JP4311554B2 - Method for using intermediate transfer sheet for molded article and intermediate transfer sheet for molded article - Google Patents

Description

The present invention provides an intermediate transfer type intermediate transfer that uses a thermal transfer sheet to record a pattern or the like on an intermediate transfer sheet by thermal transfer, and then retransfers it to a plastic molding having a three-dimensional structure via heat. Regarding the sheet.

Conventionally, there has been a demand for improving damage resistance, chemical resistance, and the like for plastic molded articles having a three-dimensional structure, and there are many examples of applying a protective film to plastic molded articles such as protective surfaces and protective glasses. Recently, there are many techniques for providing a protective layer on the surface of a molded product by transfer.

By the way, in a protective layer transfer sheet in which a protective layer is provided on the surface of a molded product by transfer, a technique of improving scratch resistance and solvent resistance by curing the protective layer is often used.
Generally, the protective layer is cured by heat or ionizing radiation (Patent Document 1). In the case of heat curing, the protective layer is cured in advance in the transfer film state. This is because heat curing generally takes time, and heat treatment after transfer is inferior in system simplicity. In addition, a defect due to thermal deformation of the image formed product may occur.

  On the other hand, in the case of ionizing radiation curing, the protective layer may be cured before transfer or after transfer. However, there are the following problems. That is, the ionizing radiation curable resin usually has a tack before curing, and cannot be formed into a roll like a thermal transfer sheet. For this reason, a separator becomes indispensable (patent document 2), leading to an increase in cost. Further, due to this tack, it is difficult to further laminate an adhesive layer on the protective layer. Eventually, it can be used only for an adherend having good adhesion to the protective layer and lacks versatility.

  Further, an intermediate transfer sheet using a base material that transmits ultraviolet light having a wavelength of less than 365 nm, such as a general-purpose biaxially stretched PET film, is provided. (Patent Documents 3 and 4) However, there is no provision of an intermediate transfer sheet using a base material that hardly transmits a wavelength of less than 365 nm, such as an easily molded PET film that is easily deformable by heat.

JP-A-5-330259 JP-A-5-57235 JP2003-231366 JP 2003-191653 A

  In addition, when a protective layer is transferred to a molded product using a protective layer transfer sheet in which an ionizing radiation curable resin is provided on an easily molded PET film or acrylic film that is easily thermally deformed, the base material must be removed before the protective layer is cured. When peeled, there is a case in which the protective layer does not peel well at the interface between the protective layer and the substrate, particularly at the bent portion of the molded product, and the protective layer coagulates and remains partially on the substrate side. If the protective layer is agglomerated and peeled off, the film may be whitened to cause defects in appearance, and it may also have adverse effects on scratch resistance and chemical resistance. In such a case, more stable peelability of the protective layer can be obtained by irradiating ionizing radiation from the base material side before peeling the base material, and curing the protective layer in advance before peeling. However, unlike the conventional general-purpose biaxially stretched PET film, the easily molded PET film and acrylic film described above have an ultraviolet absorption region shifted to the visible light side. This will be described with reference to the drawings. FIG. 1 shows a light transmittance curve of an easily molded PET film, and FIG. 2 shows a light transmittance curve of a biaxially stretched PET film. The biaxially stretched PET film exhibits a transmittance of 80% at a wavelength of 365 nm, but the easily molded PET film has a transmittance of approximately 25%. In other words, when trying to cure using the most versatile high-pressure mercury lamp as ionizing radiation, the easily molded PET film absorbs light around 365 nm, which is the main wavelength of the high-pressure mercury lamp, and the protective layer underneath it is light. Almost never arrived. For this reason, defective curing may occur, and there may be a problem that the interface cannot be peeled off well at the bent portion. In order to avoid such curing failure, a lamp such as a metal halide lamp in which the main wavelength is shifted to a higher wavelength side must be used.

It is an object of the present invention to provide a protective layer transfer sheet for molded articles that has excellent substrate releasability even at the bent portion of the molded article in the protective layer transfer process and can give excellent fastness to the transfer target. It is to be.

