinic ray-curable resin. And the like, transfer defects such as the above can be improved, and sufficient hard coat performance can be imparted to the surface of the transfer-receiving body. The present invention is based on such findings.

  Accordingly, an object of the present invention is to provide a transfer foil that can impart sufficient hard coat performance to the surface of a transfer-receiving member, does not cause transfer defects such as tailing and burrs, and has excellent peeling stability. To provide.

  According to one aspect of the present invention, a transfer foil comprising at least a base material, a release layer provided on the base material, and a protective layer provided on the release layer, A transfer foil is provided, wherein the release layer comprises an actinic ray-curable resin and a thermosetting resin, and the protective layer comprises an actinic ray-curable resin.

  In an embodiment of the present invention, the mixing ratio (in terms of solid content) of the actinic ray-curable resin and the thermosetting resin in the release layer may be 1: 5 to 1: 0.1 on a mass basis. preferable.

  In an embodiment of the present invention, the actinic ray-curable resin contained in the release layer and the protective layer preferably contains a urethane (meth) acrylate having a functional group number of 5 or more and 15 or less as a polymerization component. .

  In the aspect of the present invention, it is preferable that the actinic ray curable resin contained in the release layer and the protective layer contains urethane (meth) acrylate as a polymerization component.

  In an embodiment of the present invention, it is preferable that a receiving layer is provided on the protective layer.

  In the aspect of the present invention, it is preferable that an adhesive layer is provided between the protective layer and the receiving layer.

  According to the present invention, the transfer foil is provided on the base material, a release layer containing the actinic ray-curable resin and the thermosetting resin provided on the base material, and provided on the release layer. Since at least a protective layer containing an actinic ray-curable resin is provided, sufficient hard coat performance and plasticizer performance can be imparted to the surface of the transfer-receiving member, and transfer failure of the transfer layer occurs. It can be transferred without.

It is a cross section of a transfer foil by one embodiment of the present invention. It is a cross section of a transfer foil by one embodiment of the present invention. It is a cross section of a transfer foil by one embodiment of the present invention.

<Definition>
In the present specification, “parts”, “%”, “ratio”, and the like indicating the composition are based on mass unless otherwise specified. “PET” is an abbreviation, synonym, functional expression, common name, or industry term for “polyethylene terephthalate”. In addition, the actinic ray-curable resin means a precursor or a composition before irradiating with actinic ray, and a substance obtained by curing the actinic ray-curable resin by irradiating with actinic ray is referred to as an actinic ray-curable resin. I do. Further, the thermosetting resin means a precursor or a composition before heating, and a product obtained by heating to cure the thermosetting resin is referred to as a thermosetting resin. Further, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acrylate” means “acrylate and / or methacrylate”.

  Further, in the present specification, the actinic ray means radiation that chemically acts on the actinic ray-curable resin to promote polymerization, and specifically, visible rays, ultraviolet rays, X-rays, electron rays , Α-rays, β-rays, γ-rays and the like.

<Transfer foil>
The transfer foil according to 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 according to an embodiment of the present invention. As shown in FIG. 1, the transfer foil 1 according to the present invention includes at least a substrate 10, a release layer 20 on the substrate 10, and a protective layer 30. Further, according to one embodiment, the transfer foil 1 may be provided with an adhesive layer 40 on the protective layer 30, as shown in FIG. In addition, as described later, the adhesive layer can also play a role as a receiving layer by adjusting its configuration. However, as shown in FIG. 3, the adhesive layer 40 and the receiving layer 50 are formed on the protective layer 30. It may be provided. When transferred to a transfer target (not shown) using such a transfer foil 1, the protective layer 30 (when the adhesive layer 40 and the receiving layer 50 are provided, the protective layer 30, the adhesive layer 40, and / or the receiving layer 50 are provided). ) Is transferred as a transfer layer 60 to a transfer target. Hereinafter, each layer constituting the transfer foil according to the present invention will be described.

<Substrate>
The base material has heat resistance enough to withstand thermal energy (for example, heat of a thermal head) when transferring the transfer layer from the transfer foil to the transfer object, and mechanical strength and solvent resistance capable of supporting the transfer layer. Can be used without particular limitation. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, and coextruded film of polyethylene terephthalate / polyethylene naphthalate Polyamide-based resins such as nylon, nylon 6, and nylon 66; polyolefin-based resins such as polyethylene, polypropylene, and polymethylpentene; vinyl-based resins such as polyvinyl chloride; and acrylic-based resins such as polyacrylate, polymethacrylate, and polymethylmethacrylate. Imide resins such as polyimide, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyolefin Engineering resins such as nylene ether, polyphenylene sulfide (PPS), polyaramid, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulphite, and styrene resins such as polycarbonate, polystyrene, high impact polystyrene, AS resin and ABS resin Resin, cellophane, cellulose acetate, cellulose film such as nitrocellulose, and the like.

