JP2011011376A - Hard coat transfer foil for in-mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat transfer foil for in-mold transfer which has a design in which a printing pattern looks in three-dimensional being different from a transfer foil to which a conventional pattern printing is given, and in which there is no disappearance of a pattern in an anticipated use, and abrasion resistance is excellent.SOLUTION: The hard coat transfer foil for in-mold is characterized in that, in the transfer foil for in-mold which has a transfer layer on a mold release surface of a mold releasability base material sheet, the transfer layer is formed by laminating at least a first transparency crosslinking cured resin layer, a printing pattern layer, a second transparency crosslinking cured resin layer, a metallic luster layer or a metal tone printing layer, and an adhesive layer one by one, wherein the second transparency crosslinking type cured resin layer has a thickness of 20-100 μm.

Description

  The present invention relates to a transfer foil for in-mold, and more specifically, a hard-coat transfer for in-mold that can easily impart a high-design three-dimensional pattern to a molded article that is a transfer target and has excellent wear resistance. It is about foil.

Conventionally, for in-mold transfer foils, transfer foils with various patterns have been manufactured using a printing method typified by gravure printing. Moreover, the proposal which gives a three-dimensional effect to the design of a transfer foil has been made | formed for the purpose of providing high designability.
For example, a base sheet, a transparent layer, a decorative sheet having a light-shielding pattern mainly composed of white ink (Patent Document 1), a peelable film base material, a first pattern layer, a transparent layer, a first layer A transfer sheet having a structure in which two pattern layers, a hiding layer, and an adhesive layer are sequentially laminated has been proposed (Patent Document 2).
However, at present, it is still difficult to obtain a transfer foil in which a pattern can be seen three-dimensionally, except for a complicated and expensive transfer foil that incorporates a hologram processing technique or the like.
On the other hand, when the silk screen printing method is used, three-dimensional printing (high-rise printing) can be performed, but a transfer foil having a sharp pattern with excellent wear resistance has not yet been obtained.

JP 58-78755 A JP-A-2-310051

  The present invention has been made in view of the above circumstances, and unlike a transfer foil subjected to conventional pattern printing, the printed pattern has a design that looks three-dimensional, and in normal use the pattern An object of the present invention is to provide a hard coat transfer foil for in-mold transfer having no loss and good wear resistance.

  In order to achieve the above object, the in-mold hard coat transfer foil of the present invention has at least a first transparent cross-linked cured resin layer and a printed pattern layer as a transfer layer on the release surface of the releasable substrate sheet. The basic constitution is that the second transparent cross-linked cured resin layer, the metallic luster layer or the metallic print layer, and the adhesive layer are laminated.

  That is, in the invention according to claim 1 of the present invention, in the transfer foil for in-mold having a transfer layer on the release surface of the releasable base sheet, the transfer layer is at least a first transparent cross-linking curing. A resin layer, a printed pattern layer, a second transparent cross-linked cured resin layer, a metallic luster layer or a metallic print layer, and an adhesive layer are sequentially laminated, and the second transparent cross-linked cured resin layer has a thickness. It is a hard coat transfer foil for in-mold characterized by being 20 μm to 100 μm.

  The invention according to claim 2 of the present invention is the hard coat transfer foil for in-mold according to claim 1, wherein the metallic luster layer is a metal-deposited thin film layer.

  The invention according to claim 3 of the present invention is characterized in that the metallic tone printed layer is a layer printed on the entire surface with an ink containing a metallic pigment. This is a hard coat transfer foil for in-mold.

  The invention according to claim 4 of the present invention is characterized in that an anchor coat layer is provided between the printed picture layer and the second transparent cross-linked cured resin layer. It is the hard coat transfer foil for in-molds described in 1.

  In addition, the invention according to claim 5 of the present invention has an antistatic layer on the other surface of the releasable substrate sheet, for in-mold according to any one of claims 1 to 4 Hard coat transfer foil.

  In the invention according to claim 6 of the present invention, the releasable substrate sheet is composed of a laminate of a substrate layer and a release layer. It is the hard coat transfer foil for in-mold described.