  In addition, even when applied to the intermediate transfer sheet as an application of the same technology, the re-transfer process has excellent peelability of the substrate even at the bent part of the molded product, and gives the transferred object excellent fastness It is to provide an intermediate transfer sheet for a molded product that can be used.

Therefore, in order to solve the above-mentioned problems, the inventors have made the invention shown below.

The invention according to claim 1 is an intermediate transfer sheet for molded articles for thermal transfer image recording in which at least a protective layer, an intermediate layer, and an image receiving / adhesive layer are provided on a PET film substrate, and the protective layer is mainly ionizing radiation. It consists of an acrylic-silica hybrid resin that can be cured by irradiation. The resin has no tack before curing at room temperature, contains a sensitizer as an additive in its protective layer, and a polyester urethane whose intermediate layer is the main component. It is an intermediate transfer sheet for molded articles, which contains a resin.

On the other hand, the invention according to claim 2 is characterized in that the intermediate transfer sheet for molding is superimposed on an adherend and attached by heating and pressurization, and then the adherend is molded using a vacuum molding apparatus. after curing the protective layer by irradiation with ionizing radiation from the side, after peeling off the base material, an intermediate for molding of claim 1, wherein the use in a method of irradiating again the ionizing radiation the protective layer This is a method of using a transfer sheet.

Hereinafter, each layer constituting the protective layer transfer sheet of the present invention will be described.
As a base material used in the protective layer transfer sheet for a molded product of the present invention, in consideration of good transfer to a plastic molded product having a three-dimensional structure, the transfer sheet follows the shape of the molded product. it is preferable to heat deformation, the use of easily-molded PET film from any of processability during the transfer sheet produced good inside are particularly preferred. Although the thickness of these base materials is suitably changed according to material so that the intensity | strength and heat resistance may become appropriate, about 1.0-100 micrometers is preferable normally.

  In the protective layer transfer sheet of the present invention, a protective layer is provided on at least a part of the substrate. The protective layer is composed of at least one layer, and is cured by irradiation with ionizing radiation to obtain solvent resistance, water resistance and scratch resistance. In order to obtain the above resistance, ionizing radiation may be irradiated immediately after coating the protective layer during the production of the protective layer transfer sheet, or ionizing radiation from the back surface of the protective layer transfer sheet using a transparent substrate. May be irradiated, or may be irradiated after transfer to the adherend. Even if it is irradiated with ionizing radiation at any time, the protective layer can be cured to obtain the desired resistance, but for the following reasons, after molding, it is irradiated with ionizing radiation before peeling the substrate, It is preferable to peel the substrate after the protective layer is cured. That is, if the base material is peeled off before the protective layer is cured from the base material side, the protective layer does not peel well at the interface between the protective layer and the base material, particularly at the rounded portion of the molded product. There is a case where a part of the substrate remains. If the protective layer is agglomerated and peeled off, the film may be whitened to cause defects in appearance, and it may also have adverse effects on scratch resistance and chemical resistance. In such a case, irradiation with ionizing radiation before peeling off the substrate and curing after the protective layer is cured in advance results in more stable peelability of the protective layer.

    In the case where sufficient curing cannot be obtained by one-time irradiation of ionizing radiation from the substrate side, the protective layer is preferably irradiated again with ionizing radiation after peeling off the substrate. When the transfer layer provided with at least the protective layer is cured using the protective layer transfer sheet and the intermediate transfer sheet of the present invention, the radiation energy increases and the calorific value of the high-pressure mercury lamp also increases with one ionizing radiation. Since the molded product is adversely affected by heat generation, the method of irradiating twice as described above is preferable.

  The protective layer contains at least an ionizing radiation curable resin, a photoinitiator, and a sensitizer. As described above, when an easily molded PET film (thickness 50 μm) of a base material suitable for the application of the present invention is used, when a high-pressure mercury lamp is used as a lamp as shown in FIG. The light transmittance is about 25%, and sufficient light does not reach the protective layer. Depending on the photoinitiator, molecular cleavage is difficult to occur. Therefore, the inclusion of a sensitizer facilitates the cleavage of the photoinitiator molecule.