  The substrate may be a copolymer resin or a mixture (including an alloy) containing the above-described resin as a main component, or a laminate including a plurality of layers. The substrate may be a stretched film or an unstretched film, but it is preferable to use a film stretched in a uniaxial or biaxial direction for the purpose of improving strength. The substrate is used in the form of a film, sheet or board composed of at least one layer of these resins. Among the base materials made of the above resins, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their excellent heat resistance and mechanical strength, and among them, polyethylene terephthalate films are more preferable.

  Moreover, in order to prevent blocking, irregularities can be provided on the surface of the base material as necessary. Means for forming irregularities on the substrate include kneading a matting agent, sandblasting, hairline processing, matte coating, chemical etching, and the like. In the case of a mat coating, either an organic substance or an inorganic substance may be used.

  The thickness of the substrate is preferably 0.5 μm or more and 50 μm or less, more preferably 4 μm or more and 20 μm or less. If the thickness of the base material is within the above numerical range, high mechanical strength and transferability can be realized.

  In order to provide a release layer on the surface of the base material, as described later, a corona discharge treatment, a plasma treatment, an ozone treatment, a frame treatment, a primer (anchor coat, adhesion promotion Coating, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, application of an antistatic layer, and the like, may be performed. In addition, additives such as a filler, a plasticizer, a colorant, and an antistatic agent may be added to the base material as necessary.

<Release layer>
Next, the release layer of the transfer foil according to the present invention will be described. The release layer provided on the base material is a layer for transferring the transfer layer provided on these layers from the transfer foil and transferring the transfer layer to the transfer target body. ,. When the transfer layer is peeled from the transfer foil, the release layer remains on the substrate side.

  The actinic ray-curable resin may appropriately include, as a polymerization component, a polymer, a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond such as a (meth) acryloyl group and a (meth) acryloyloxy group in the molecule or an epoxy group. It is preferable to include a mixed composition or the like.

  The actinic ray-curable resin forming the release layer preferably contains urethane (meth) acrylate, particularly, a polyfunctional urethane (meth) acrylate as a polymerization component. When the release layer contains a polyfunctional urethane (meth) acrylate, the solvent resistance can be improved. The number of functional groups of the polyfunctional urethane (meth) acrylate is preferably 5 or more and 15 or less, more preferably 6 or more and 15 or less. The polyfunctional urethane (meth) acrylate is preferably contained in an amount of 10% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 85% by mass or less based on the total solid content of the release layer. . The functional group is, for example, a group having an unsaturated double bond such as a vinyl group.

  Urethane (meth) acrylates include, for example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate, xylene diisocyanate, and 1,2 -It can be obtained by introducing (meth) acrylic acid into a urethane resin, such as polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate or trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate. .

  Further, from the viewpoint of compatibility between solvent resistance and flexibility, urethane (meth) acrylate having a functional group number of about 2 or more and about 4 or less and / or (meth) acrylate having a functional group number of from 2 or more and 5 or less, It is preferable to include a polyfunctional urethane (meth) acrylate in combination. Urethane (meth) acrylate and (meth) acrylate having a functional group number of about 2 or more and about 5 or less are preferably contained in a total amount of 10% by mass or more and 90% by mass or less based on the total solid content of the release layer. And more preferably 50% by mass or more and 85% by mass or less.

  Further, the mass average molecular weight of the polyfunctional and urethane (meth) acrylate having a functional group number of about 2 or more and about 4 or less is preferably in the range of 400 or more and 20000 or less, and more preferably 500 or more and 10000 or less. . When the mass average molecular weight of the urethane (meth) acrylate falls within the above numerical range, the abrasion resistance can be improved. In addition, by setting the molecular weight to 20,000 or less, good foil breakability can be realized. For the same reason, the weight average molecular weight of the (meth) acrylate having a functional group number of about 2 or more and about 5 or less is preferably in a range of 200 or more and 5000 or less. In addition, in this invention, "mass average molecular weight" means the value measured by gel permeation chromatography using polystyrene as a standard substance, and can be measured by the method based on JIS-K-7252-1.

  Further, the actinic ray-curable resin forming the release layer may contain an unsaturated bond-containing (meth) acrylate copolymer as a polymerization component. Examples of the unsaturated bond-containing (meth) acrylate copolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, and pyromellitic acid , Fumaric acid, glutaric acid, pimelic acid, sebacic acid, dodecanoic acid, polybasic acids such as tetrahydrophthalic acid and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetra Polyesters obtained by bonding polyhydric alcohols such as ethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol ( Polyester (meth) acrylates in which acrylic acid is introduced, for example, (meth) acrylic acid is introduced into epoxy resin such as bisphenol A / epichlorohydrin / (meth) acrylic acid, phenol novolak / epichlorohydrin / (meth) acrylic acid Epoxy (meth) acrylates, melamine (meth) acrylates, and triazine (meth) acrylates are exemplified.