The in-mold hard coat transfer foil of the present invention has a first transparent cross-linked cured resin layer as a hard coat in the outermost layer in a state of being transferred to a molded product, and a printed pattern layer is provided thereunder. Therefore, it exhibits good wear resistance, and there is no disappearance of the pattern in normal use.
Further, the in-mold hard coat transfer foil of the present invention is a transparent layer having a thickness of 20 μm to 100 μm on the inner layer side of the printed pattern layer formed of a highly concealing ink in a state where it is transferred to a molded product. Since it has a second transparent cross-linked cured resin layer and a metal glossy layer or a metallic print layer with good light reflectivity is provided below it, the shadow of the printed pattern layer is a thick transparent layer. The projected image is projected onto the metallic glossy layer or the metallic print layer through the second transparent cross-linked cured resin layer, and the reflected image is again visually recognized through the second transparent cross-linked cured resin layer. Due to the parallax between both the real image and the reflected image, the design looks three-dimensional and can exhibit high design.

  Further, by providing an anchor coat layer between the printed pattern layer and the second transparent crosslinked cured resin layer, the second transparent crosslinked cured resin layer, the anchor coat layer, the printed pattern layer, and the first transparent layer. Adhesion with the cross-linked cured resin layer can be improved.

  In addition, by providing an antistatic layer on the other surface of the releasable substrate sheet, the in-mold hard coat transfer foil of the present invention exhibits antistatic properties even during production or storage of the transfer foil. In such a configuration, dust does not adhere, and the appearance of the molded product serving as the transfer target can be prevented from being damaged by the dust.

  Moreover, since the release layer bears releasability when the releasable base sheet is composed of a laminate of a base material layer and a release layer, the material selection of the base material layer The degree of freedom increases, the releasability at the time of transfer is stable, and transfer can be performed more easily.

It is a schematic sectional drawing which shows an example of the hard coat transfer foil for in-mold which concerns on this invention. It is a schematic sectional drawing which shows the other example of the hard-coat transfer foil for in-molds which concerns on this invention. It is a schematic sectional drawing which shows the other example of the hard-coat transfer foil for in-molds which concerns on this invention. It is a schematic sectional drawing which shows the other example of the hard-coat transfer foil for in-molds which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail.

(In-mold hard coat transfer foil)
As shown in FIG. 1, the in-mold hard coat transfer foil according to the present invention has at least a first transparent cross-linked cured resin layer 4 as a transfer layer 3 on a release surface of a releasable base sheet 2. The basic structure is that the printed pattern layer 5, the second transparent cross-linked cured resin layer 6, the metallic luster layer or metallic print layer 7, and the adhesive layer 8 are laminated.
The printed picture layer 5 is formed of a highly concealed ink colored with white ink or the like, and the second transparent cross-linked curable resin layer 6 is a transparent layer having a thickness of 20 μm to 100 μm.
The metallic gloss layer or the metallic tone printed layer 7 is a layer printed on the whole surface with an ink containing a metallic pigment such as a metallic vapor-deposited thin film layer formed by vapor-depositing metallic aluminum or the like, or aluminum flakes.
By adopting such a configuration, the shadow of the pattern formed by the highly concealable ink of the printed pattern layer 5 is transferred to the metallic gloss layer or the metal via the second transparent crosslinked cured resin layer 6 which is a thick transparent layer. Since the projected image is projected onto the tone print layer 7 and the reflected image is again visually recognized through the second transparent cross-linked cured resin layer 6, the pattern is three-dimensional due to the parallax between the real image and the reflected image of the pattern. It can be seen and can exhibit high design properties.
Further, when in-mold transfer is performed using the in-mold hard coat transfer foil according to the present invention, the transfer layer 3 is peeled off from the releasable substrate sheet 2 and is formed through the adhesive layer 8. The first transparent crosslinked cured resin layer 4 is disposed on the outermost surface, and the printed picture layer 5 is disposed on the inner layer side of the first transparent crosslinked cured resin layer 4. Therefore, good wear resistance is exhibited by the action of the first transparent cross-linked cured resin layer 4 as a hard coat, and the printed pattern layer 5 can be prevented from being damaged in normal use.