The resin constituting the protective layer may be any resin that can be cured by ionizing radiation. Various acrylate oligomers and prepolymers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, and silicone acrylate having an acryloyl group or a methacryloyl group. Alternatively, a polyfunctional monomer such as styrene and a polyfunctional monomer such as trimethylolpropane triacrylate may be used alone or in combination of two or more with polyene-thiol resin or the like.
More preferably, the protective layer preferably contains an ionizing radiation curable acrylic-silica hybrid resin as a main component in order to obtain a more robust protective layer. The acrylic-silica hybrid resin preferably has a silica component of 15% by weight to 60% by weight, more preferably 20% by weight to 30% by weight. Outside the above range, the film strength is lowered, and the function as a protective layer may be deteriorated.

  However, since most of these resins are liquid or viscous before curing, the protective layer transfer sheet needs to have a release film on the surface in order to cause the protective layer to tack.

  Therefore, it is preferable that the acrylic-silica hybrid resin has no tack at room temperature before curing. If there is no tack, when the protective layer transfer sheet is rolled up, the protective layer sticks to the opposite surface of the film and peels off from the base material. In the case of further laminating an adhesive layer on the film, there is an advantage that the film design becomes easy, for example, it becomes easier to laminate.

  Moreover, it is preferable that Tg before hardening of this acrylic-silica hybrid resin is 30 degreeC or more. If it is less than 30 degreeC, there exists a tendency for tack to come out easily at normal temperature.

  Of course, the above-mentioned monomers, oligomers and the like may be added as long as the acrylic-silica hybrid resin does not cause tackiness.

In addition to the ionizing radiation curable resin, a thermoplastic resin can be added. Examples of the thermoplastic resin include acrylic resins, vinyl acetate resins, epoxy resins, polyester resins, polycarbonate resins, butyral resins, gelatin, cellulose resins, polyamide resins, vinyl chloride resins, urethane resins. Examples thereof include resins.
As other additives, ultraviolet absorbers, colored pigments, white pigments, extender pigments, fillers, antistatic agents, antioxidants, fluorescent whitening agents, dyes, and the like can be used as necessary.

  The thickness of the protective layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is less than the said range, hardening as a protective layer will be thin, and if it exceeds the said range, it will become expensive.

  Furthermore, in the present invention, it is essential to add a so-called sensitizer that promotes the photocuring reaction. Examples of sensitizers include aliphatic amines, amines containing aromatic groups, amine compounds such as nitrogen heterocyclic compounds such as piperidine, urea compounds such as allyl and O-tolylthiourea, sodium diethyldithiophosphate, Sulfur compounds such as soluble salts of aromatic sulfinic acids, nitrile compounds such as N, N-disubstituted-P-aminobenzonitrile compounds, phosphorus compounds such as tri-n-butylphosphine and sodium diethyl phosphate, Michler's ketone, Other nitrogen compounds such as N-nitrosohydroxylamine derivatives and oxazoline compounds, and chlorine compounds such as carbon tetrachloride and hexachloroethane may be mentioned.

  The addition amount of the sensitizer is preferably about 0.1% by weight to 10% by weight with respect to the ionizing radiation curable resin, and more preferably 2% by weight to 5% by weight.

  In the present invention, a thermoplastic adhesive layer is preferably provided on the protective layer in order to improve the adhesion of the protective layer to the transfer target. For this adhesive layer, it is preferable to select a resin according to the material of the transfer object, but in general, it is preferably formed from a thermoplastic resin as shown below, for example, acrylic resin, acetic acid From resins with good thermal adhesive properties such as vinyl resins, epoxy resins, polyester resins, polycarbonate resins, butyral resins, gelatin, cellulose resins, polyamide resins, vinyl chloride resins, urethane resins, etc. A material having an appropriate glass transition temperature is selected.

  As an additive for the adhesive layer, an ultraviolet absorber, a color pigment, a white pigment, an extender pigment, a filler, an antistatic agent, an antioxidant, a fluorescent whitening agent, a dye and the like may be used as necessary. it can.