  The actinic ray-curable resin forming the release layer may contain, as a polymerization component, the following prepolymer, oligomer and / or monomer other than the unsaturated bond-containing acrylic copolymer.

  Examples of the prepolymer include silicone resin acrylates such as polysiloxane (meth) acrylate, polysiloxane diisocyanate / 2-hydroxyethyl (meth) acrylate, and other alkyds obtained by introducing a (meth) acryloyl group into an oil-modified alkyd resin. Modified (meth) acrylates and spirane resin acrylates are exemplified.

  As the monomer or oligomer, generally known as an actinic ray-polymerizable monomer / oligomer, for example, an acrylate compound or a methacrylate compound having an ethylenic double bond, and the like. It has at least a methacryloyl group or an acryloyl group. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Acrylates of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylates such as 1,3-dioxolane acrylate, or methacrylate, itaconate, crotonate, methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with maleate, Maleic acid esters such as ethylene glycol diacrylate, triethylene glycol diacryle Pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclo Decane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl of 1,6-hexanediol Bifunctional acrylates such as diacrylate of terephthalate, or methacrylic acid, itaconic acid, crotonic acid or maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate or maleate, for example, trimethylolpropane triacrylate, dimethyltriol Propane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Pyrogallol triacrylate, propionic acid / dipentaerythri Methacrylate, methacrylate, itaconate, crotonate, maleate, etc. Itaconic acid, crotonic acid, maleic acid ester, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylate benzoate, Alkylene glycol type acrylic modified acrylate, modified urethane acrylate not limited to the number of functional groups described above, etc. And the like.

  As the thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, urea resin, resorcinol resin, furan resin, polyimide resin, polybenzothiazole resin, Examples include amino alkyd resins, melamine / urea co-condensation resins, silicon resins and polysiloxane resins.

  The content of the actinic ray-curable resin in the release layer is preferably from 10% by mass to 90% by mass, and more preferably from 50% by mass to 85% by mass, based on the total solid content of the release layer. Is more preferred. When the content of the actinic ray-curable resin is within the above numerical range, transferability can be improved. Further, the content of the thermosetting resin is preferably 8% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 20% by mass or less, based on the total solid content of the release layer. . When the content of the thermosetting resin is within the above numerical range, transferability can be improved. Further, the compounding ratio (in terms of solid content) of the actinic ray-curable resin and the thermosetting resin is preferably 1: 5 to 1: 0.1 on a mass basis, and is 1: 2 to 1: 0.5. Is more preferable. When the compounding ratio is within the above numerical range, the transferability of the transfer foil can be improved.

  Further, the release layer preferably contains a photopolymerization initiator and / or a thermal polymerization initiator. The content of the polymerization initiator is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 4% by mass or less based on the total solid content of the release layer. More preferably, it is 1% by mass or more and 3% by mass or less.

  The release layer may further contain, as additives, a leveling agent, a polymerization terminator, a plasticizer, an antifoaming agent, a silane coupling agent, a lubricant and the like. Examples of the leveling agent include a polyoxyalkylene surfactant, a fatty acid ester surfactant, and a vinyl polymer.

  The release layer is, for example, a coating solution comprising a composition containing an actinic ray-curable resin and a thermosetting resin as described above, roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod By a known means such as a coat, a coating film is formed by applying the composition on a substrate, irradiating ultraviolet rays to cure the actinic ray-curable resin, and then heating and drying at a temperature of about 80 to 200 ° C. It can be formed by curing a curable resin. Irradiation of ultraviolet light can be performed using a conventionally known ultraviolet irradiation device, and various types of high-pressure mercury lamp, low-pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, electrodeless ultraviolet lamp, LED, and the like can be used without limitation. it can. Irradiation with an electron beam is performed using either a high-energy electron beam irradiation device that irradiates an electron beam with an energy of 100 keV or more and 300 keV or less, or a low-energy electron beam irradiation device that irradiates an electron beam with an energy of 100 keV or less. The irradiation method may be a scanning type or curtain type irradiation device.

Usually, the releasing layer, with coating weight of solids, 0.1 or more, preferably 5 g / ^{m 2} or less, 0.3 g / ^{m 2} or more, more preferably 3 g / ^{m 2} or less, 0. 5 g / m ² or more and 1.5 g / m ² or less are more preferable. When the coating amount is within the above numerical range, the transferability of the transfer foil can be improved.