In addition, the in-mold hard coat transfer foil according to the present invention may have an anchor coat layer 9 between the printed picture layer 5 and the second transparent crosslinked cured resin layer 6 as shown in FIG. good.
By setting it as such a structure, the adhesiveness of a 2nd transparent crosslinked cured resin layer, an anchor coat layer, a printed pattern layer, and a 1st transparent crosslinked cured resin layer can be improved.

In addition, the in-mold hard coat transfer foil according to the present invention may be configured to have an antistatic layer 10 on the other surface of the releasable substrate sheet 2 as shown in FIG.
By adopting such a configuration, the in-mold hard coat transfer foil 1 of the present invention exhibits antistatic properties at the time of manufacture and storage of the transfer foil, so that dust does not adhere and the transfer layer 3 is transferred. This is preferable in that the appearance of the article can be prevented from being damaged by dust.

In addition, the in-mold hard coat transfer foil according to the present invention may have a configuration in which the releasable base sheet 2 is composed of a laminate of a base layer 11 and a release layer 12, as shown in FIG. good.
By adopting such a configuration, in the in-mold hard coat transfer foil 1 of the present invention, since the release layer 12 is responsible for release properties, the degree of freedom in selecting the material of the base material layer 11 is increased, and at the time of transfer. This is preferable in that the peelability is stable and the transfer can be performed more easily.

  Next, each material which comprises the hard coat transfer foil for in-mold which concerns on this invention, and a manufacturing method are demonstrated.

(Releasable substrate sheet)
As shown in FIG. 1, the layer structure of the releasable substrate sheet 2 may be a single layer made of a material having sufficient releasability with the transfer layer 3 or may be shown in FIG. Thus, the laminated body of the base material layer 11 and the mold release layer 12 may be sufficient.

When the releasable substrate sheet 2 is composed of a single layer, it is necessary to select a material having good releasability from the transfer layer 3. From this point, as the material of the releasable base sheet 2, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, ethylene glycol-1,4 hexamethylenedi Polyester resins such as methanol-terephthalic acid copolymer, polyester-based thermoplastic elastomer, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene-butene copolymer, polyolefin resin such as olefin-based thermoplastic elastomer, nylon 6, Polyamide resin such as nylon 66, polyvinyl chloride, etc. can be used. Among these, a uniaxial or biaxially stretched polyester film is more preferable because of its excellent heat resistance.
The thickness of the releasable substrate sheet 2 is preferably about 5 μm to 200 μm.

(Release layer)
On the other hand, when the releasable base material sheet 2 is composed of a laminate of the base material layer 11 and the release layer 12, the release layer 12 bears the release performance with respect to the transfer layer 3, and therefore the release layer 12 However, what is necessary is just to be comprised with the material illustrated with the said single-layer mold release base material sheet 2, and various resin which has flexibility can be used for the base material layer 11. FIG.

As a material for the release layer 12, a release resin having release properties with respect to the first transparent crosslinked cured resin layer 4, a resin containing a release agent, a curable resin that is crosslinked with ionizing radiation, and the like are applied. it can.
As the releasable resin, for example, acrylic resin, melamine resin, polyester resin, urethane resin, fluorine resin, silicone resin, epoxy resin and the like can be used. These resins are used alone or in combination of two or more. Examples of mixing two or more types include a mixture of an acrylic resin and a silicone resin, a mixture of an acrylic resin and a melamine resin, and the like.
Examples of the resin containing a release agent include an acrylic resin, a vinyl resin, a polyester resin, and a fiber resin obtained by adding or copolymerizing a release agent such as fluorine resin, silicone resin, or various waxes. Resins can be used.
Examples of the curable resin that crosslinks with ionizing radiation include (meth) acrylate-based and epoxy-based monomers having a functional group that is polymerized (cured) by ionizing radiation such as ultraviolet (UV) and electron beam (EB). A resin containing an oligomer or the like can be used.