  The thickness of the adhesive layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is less than the above range, the adhesive strength is too low, so that it does not contribute much to the improvement of the adhesion of the protective layer.

  The protective layer transfer sheet of the present invention is provided with a heat-resistant slide to prevent adverse effects such as sticking and wrinkles due to heat from a thermal head or a heat roller on the back surface of the substrate, that is, the surface opposite to the surface provided with the protective layer. An adhesive layer may be provided. The resin for forming the heat-resistant slipping layer may be any conventionally known resin such as polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene. Resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetopropionate resin, cellulose acetate Butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polycarbonate resin, chlorinated poly Olefin resins.

  In addition, in order to improve the heat resistance of the heat resistant slipping layer, the coating film strength and the adhesion to the substrate, a reaction cured product of a thermoplastic resin having a reactive group in the resin and a polyisocyanate, or an unsaturated bond. The reaction product with the monomer and oligomer which can be used can be used, and the curing method is not particularly limited, such as heating, irradiation with ionizing radiation, and the curing means. The slipperiness imparting agent that is added to or overcoated with the heat resistant slipping layer made of these resins includes phosphate ester, silicone oil, graphite powder, silicone graft polymer, fluorine graft polymer, acrylic silicone graft polymer, acrylic siloxane, and aryl. Examples thereof include silicone polymers such as siloxane. The heat resistant slipping layer is prepared by dissolving or dispersing the above-described resin, slipperiness imparting agent, and filler with an appropriate solvent to prepare a heat resistant slipping layer forming ink. It can be applied to the back surface of the material by a forming means such as a bar coating method, a gravure printing method, a screen printing method, a reverse coating method using a gravure plate, and then dried. The coating thickness of the heat resistant slipping layer is about 0.1 to 2.0 μm in terms of solid content.

  When the protective layer is difficult to peel from the base material, a release layer can be formed between the base material and the protective layer. The release layer includes, for example, waxes, silicone wax, silicone resin, fluorine resin, acrylic resin, polyvinyl alcohol resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acrylic vinyl ether resin, maleic anhydride resin, and It can be formed by applying and drying a coating solution containing at least one copolymer of these resin groups by a conventionally known method such as gravure coating or gravure reverse coating.

  The release layer can be appropriately selected from those that move to the transfer medium during thermal transfer, those that remain on the substrate side, or those that cohesively break, but the release layer is non-transferable, and thermal transfer The release layer remains on the base material side, so that the interface between the release layer and the transfer protective layer becomes the surface of the protective layer after the heat transfer, surface gloss, transfer stability of the protective layer, etc. Since it is excellent in this point, it is preferably performed. The mold release layer can be formed by a conventionally known coating method, and the coating amount is about 0.01 μm to 5.0 μm in a dry state. If a matte protective layer is desired after transfer, various types of particles are included in the release layer, or the surface of the release layer on the protective layer side is matted to form a surface mat. You can also If the substrate and the protective layer are peelable, the protective layer can be peeled directly from the substrate by thermal transfer without providing the release layer.

  In addition, by applying the technology of the protective layer transfer sheet of the present invention, production of cards such as ID cards, identification cards and licenses, decoration of media such as CD-R and DVD-R, etc. Decoration of a plastic molded product having a dimensional structure can be performed while having a high surface protection function. For use in such applications, a color image and / or a character image is formed by a thermal printer using a thermal transfer sheet on a receiver or a card, and the protective layer transfer sheet of the present invention is used thereon. It is also possible to impart a surface protection function by forming a protective layer by transferring the transfer protective layer.

  Furthermore, the card can be provided with embossing, signing, IC memory, magnetic layer, hologram, other printing, and the like, and embossing, signing, magnetic layer, etc. can be provided after transfer of the protective layer.

  On the other hand, an intermediate transfer sheet can be obtained by further applying the technology. That is, an image receiving / adhesive layer having an image receiving function in addition to the adhesive layer described above may be laminated on the protective layer. For example, character information can be formed on an intermediate transfer sheet by a melt transfer method, and an image such as a photograph can be formed by a sublimation transfer method. If an intermediate transfer sheet preprinted with such characters and image information is transferred to a desired article, a decorative molded product having a three-dimensional structure having a high surface protection function can be produced.