<Protective layer>
Next, the protective layer will be described. The protective layer serves to protect the surface of the transfer-receiving member, and includes an actinic ray-curable resin.

  The actinic ray-curable resin may appropriately include, as a polymerization component, a polymer, a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond such as a (meth) acryloyl group and a (meth) acryloyloxy group in the molecule or an epoxy group. It is preferable to include a mixed composition or the like.

  Like the release layer, the actinic ray-curable resin forming the protective layer preferably contains urethane (meth) acrylate, particularly, a polyfunctional urethane (meth) acrylate as a polymerization component. When the protective layer contains polyfunctional urethane (meth) acrylate, solvent resistance can be improved. The number of functional groups of the polyfunctional urethane (meth) acrylate is preferably 5 or more and 15 or less, more preferably 6 or more and 15 or less. The polyfunctional urethane (meth) acrylate is preferably contained in an amount of 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 50% by mass or less based on the total solid content of the protective layer. The functional group is, for example, a group having an unsaturated double bond such as a vinyl group.

  Urethane (meth) acrylates include, for example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate, xylene diisocyanate, and 1,2 -It can be obtained by introducing (meth) acrylic acid into a urethane resin, such as polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate or trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate. .

  Further, from the viewpoint of compatibility between solvent resistance and flexibility, urethane (meth) acrylate having a functional group number of about 2 or more and about 4 or less and / or (meth) acrylate having a functional group number of from 2 or more and 5 or less, It is preferable to include a urethane (meth) acrylate having a multifunctional group in combination. Urethane (meth) acrylate and (meth) acrylate having a functional group number of about 2 or more and about 5 or less are preferably contained in a total amount of 5% by mass or more and 80% by mass or less based on the total solid content of the protective layer, More preferably, the content is 10% by mass or more and 70% by mass or less.

  Further, the mass average molecular weight of the polyfunctional and urethane (meth) acrylate having a functional group number of about 2 or more and about 4 or less is preferably in the range of 400 or more and 20000 or less, and more preferably 500 or more and 10000 or less. . When the mass average molecular weight of the urethane (meth) acrylate falls within the above numerical range, the abrasion resistance can be improved. In addition, by setting the molecular weight to 20,000 or less, good foil breakability can be realized. For the same reason, the weight average molecular weight of the (meth) acrylate having a functional group number of about 2 or more and about 5 or less is preferably in a range of 200 or more and 5000 or less. In addition, in this invention, "mass average molecular weight" means the value measured by gel permeation chromatography using polystyrene as a standard substance, and can be measured by the method based on JIS-K-7252-1.

  The actinic ray-curable resin forming the protective layer may contain an unsaturated bond-containing (meth) acrylate copolymer as a polymerization component. Examples of the unsaturated bond-containing (meth) acrylate copolymer include, for example, adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, and pyromellitic acid , Fumaric acid, glutaric acid, pimelic acid, sebacic acid, dodecanoic acid, polybasic acids such as tetrahydrophthalic acid and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetra Polyesters obtained by bonding polyhydric alcohols such as ethylene glycol, polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol ( Polyester (meth) acrylates in which acrylic acid is introduced, for example, (meth) acrylic acid is introduced into epoxy resin such as bisphenol A / epichlorohydrin / (meth) acrylic acid, phenol novolak / epichlorohydrin / (meth) acrylic acid Epoxy (meth) acrylates, melamine (meth) acrylates, and triazine (meth) acrylates are exemplified.

  The actinic ray-curable resin forming the protective layer may contain, as a polymerization component, the following prepolymer, oligomer and / or monomer other than the unsaturated bond-containing acrylic copolymer.

  Examples of the prepolymer include silicone acrylates such as polysiloxane (meth) acrylate, polysiloxane diisocyanate / 2-hydroxyethyl (meth) acrylate, and other alkyds obtained by introducing a (meth) acryloyl group into an oil-modified alkyd resin. Modified (meth) acrylates and spirane resin acrylates are exemplified.

  As the monomer or oligomer, generally known as an actinic ray-polymerizable monomer / oligomer, for example, an acrylate compound or a methacrylate compound having an ethylenic double bond, and the like. It has at least a methacryloyl group or an acryloyl group. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Acrylate of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylates such as 1,3-dioxolane acrylate, or methacrylate, itaconate, crotonate, methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with maleate, Maleic acid esters such as ethylene glycol diacrylate, triethylene glycol diacryle Pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclo Decane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl of 1,6-hexanediol Bifunctional acrylates such as diacrylate of terephthalate, or methacrylic acid, itaconic acid, crotonic acid or maleic acid ester in which these acrylates are replaced with methacrylate, itaconate, crotonate or maleate, for example, trimethylolpropane triacrylate, dimethyltriol Propane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Pyrogallol triacrylate, propionic acid / dipentaerythri Triacrylate, propionic acid / dipentaerythritol tetraacrylate, polyfunctional acrylate acid such as hydroxypivalyl aldehyde-modified dimethylolpropane triacrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Itaconic acid, crotonic acid, maleic acid ester, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylate benzoate, Alkylene glycol type acrylic modified acrylate, modified urethane acrylate not limited to the number of functional groups mentioned above, etc. And the like.