As a method for forming the release layer 12, the above resin is dispersed or dissolved in a solvent, roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat, kiss coat, knife coat, die coat, A method of forming by removing the solvent by applying and drying by a coating method such as comma coating, flow coating, or spray coating can be used.
If necessary, heat drying or aging is performed at a temperature of 30 ° C. to 200 ° C. In the case of an ionizing radiation curable resin, ionizing radiation is irradiated to cause crosslinking.
The thickness of the release layer 12 is usually about 0.1 μm to 5.0 μm, preferably about 0.3 μm to 3.0 μm. The thinner the thickness is, the better. However, when the thickness is 0.3 μm or more, better film formation is obtained and the peeling force is stabilized.

(Antistatic layer)
Moreover, in this invention, as shown in FIG.3 and FIG.4, it is good also as a structure which has the antistatic layer 10 in the other surface of the releasable base material sheet 2. FIG. The antistatic layer 10 is for preventing dust from adhering due to the generation of static electricity during the production, storage, and transfer of the hard coat transfer foil for in-mold. An inhibitor can be applied.

  Examples of the antistatic agent used in the antistatic layer 10 include polyethylene glycols such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, and alkylphenol ethylene oxide. Polyhydric alcohols such as adducts, alkylene oxides such as polyethylene oxide, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines , Nonionic surfactants such as polyhydric alcohol esters, carboxylates such as alkali metal salts of higher fatty acids, higher alcohol sulfates, high Sulfate esters such as alkyl ether sulfates, sulfonates such as alkylbenzene sulfonates and paraffin sulfonates, phosphate esters such as higher alcohol phosphates, phosphates, phosphonates, phosphonates Anionic surfactants such as higher alkylamines, cyclic amines, hydantoin derivatives, amideamines, ester amides, quaternary ammonium salts such as alkyltrimethylammonium salts, pyridine and other heterocyclic rings, cation interfaces such as phosphonium or sulfoniums Activators, amino acids such as higher alkylaminopropionates, aminosulfonic acids, sulfuric or phosphoric acid esters of aminoalcohols, higher alkyldimethylbetaines, higher alkyldihydroxyethylbetaines, etc. Surfactants such as amphoteric surfactants such as alkylbetaines, natural surfactants such as saponin, carbon black, graphite, modified graphite, carbon black graft polymer, tin oxide-indium oxide, tin oxide-antimony oxide, Conductive powders such as tin oxide and titanium oxide-tin oxide-antimony oxide can be used.

In addition, a high molecular weight antistatic agent in which a conductivity-providing functional group of a low molecular weight antistatic agent such as a surfactant is bonded to a polymer can also be applied.
Examples of the polymer-type antistatic agent include polyether type (polyethylene oxide, polyethylene oxide crosslinked product, copolymer of polyethylene oxide and other resin, polyethylene glycol, copolymer of polyethylene glycol and other resin) and the like. Ionic, quaternary ammonium salt (quaternary ammonium base-containing copolymer (quaternary ammonium base-containing (meth) acrylate copolymer, quaternary ammonium base-containing maleimide copolymer, quaternary ammonium base A cationic system such as a methacrylimide-containing copolymer).

  Furthermore, polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly (1,6-heptadiyne), polybiphenylene (polyparaphenylene), polyparafinylene sulfide, polyphenylacetylene, polo (2,5-thienylene), or Conductive polymers such as these derivatives can also be applied.

  These antistatic agents may be used alone or in combination, and may be applied alone or mixed in another binder. These surfactant contents are about 0.001-10 mass%. Moreover, you may add additives, such as a plasticizer, a stabilizer, a hardening | curing agent, a dispersing agent chelating agent, a pH adjuster, antiseptic | preservative, and an antifoamer, as needed.

(Transfer layer)
Next, the transfer layer of the in-mold hard coat transfer foil according to the present invention will be described.
As shown in FIG. 1, the transfer layer 3 includes at least a first transparent cross-linked cured resin layer 4, a printed pattern layer 5, a second transparent cross-linked cured resin layer 6, a metallic gloss layer or a metallic tone printed layer 7, and The basic configuration is that the adhesive layer 8 is laminated.
Moreover, as shown in FIG. 2, it is good also as a structure which has the anchor coat layer 9 between the printed pattern layer 5 and the 2nd transparent bridge | crosslinking cured resin layer 6, as needed.