More preferably, an intermediate layer is provided between the protective layer and the image receiving / adhesive layer. By providing the intermediate layer, it is possible to prevent the adhesiveness with the image receiving layer from being lowered after the protective layer is cured. It is preferable to contain a polyester urethane resin as a main component of the intermediate layer. In addition to the polyester urethane, a thermoplastic resin can be added to the intermediate layer.
Examples of the thermoplastic resin include acrylic resins, vinyl acetate resins, epoxy resins, polyester resins, polycarbonate resins, butyral resins, gelatin, cellulose resins, polyamide resins, vinyl chloride resins, urethane resins. Examples thereof include resins.
The thickness of the intermediate layer is preferably in the range of 0.1 to 10.0 μm. If the thickness is less than the above range, sufficient adhesion to the protective layer and the image receiving / adhesive layer cannot be obtained.
Moreover, when the thickness is equal to or greater than the above, foil breakage is reduced.

  When transferring, thermal transfer printers may set transfer conditions separately for sublimation transfer, melt transfer, and protective layer transfer, or use a common printer to adjust the printing energy appropriately. You may go. In the protective layer transfer sheet and the intermediate transfer sheet of the present invention, the heating means is not limited to a thermal transfer printer, and other heating plates, hot stampers, hot rolls, line heaters, irons, and the like can also be used for transfer. The protective layer may be transferred to the entire surface of the formed image or may be transferred only to a specific portion.

According to the present invention, even when transferring to a plastic molded product having a bent portion, the protective layer can be transferred well without causing poor peeling.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “part” or “%” is based on mass unless otherwise specified.

The protective layer coating solution 1 was applied to the surface of a 50 μm easily-molded PET film having a heat-resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, the protective layer transfer sheet 1 was obtained by applying the adhesive layer coating liquid 1 on the protective layer with a bar coater so that the dry coating thickness was 0.5 μm.

Coating liquid for protective layer 1
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 23%, Tg 45 ° C., Mw 20,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
Sensitizer 0.6 parts (UV634A, manufactured by Seiko Advance)
MEK 30 parts Adhesive layer coating solution 1
50 parts of polyester urethane resin (Byron UR-3200, solid content 30%, manufactured by Toyobo)
50 parts of toluene

The protective layer coating solution 2 was applied to the surface of a 50 μm easily-molded PET film having a heat-resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, in the same manner as in Example 1 on the protective layer, the adhesive layer coating solution 1 was applied with a bar coater so that the dry coating thickness was 0.5 μm, and a protective layer transfer sheet 2 was obtained. It was.

Protective layer coating solution 2
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 20%, Tg 55 ° C., Mw 25,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
Sensitizer 1.0 parts (Kayacure EPA, Nippon Kayaku)
30 parts of MEK

The protective layer coating solution 1 was applied to the surface of a 50 μm easily-molded PET film having a heat-resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, 1.0 μm of the intermediate layer coating solution 1 is applied, and further, the image receiving / adhesive layer coating solution 1 is applied thereon with a bar coater so that the dry coating thickness is 1.5 μm. An intermediate transfer sheet 1 was obtained.

Intermediate layer coating solution 1
50 parts of polyester urethane resin (Byron UR-3200, solid content 30%, manufactured by Toyobo)
Toluene 50 parts Coating solution 1 for image-receiving and adhesive layer
10 parts of styrene resin (softening point 130 ° C)
10 parts of epoxy resin (softening point 110 ° C)
Toluene 40 parts MEK 40 parts

[Comparative Example 1] The protective layer coating solution 3 was applied to the surface of a 50 μm easily-molded PET film having a heat-resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, the protective layer transfer sheet 3 was obtained by applying the adhesive layer coating liquid 1 of Example 1 on the protective layer with a bar coater so that the dry coating thickness was 0.5 μm.