  The content of the actinic ray-curable resin in the protective layer is preferably 1% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 80% by mass or less based on the total solid content of the release layer. More preferably, it is 30% by mass or more and 70% by mass or less. When the content of the actinic ray-curable resin is within the above numerical range, the transferability of the transfer foil can be improved.

  Also, the protective layer preferably contains a photopolymerization initiator. It is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less, even more preferably 1% by mass or more and 3% by mass or less. .

  The protective layer may contain a filler other than the above-mentioned resin. In the present invention, by exposure as described below, it is possible to improve both the peeling stability and durability of the transfer foil, but since the breaking strength of the protective layer is improved, the protective layer has a certain thickness. When it has, the transfer efficiency of the transfer layer is deteriorated because the transfer layer is not easily peeled from the base material, transfer failure occurs, and the peeling stability tends to decrease. By including a filler in the protective layer, even when the thickness of the protective layer exceeds 20 μm, the breakability is improved, and both the peeling stability and the durability of the transfer foil can be improved.

  The filler contained in the protective layer preferably has an average particle size of 40 nm or less. When the average particle diameter of the filler is 40 nm or less, the transparency of the protective layer can be maintained. Further, the average particle size is preferably 10 nm or more. When the average particle diameter of the filler is 10 nm or more, the dispersibility can be maintained, and the stability of the protective layer coating liquid can be maintained. The “average particle diameter” means a volume average particle diameter, and is measured by a known method using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device, manufactured by Nikkiso Co., Ltd.). can do.

  Examples of the filler include an inorganic filler such as an organic filler, carbon black, graphite, and microsilica, and an organic-inorganic hybrid filler. The filler may be a powder or a sol. From the viewpoint of dispersibility, inorganic particles are preferable among the above-mentioned fillers.

  Examples of the inorganic particles include metal oxide particles such as silica particles (corodyl silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, and the like. From the viewpoint, it is preferable to use silica particles. Further, it is preferable that the inorganic particles have been subjected to a surface treatment using a silane coupling agent such as γ-aminopropyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane.

  The filler is preferably contained in an amount of 5% by mass or more and 60% by mass or less based on the total solid content of the protective layer. When the content of the filler is within the above numerical range, the transferability of the transfer foil and the abrasion resistance of the printed matter obtained by using the transfer foil can be improved, and the protective layer becomes brittle, cracks and the like. Can be prevented from occurring.

  The thickness of the protective layer is preferably 5 μm or more and 20 μm or less. By setting the thickness of the protective layer within the above numerical range, high durability can be imparted while preventing poor transfer.

  Protective layer, a coating solution comprising a composition containing an actinic ray-curable resin as described above, roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, known means such as rod coating, It can be formed by coating on the intermediate layer to form a coating film and curing with actinic rays. For example, ultraviolet irradiation can be performed using a conventionally known ultraviolet irradiation apparatus, and various types of high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, electrodeless ultraviolet lamps, and LEDs can be used without limitation. be able to. Irradiation with an electron beam is performed using either a high-energy electron beam irradiation device that irradiates an electron beam with an energy of 100 keV or more and 300 keV or less, or a low-energy electron beam irradiation device that irradiates an electron beam with an energy of 100 keV or less. The irradiation method may be a scanning type or curtain type irradiation device.

<Adhesive layer>
Next, the adhesive layer provided in the transfer foil according to the present invention as desired will be described.
The adhesive layer is provided on the protective layer and improves the adhesiveness between the transfer layer and the transfer object. Further, the adhesive layer may function as a receptor layer in which an image is formed by thermal transfer from a thermal transfer sheet having a color material layer by thermal transfer. Then, the transfer portion of the transfer foil on which the image is formed is transferred to the transfer target, and as a result, a print is formed.