(First transparent cross-linked cured resin layer)
As the resin constituting the first transparent crosslinked cured resin layer 4, a resin composition that is crosslinked and cured by a chemical reaction at room temperature, ionizing radiation such as heat or ultraviolet rays, and the like, preferably an ionizing radiation curable resin. . The thickness of the first transparent crosslinked cured resin layer 3 is usually 1 to 10 μm.

  Examples of the thermosetting resin include thermosetting resins such as polyurethane resin, phenol resin, urea resin, melamine resin, epoxy resin, and unsaturated polyester resin. The polyurethane resin is a resin obtained by a reaction between a polyvalent alcohol (polyol) and a polyvalent isocyanate (polyisocyanate).

  Examples of the polyhydric alcohol include polyhydric alcohols such as ethylene glycol, trimethylolpropane, pentaerythritol, glycerin, α-methylglucoside, sorbitol, dipentaerythritol, ethylene oxide, propylene oxide, 1,2-, 2, Polyoxyalkylene polyols and acrylic polyols to which alkylene oxides (2 to 18 carbon atoms of the alkylene group) such as 3- or 1,3-butylene oxide, styrene oxide, α-olefin oxide having 6 to 18 carbon atoms, epichlorohydrin are added Polyester polyol, polyether polyol, etc. are used.

  Polyvalent isocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate and other aromatic polyisocyanates, tetra Aliphatic polyisocyanates such as methylene diisocyanate and hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) And polyisocyanates such as alicyclic polyisocyanates.

As a composition of an ionizing radiation curable resin, in a molecule such as a (meth) acrylate of a polyfunctional compound such as a polyhydric alcohol (hereinafter, acrylate and methacrylate are described as (meth) acrylate in this specification). From a compound having a radical polymerization type unsaturated group, a compound having a cationic polymerization type functional group in a molecule such as an epoxy compound, or a monomer (monomer) or an oligomer (or prepolymer) of a compound such as an unsaturated polyester A known one can be applied.
These monomers and oligomers (or prepolymers) may be used alone, or different monomers, different oligomers (or prepolymers), or monomers and oligomers (or prepolymers). (Polymer) may be mixed and used.

  Examples of the monomer of (meth) acrylate include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( A meth) acrylate etc. can be illustrated.

Examples of the (meth) acrylate oligomer (or prepolymer) include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate.
Examples of the epoxy compound include bisphenol type epoxy resins and novolac type epoxy resins.

  Here, what is normally used as said monomer and oligomer (or prepolymer) is a liquid at room temperature (normal temperature) in an uncrosslinked state, and becomes a solid only after crosslinking. However, in the case of in-mold transfer of the transfer foil, it is preferable to use a transfer foil that is in a solid state even at an uncrosslinked stage and becomes a crosslinked solid upon irradiation with ionizing radiation.

Here, in this invention, the following methods can be used as a usage form of the said ionizing radiation curable resin composition.
First, the ionizing radiation curable resin composition is dissolved (or dispersed) in a solvent to form a liquid, and then coated on the releasable substrate sheet 2 by a method such as a slit coat method, and then a solvent. Is evaporated and dried to be non-adhered and solidified in an uncrosslinked state to produce a transparent crosslinked cured resin layer in an uncrosslinked state.
In that case, if necessary, by applying an appropriate amount of ionizing radiation within the range that does not impair the shape followability to the surface shape of the transfer object, it is made more incomplete (partially) cross-linked. The transparent cross-linked cured resin layer may be prevented from flowing due to heat or stress during transfer.

Next, using the transfer foil, the transfer layer is transferred while following the surface shape of the transfer object. At this time, since the transparent cross-linked cured resin layer is not completely cross-linked, it maintains thermoplasticity and can follow the surface shape of the transfer target. Thereafter, the transparent crosslinked cured resin layer is completely crosslinked and cured by irradiating ionizing radiation again.
Thereby, the transparent crosslinked cured resin layer exhibits sufficient scratch resistance (hard coat property).