Protective layer coating solution 3
20 parts of methacrylic acid methyl ester resin (Dianar BR80, manufactured by Mitsubishi Rayon)
80 parts of MEK

[Comparative Example 2] The protective layer coating solution 4 was applied to the surface of a 50 μm easily-molded PET film having a heat-resistant slip treatment on the back surface with a bar coater so that the dry coating thickness was 5 μm. Subsequently, the protective layer transfer sheet 4 was obtained by applying the adhesive layer coating solution 1 on the protective layer with a bar coater so that the dry coating thickness was 0.5 μm.

Protective layer coating solution 4
70 parts of UV curable acrylic silica hybrid resin (solid content 30%, silica component 23%, Tg 45 ° C., Mw 20,000)
Photoinitiator 1.0 part (Darocur 1173, Ciba Specialty Chemicals)
30 parts of MEK

  The protective layer transfer sheets 1, 2, 3, and 4 obtained as described above were attached to a transparent acrylic plate 150 mm long × 150 mm wide × 2 mm thick using a thermal laminator (VA2-700, manufactured by Taisei). Then, the acrylic board was shape | molded so that the film side might become a hemispherical convex with a radius of 30 mm using the vacuum forming apparatus (made in-house). The molded product thus obtained was irradiated with UV light with an integrated light quantity of 400 mj / cm 2 from the substrate side with a conveyor-type UV irradiation device (GS30 made of GS, using a high-pressure mercury lamp with a main wavelength of 365 nm) to cure the protective layer. . After peeling off the substrate, UV light was irradiated again from the surface of the molded product under the same conditions.

Next, using a thermal transfer evaluation machine (manufactured in-house) on the intermediate transfer sheet 1, Y, M, and C thermal transfer sheets are sequentially printed to form a color image, and then, similarly to the above, 150 mm long × 150 mm wide × A 2 mm thick acrylic plate was attached with a thermal laminator. Then, the transparent acrylic board was shape | molded so that the film side might become a hemispherical convex with a radius of 30 mm using the vacuum forming apparatus (made in-house). The molded product thus obtained is irradiated with UV light with an integrated light amount of 400 mj / cm ² from the substrate side with a conveyor-type UV irradiation device (CS30 manufactured by GS, using a high-pressure mercury lamp with a main wavelength of 365 nm) to cure the protective layer. did. After peeling off the substrate, UV light was irradiated again from the surface of the molded product under the same conditions.
The following evaluation was implemented about the sample produced as mentioned above. The items other than the peelability of the substrate were evaluated after re-irradiation with UV light.

(Evaluation)
Evaluation of the peeling state of the protective layer when peeling off the hemispherical round portion of the base material ○: Interfacial peeling from the base material, ×: Water / solvent resistance in which the protective layer is agglomerated and peeled and whitening is observed One drop of water, ethanol, MEK, and toluene is dropped on the sex sample, and the state of the sample is observed after 30 minutes.
○: No change, Δ: Slightly attacked, X: Scratch resistant sample completely rubbed with steel wool (Bonster # 0000) applied with a load of 250 g / cm ² 10 times.
○: No change, Δ: Some scratches, ×: Large scratches The above evaluation results are shown in Table 1.

Light transmission curve of easily molded PET film Light transmission curve of biaxially stretched PET film

Claims (2)

In an intermediate transfer sheet for molded products for thermal transfer image recording, in which at least a protective layer, an intermediate layer, and an image receiving / adhesive layer are provided on a PET film substrate, the protective layer is an acrylic that can be cured mainly by irradiation with ionizing radiation. It consists of a silica hybrid resin, the resin has no tack before curing at normal temperature, contains a sensitizer as an additive in the protective layer, and the intermediate layer contains a polyester urethane resin as a main component Intermediate transfer sheet for molded products. The intermediate transfer sheet for molded product is superimposed on the adherend and attached by heating and pressing, and then the adherend is molded using a vacuum forming apparatus, and the protective layer is irradiated with ionizing radiation from the substrate side. after curing, after peeling off the base material, the use of the intermediate transfer sheet for molding of claim 1, wherein the use in a method of irradiating again the ionizing radiation the protective layer.

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