  Examples of the material for forming the adhesive layer include a heat-adhesive type adhesive which is melted or softened by heat and adheres, and specifically, an ionomer resin, an acid-modified polyolefin resin, ethylene- (meth) acrylic resin Acid copolymers, ethylene- (meth) acrylate copolymers, polyester resins, polyamide resins, vinyl resins, (meth) acrylic resins such as acrylic and methacrylic resins, acrylate ester resins, maleic Acid resin, butyral resin, alkyd resin, polyethylene oxide resin, phenol resin, urea resin, melamine resin, melamine-alkyd resin, cellulose resin, polyurethane resin, polyvinyl ether resin, silicone Resin, rubber resin and the like. These resins are used alone or in combination of two or more. Among them, vinyl resin, acrylic resin, butyral resin, and polyester resin are preferable in terms of adhesive strength and the like. More preferred are vinyl resins, (meth) acrylic resins such as ethylene- (meth) ethyl acrylate copolymer, and acrylate resins.

  When the adhesive layer functions as a receptor layer, it is preferable to use a resin that easily accepts a heat-transferring coloring material such as a sublimable dye or a hot-melt ink. For example, vinyl resins such as polyolefin resins, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate polymers, ethylene-vinyl acetate copolymers or polyacrylates, and polyester resins such as PET and polybutylene terephthalate. Resins, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene or propylene and other vinyl polymers, cellulose resins such as ionomers or cellulose diastase, polycarbonate and the like can be used. A vinyl chloride-vinyl acetate polymer or polyvinyl chloride is preferred, and a vinyl chloride-vinyl acetate polymer is particularly preferred.

  Usually, the thickness of the adhesive layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 3 μm or less.

<Receiving layer>
Next, the receiving layer of the transfer foil according to the present invention, if desired, will be described.
As described above, the adhesive layer plays a role as a receiving layer by adjusting its configuration, but the transfer foil may have a receiving layer separately from this. In this case, the receiving layer is provided on the adhesive layer, and an image is formed on the receiving layer by thermal transfer from a thermal transfer sheet having a color material layer by thermal transfer. Then, the transfer portion of the transfer foil on which the image is formed is transferred to the transfer target, and as a result, a print is formed.

  For this reason, as a material for forming the receiving layer, the same material as the material for forming the adhesive layer when the adhesive layer functions as the receiving layer can be used.

  When the receiving layer is transferred to the transfer-receiving body via an adhesive or the like, the adhesiveness of the receiving layer itself is not always required. However, when the receiving layer is transferred to the transfer-receiving body without using an adhesive or the like, it is preferable to form the receiving layer using an adhesive resin material such as a vinyl chloride-vinyl acetate copolymer. .

  Usually, the thickness of the receiving layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 3 μm or less.

  The receiving layer is formed by adding one or more materials selected from the above-mentioned materials and various additives as necessary, dissolving or dispersing in an appropriate solvent such as water or an organic solvent, and coating the receiving layer. A liquid can be prepared by applying and drying the liquid by means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate.

  Further, in the transfer foil of the present invention, it is possible to further provide the above-mentioned adhesive layer having no function as the receiving layer on the receiving layer.

<Transfer of transfer layer>
As a method of transferring the transfer layer onto the transfer object using the transfer foil according to the present invention, a known transfer method may be used, for example, hot stamping by hot stamping (foil stamping), whole surface or stripe transfer by a hot roll, Known methods such as a thermal printer (also called a thermal transfer printer) using a thermal head (thermal printing head) can be applied. Of these, transfer by a hot roll is preferred.

  The transfer object is not particularly limited as long as it is a use requiring durability such as abrasion resistance and plasticizer resistance. Examples thereof include natural fiber paper, coated paper, tracing paper, and heat transfer. Any material such as a plastic film, glass, metal, ceramics, wood, cloth or a medium having dye receptivity which does not deform. Further, since an IC card or the like usually requires designability and security, when the transfer foil according to the present invention does not have a receiving layer, a printing layer or Generally, a hologram layer and the like are provided.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
Using a 12 μm thick polyethylene terephthalate (PET) film as a base material, apply a release layer coating solution having the following composition to one surface by gravure coating so that the thickness after drying becomes 1 μm and drying. After that, ultraviolet irradiation was performed at an integrated exposure amount of 220 mJ / cm ² using a UV exposure device (Fusion UV, F600V, LH10 lamp, H bulb, and cold mirror). Further, heating and drying were performed at 110 ° C. for 1 minute to form a release layer. The compounding ratio (in terms of solid content) of the actinic ray-curable resin and the thermosetting resin was 1: 2 on a mass basis.