On the other hand, as an example of an ionizing radiation curable resin composition that is in a solid state even in an uncrosslinked stage,
(1) oligomers (or prepolymers) such as (meth) acrylates, epoxy resins, or unsaturated polyesters having a high molecular weight and a melting point or melting temperature of room temperature or higher (usually 80 ° C. or higher),
(2) A monomer or oligomer (or prepolymer) such as liquid (meth) acrylate, epoxy resin, or unsaturated polyester in an uncrosslinked state at room temperature, and a solid acrylic resin, urethane resin, or the like at room temperature And a non-adhesive solid made at room temperature by adding the above thermoplastic resin.

Furthermore, various ionizing radiation curable resin compositions listed above may be used by adding additives such as reactive diluents, photopolymerization initiators, photosensitizers, and fillers as necessary. Can do.
Examples of reactive diluents include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, N-vinylpyrrolidone, and polyfunctional monomers such as tripropylene glycol diacrylate, trimethylolpropane tri (meta ) Acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
The photopolymerization initiator is required to be added when using light such as ultraviolet rays and visible rays as ionizing radiation. Photopolymerization initiators include acetophenones, benzophenones, thioxanthones, etc., in the case of compounds having radically polymerizable unsaturated groups in the molecule, and in the case of compounds having cationically polymerizable functional groups in the molecule. Includes aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and the like.
Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and the like can be used by mixing.

(Print pattern layer)
The printed picture layer 5 is formed by printing a pattern such as a desired character, pattern, or pattern. As the ink that is usually used, a colored ink obtained by adding a pigment, a dye, an additive, or the like to a vehicle with a synthetic resin such as acrylic, vinyl, or urethane as necessary is used.
In the present invention, a highly concealed colored ink obtained by coloring a white ink or the like mainly composed of a white pigment is used in order to produce a three-dimensional effect.

  Examples of the vehicle include acrylic monomers such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, or homopolymers of methacrylic monomers, or acrylic monomers and methacrylic acid thereof. Copolymers based on co-monomers, styrene resins such as polystyrene and poly-α-methylstyrene and styrene copolymers, cellulose acetate, vinyl chloride, vinyl acetate, urethane resins, polyester resins and alcohol-insoluble systems Resins are preferred, and one or more of these can be selected and used.

Further, in order to improve the strength between the ink layers, it is possible to use a two-component curing type resin system. In this case, a necessary amount of a curing agent can be added and used.
As means for forming the printed pattern layer 5, a known printing method such as gravure printing, offset printing, electrostatic printing, and jet printing can be used.

(Anchor coat layer)
Since the first transparent cross-linked cured resin layer 4 and / or the second transparent cross-linked cured resin layer 6 may lack adhesion with other layers, as shown in FIG. A transparent anchor coat layer 9 can be provided. The adhesion between the second transparent cross-linked cured resin layer 6, the printed pattern layer 5, and the first transparent cross-linked cured resin layer 4 is improved via the anchor coat layer 9.

  Examples of the anchor coat layer 9 include polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, and ethylene. A copolymer with vinyl acetate or acrylic acid, an epoxy resin, or the like can be used. Preferred is a polyurethane resin composed of isocyanate or isocyanate and a polyhydric alcohol.

  These resins are appropriately dissolved or dispersed in a solvent to form a coating solution, which is coated by a known coating method and dried to form the anchor coat layer 9. In addition, when a resin, a monomer, an oligomer, a prepolymer, and the like, a reaction initiator, a curing agent, a crosslinking agent, and the like are appropriately combined, or when a main agent and a curing agent are combined, they are applied and dried, You may form by making it react by the aging process after drying. The thickness of the anchor coat layer 9 is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(Second transparent cross-linked cured resin layer)
As the resin constituting the second transparent cross-linked cured resin layer 6, as with the first transparent cross-linked cured resin layer 3 described above, a resin that cross-links and cures by chemical reaction at room temperature, ionizing radiation such as heat or ultraviolet rays, etc. A composition can be applied, and preferably an ionizing radiation curable resin can be used.
However, the second transparent crosslinked cured resin layer 6 is projected on the metallic glossy layer or the metallic tone printed layer 7 through the second transparent crosslinked cured resin layer 6 which is a thick transparent layer, The reflected image is visually recognized again through the second transparent cross-linked cured resin layer 6, and acts to make the pattern look three-dimensional due to the parallax between the real image and the reflected image of the pattern. To do. Therefore, the thickness of the second transparent cross-linked cured resin layer 6 is preferably 20 μm to 100 μm.