In addition, the measurement of the integrated exposure amount was performed using a micro cure model MC-2 by a UV illuminance meter micro cure data reader manufactured by Fusion UV Systems Japan Co., Ltd.
<Release layer coating liquid composition A>
3.5 parts of actinic ray-curable resin / trifunctional acrylate (trade name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
2.0 parts of 15-functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
36 parts of a thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content: 50%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Celltop 226)
0.1 parts of aluminum catalyst (solid content 10%) (trade name: Celltop CAT-A, manufactured by Daicel Chemical Industries, Ltd.)
・ Toluene 30 parts ・ MEK 20 parts

Next, a protective layer coating solution having the following composition is applied onto the formed release layer by gravure coating so that the thickness after drying becomes 6 μm, and after drying, a UV exposure device (Fusion UV) is used. , F600V, LH10 lamp, H bulb and cold mirror were used to irradiate ultraviolet rays to form a protective layer.
<Protective layer coating liquid composition>
20 parts of trifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-9300)
20 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
・ 10 parts of 15-functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
・ 5 parts of unsaturated bond-containing acrylic copolymer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester C24T)
・ 5 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907)
-40 parts of filler (silica) (average particle size: 12 nm, manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-AC2140Z)
・ Toluene 200 parts ・ MEK 200 parts

Subsequently, on the protective layer formed as described above, an adhesive layer coating solution having the following composition is applied by gravure coating so that the thickness after drying becomes 2 μm, and dried to form an adhesive layer. A transfer foil was obtained.
<Adhesive layer coating liquid composition>
・ 95 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: CNL)
・ Epoxy-modified silicone oil 5 parts (Shin-Etsu Chemical Co., Ltd., trade name: KP-1800U)
・ Toluene 200 parts ・ MEK 200 parts

(Example 2)
A transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating liquid was changed to the composition shown below. The compounding ratio (solid content conversion) of the actinic ray-curable resin and the thermosetting resin was 1: 1 on a mass basis <Release layer coating liquid composition B>.
3.5 parts of actinic ray-curable resin / trifunctional acrylate (trade name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
2.0 parts of 15-functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
18 parts of thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content: 50%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Celltop 226)
0.1 parts of aluminum catalyst (solid content 10%) (trade name: Celltop CAT-A, manufactured by Daicel Chemical Industries, Ltd.)
・ 30 parts of toluene ・ 20 parts of MEK

(Example 3)
A transfer foil was prepared in the same manner as in Example 2 except that the thickness of the release layer after drying was changed to 0.7 μm.

(Example 4)
A transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating liquid was changed to the composition shown below. The compounding ratio (in terms of solid content) of the actinic ray-curable resin and the thermosetting resin was 1: 0.5 on a mass basis.
<Release layer coating liquid composition C>
3.5 parts of actinic ray-curable resin / trifunctional acrylate (trade name: NK Ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
3.5 parts of bifunctional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
2.0 parts of 15-functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
-Photopolymerization initiator 0.2 parts (Ciba Specialty Chemicals, trade name: Irgacure 184)
9 parts of thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content: 50%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Celltop 226)
0.1 parts of aluminum catalyst (solid content 10%) (trade name: Celltop CAT-A, manufactured by Daicel Chemical Industries, Ltd.)
・ Toluene 30 parts ・ MEK 20 parts

(Example 5)
A transfer foil was produced in the same manner as in Example 2 except that an intermediate layer of the following coating liquid was provided between the protective layer and the adhesive layer.
<Intermediate layer coating liquid composition>
-3.3 parts of polyester resin (Toyobo Co., Ltd., trade name: Byron 200)
-2.7 parts of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: CNL)
1.5 parts of isocyanate curing agent (trade name: XEL curing agent, manufactured by The Inktech Co., Ltd.)
・ Methyl ethyl ketone / toluene (mass ratio 2/1) 10 parts

(Comparative Example 1)
In Example 1, a transfer foil was prepared in the same manner as in Example 1, except that heating and drying at 110 ° C. for 1 minute after ultraviolet irradiation was not performed during the formation of the release layer.

(Comparative Example 2)
A film in which a release layer of a melamine resin is applied to one surface of a PET film having a thickness of 12 μm is used as a base material, and a second release layer coating solution having the following composition is gravure coated on the release layer. Coating was performed so that the thickness after drying was 0.3 μm.
Otherwise, a transfer foil was prepared in the same manner as in Example 1.
<Composition of release layer coating liquid>
-Carnauba wax (manufactured by Konishi Co., Ltd., trade name: WE-95, solid content 40%) 2 parts-Polyethylene wax (solid content 40%) 7 parts-Styrene-butadiene rubber 1 part (manufactured by Nippon Zeon Co., Ltd.) (Product name: Nipol LX430, average particle diameter 150 nm, solid content 49%, Tg: 12 ° C)
・ 100 parts of pure water / IPA (1: 1)

(Comparative Example 3)
A transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating liquid was changed as follows.
<Release layer coating liquid composition D>
1.5 parts of actinic ray-curable resin / trifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-9300)
1.5 parts of bifunctional urethane acrylate (bifunctional, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK oligomer UA122-P)
0.8 parts of 15-functional urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester U-15HA)
・ 0.1 part of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907)
・ Toluene 20 parts ・ MEK 20 parts