  The second transparent cross-linked cured resin layer 6 is formed by dissolving (or dispersing) the above-mentioned ionizing radiation curable resin composition in a solvent to form a liquid, and then slits on the printed pattern layer 5 or the anchor coat layer 9. Coating is performed by a method such as a coating method, and then the solvent is evaporated and dried, followed by irradiation with ionizing radiation to completely crosslink and cure.

(Glossy metallic layer or metallic print layer)
The metallic gloss layer or the metallic tone printed layer 7 is provided on the second transparent cross-linked cured resin layer, and projects the reflected image of the printed picture layer 5 through the second transparent cross-linked cured resin layer. The in-mold hard coat transfer foil according to the present invention expresses a three-dimensional effect.

The metallic gloss layer or the metallic tone printed layer 7 can be a metal vapor-deposited thin film layer made of metal or the like formed by vapor deposition, for example.
Depending on the metallic luster color to be developed, the material may be a metal such as aluminum, tin, chromium, nickel, gold, platinum, silver, copper, indium, titanium, zinc, or an oxide thereof, and an alloy thereof or Compounds can be used.
As a method for forming the metal thin film layer, a method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plating method can be used.

  Moreover, the metallic luster layer or the metallic tone printing layer 7 can be a layer printed on the entire surface with an ink containing a metallic pigment such as aluminum flakes, for example. As a method for forming the metallic print layer, a known printing method such as a gravure printing method or a screen printing method can be used.

(Adhesive layer)
In the present invention, the adhesive layer 8 is used for adhering the transfer layer 3 to a molded product, and has an adhesive strength at room temperature, or expresses an adhesive or adhesive strength by a treatment such as heating. Can be used.

The material of the adhesive layer 8 is not particularly limited as long as it has adhesiveness and / or tackiness, and includes what is called an adhesive, a pressure-sensitive adhesive, and a hot melt.
For example, acrylic, epoxy, vinyl acetate, vinyl chloride, isocyanate, silicone, styrene-butadiene, vinyl chloride-vinyl acetate, ethylene-vinyl acetate, polyester, rubber chloride, chlorinated polypropylene Examples thereof include emulsion resins, organic solvent-type resins, water-soluble resins, etc., each of which uses a single resin such as a polyurethane resin or a polyurethane resin alone, or a mixture thereof.

As a method for forming the adhesive layer 8, a coating liquid obtained by diluting the above resin with water or an organic solvent is used as a printing method such as gravure printing, offset printing, or screen printing, or roll coating, bar coating, comma A coating method such as coating, spray coating, or extrusion coating may be used, followed by drying or cooling.
The thickness of the adhesive layer 5 is not particularly limited, but is usually about 1 μm to 10 μm.

(Transfer)
The material to be transferred to the in-mold hard coat transfer foil of the present invention is not limited in material and shape. For example, the material is a polyolefin resin such as polyethylene or polypropylene, an acrylic resin, or a vinyl chloride resin. , Acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, phenol resin, or other metals or metal compounds such as aluminum, iron, stainless steel, brass, wood plywood, wood veneer, medium Wood such as density fiberboard (MDF), ceramics such as glass and ceramics, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), cement such as slag cement, calcium silicate, paper, fabric, non-woven fabric, etc. And is optional.
Also, the shape is arbitrary such as a sheet (film), a flat plate, a curved plate, a rod-shaped body, a three-dimensional object and the like. Depending on the uneven shape of the surface to be transferred, transfer can be performed by employing an appropriate transfer method described later. In the injection molding simultaneous painting transfer method, the shape of the transfer object is formed simultaneously with the transfer (resin molding).

EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to this.
Example 1
A biaxially stretched polyethylene terephthalate film with a thickness of 38 μm was used as the base layer of the releasable base sheet, and Denatron (manufactured by Nagase Sangyo Co., Ltd., conductive organic polymer / product) Name) was applied by gravure printing so that the thickness was 0.5 μm (after drying) and dried to form an antistatic layer.