(Comparative Example 4)
A transfer foil was prepared in the same manner as in Example 1 except that the composition of the release layer coating liquid was changed as follows.
<Release layer coating composition E>
8 parts of thermosetting resin / epoxy group-containing silicone-modified acrylic resin (solid content: 50%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Celltop 226)
0.3 parts of aluminum catalyst (solid content: 10%) (manufactured by Daicel Chemical Industries, Ltd., trade name: Celltop CAT-A)
・ Toluene 20 parts ・ MEK 20 parts

<Evaluation of transfer foil>
A card substrate having the following material composition was used as a transfer object.
<Composition of card base material>
100 parts of polyvinyl chloride compound (degree of polymerization 800) (containing 10% of additives such as stabilizers)
White pigment (titanium oxide) 10 parts Plasticizer (DOP) 0.5 parts

  Images were printed on the receiving layers of the transfer foils according to Examples 1 and 2 and Comparative Examples 1 to 4 using HDP5000 (FARGO) using a thermal transfer ribbon for HDP5000 (FARGO).

  Next, the transfer layer was transferred to the adhered layer of the transfer object using HDP5000 (manufactured by FARGO) at a surface temperature of the heat roller of 175 ° C. and a speed of 2.3 sec / inch.

<< Evaluation of turbidity >>
Under the above transfer conditions, the transfer layer on the card base material was visually confirmed, and an evaluation test was performed according to the following evaluation criteria. The evaluation results were as shown in Table 1 below.
：: The transfer layer is transparent Δ: The transfer layer is slightly white and cloudy, but there is no problem in quality.
×: The transfer layer is white and cloudy

<< Foil breakability test >>
Under the above-mentioned transfer conditions, the cut-off property (tailing) of the transfer layer to the card base material was visually confirmed, and an evaluation test was performed according to the following evaluation criteria. The evaluation results were as shown in Table 1 below.
◎: No tailing occurs (0.5 mm or less)
：: almost no tailing (1 mm or less)
Δ: Tail occurs (1 mm or more and 2 mm or less)
×: considerable tailing occurs (4 mm or more)

<< Transferability test >>
After transferring 100 sheets continuously under the above-described transfer conditions, the outer space characteristics of the card were visually evaluated to determine the number of untransferred cards. The evaluation criteria were as follows. The evaluation results were as shown in Table 1 below.
◎: 0 problematic cards ○: 1 to 9 problematic cards △: 10 to 20 problematic cards ×: 20 or more problematic cards

<< Surface strength test >>
The transfer layer on the card surface was subjected to a wear resistance test (Taber test) in accordance with ANSI-INCITS 322-2002, 5.9 Surface Abrasion, and the degree of wear was visually observed at every predetermined number of cycles. An evaluation test was performed. The evaluation results were as shown in Table 1.
◎: Good image after 1500 cycles. サ イ ク ル: Good image after 1000 cycles. Δ: Image not good after 1000 cycles but no practical problem. ×: 1000 cycles. Later image is bad

Reference Signs List 1 transfer foil 10 base material 20 release layer 30 protective layer 40 adhesive layer 50 receiving layer 60 transfer layer

Claims (5)

A transfer foil including at least a base material, a release layer provided on the base material, and a protective layer provided releasably on the release layer,
The release layer comprises an actinic ray-curable resin and a thermosetting resin,
The protective layer comprises an actinic ray curable resin,
The actinic ray-curable resin is a cured product of an actinic ray-curable resin having an unsaturated double bond,
The thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, urea resin, resorcinol resin, furan resin, polyimide resin, polybenzothiazole resin, One or more resin materials selected from amino alkyd resins, melamine / urea co-condensation resins, silicon resins and polysiloxane resins,
A transfer foil, wherein a mixing ratio (in terms of solid content) of the actinic ray-curable resin and the thermosetting resin in the release layer is 1: 5 to 1: 1 on a mass basis . The transfer foil according to claim 1 , wherein the actinic ray-curable resin contained in the release layer and the protective layer is a cured product of an actinic ray-curable resin containing urethane (meth) acrylate as a polymerization component . The actinic ray-curable resin contained in the release layer and the protective layer is a cured product of an actinic ray-curable resin containing a urethane (meth) acrylate having a functional group number of 5 or more and 15 or less as a polymerization component. transfer foil mounting serial to claim 1 or 2. The transfer foil according to any one of claims 1 to 3 , wherein an adhesive layer is further provided on the protective layer. The transfer foil according to claim 4 , wherein an intermediate layer is provided between the protective layer and the adhesive layer.

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