  Next, gravure EX-114 (manufactured by Dainichi Seika Kogyo Co., Ltd., release agent / trade name) on the other surface of the base material layer so that the thickness becomes 1.0 μm (after drying). It was applied by a roll coating method and dried to form a release layer.

Next, the following layers were sequentially laminated on the release layer as a transfer layer.
First, as a resin liquid (composition) for forming the first transparent cross-linked cured resin layer, EXF (produced by Dainichi Seika Kogyo Co., Ltd., ionizing radiation curable resin / trade name) has a thickness of 5.0 μm (after curing). The first transparent cross-linking curing was performed by applying a UV coating at a running speed of 40 m / min using a high-pressure mercury lamp (Ushio Electric Co., Ltd., curing device / trade name) 80 W / cm. A resin layer was formed.

  Next, on the surface of the first transparent cross-linked cured resin layer, a printing pattern layer is formed by gravure printing using urethane printing ink VM (manufactured by Dainichi Seika Kogyo Co., Ltd., two-component curable printing ink / trade name). Formed.

  Next, TM-AC (manufactured by Dainichi Seika Kogyo Co., Ltd., two-component curable primer layer composition / trade name) is gravured on the printed pattern layer surface so that the thickness becomes 2.5 μm (after drying). The anchor coat layer was formed by applying and drying by a printing method.

  Next, as a resin liquid (composition) for forming a second transparent cross-linked cured resin layer on the surface of the anchor coat layer, EXF (produced by Dainichi Seika Kogyo Co., Ltd., ionizing radiation curable resin / trade name) is thickened. The film is applied by slit coating so that the thickness is 50 μm (after curing), and irradiated with ultraviolet rays at a traveling speed of 40 m / min using a high-pressure mercury lamp (Ushio Electric Co., Ltd., curing device / product name) 80 W / cm. A second transparent cross-linked cured resin layer was formed.

  Next, a 60 nm thick aluminum metal deposition thin film layer was formed as a metallic luster layer by vacuum deposition.

  Furthermore, TM-HS (manufactured by Dainichi Seika Kogyo Co., Ltd., adhesive layer composition / trade name) is applied by gravure printing so that the thickness is 5.0 μm (after drying) to form an adhesive layer. Thus, a hard coat transfer foil for in-mold according to the present invention was obtained.

  When the in-mold hard coat transfer foil prepared as described above was used for injection molding and transferred to a molded product, a molded product having an unprecedented three-dimensional effect could be obtained.

DESCRIPTION OF SYMBOLS 1 Hard coat transfer foil for in-mold 2 Releasable base material sheet 3 Transfer layer 4 1st transparent crosslinked cured resin layer 5 Print pattern layer 6 2nd transparent crosslinked cured resin layer 7 Metal gloss layer or metallic tone printed layer 8 Adhesive layer 9 Anchor coat layer 10 Antistatic layer 11 Base material layer 12 Release layer

Claims (6)

In the in-mold transfer foil having a transfer layer on the release surface of the releasable substrate sheet,
The transfer layer is
At least a first transparent cross-linked cured resin layer, a printed pattern layer, a second transparent cross-linked cured resin layer, a metallic gloss layer or a metallic print layer, and an adhesive layer are sequentially laminated,
The hard coating transfer foil for in-mold, wherein the second transparent cross-linked curable resin layer has a thickness of 20 μm to 100 μm.   The hard coat transfer foil for in-mold according to claim 1, wherein the metallic gloss layer is a metal-deposited thin film layer.   The hard coat transfer foil for in-mold according to any one of claims 1 to 2, wherein the metallic printing layer is a layer printed on the entire surface with an ink containing a metallic pigment.   The hard coat transfer foil for in-mold according to any one of claims 1 to 3, further comprising an anchor coat layer between the printed pattern layer and the second transparent cross-linked cured resin layer.   The hard coat transfer foil for in-mold according to any one of claims 1 to 4, further comprising an antistatic layer on the other surface of the releasable substrate sheet. The hard coat transfer foil for in-mold according to any one of claims 1 to 5, wherein the releasable substrate sheet comprises a laminate of a substrate layer and a release layer.

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