JP5610525B2 - Heat transfer sheet and method for producing the same - Google Patents

Description

  The present invention relates to a heat transfer sheet that can be suitably used for applying a decorative pattern such as a pattern or a pattern having a metal thin film layer such as a metallic luster or a hologram to the surface of a fishing tackle or sports equipment, and a method for manufacturing the same.

  Conventionally, applying decorative patterns such as metallic luster and holograms to various products has been widely performed, and a hot stamping method (foil stamping) is widely known as this method. An example of a known transfer foil (hot stamping foil) used in this foil pressing process is shown in FIG. A transfer foil 31 for hot stamping has a protective layer 34 made of a thermoplastic resin which may be colored on a base sheet 32 (mounting paper) 32 having a thin release layer 33 and a thickness of about 12 to 15 μm, and this protective layer. 34, a metal thin film layer (metal foil layer) 35 having a thickness of about 300 to 500 mm formed by vapor deposition or the like, and a heat-sensitive adhesive layer 36 provided on the metal thin film layer 35. The hologram foil can be obtained by forming the protective layer, embossing the surface of the hologram foil to be a hologram surface, and then depositing a metal on the surface by vapor deposition or the like. In the foil stamping process, the heat-sensitive adhesive layer side of the transfer foil having a metallic luster such as silver foil (silver foil), gold foil (gold foil), and hologram foil having the above-described layer structure is opposed to the substrate to be decorated. After stamping with a stamper and adhering the transfer foil to the substrate to be decorated, foil transfer is performed by peeling the transfer foil from the substrate to be decorated, leaving only the heat-pressed and bonded foil portion. Although this foil stamping process using a hot stamper can be pressed onto a gently curved surface, for example, a substrate having a small diameter such as a fishing rod or a golf shaft, a substrate having a curved surface with an extremely small radius of curvature, or a complicated surface There was a limit to stamping a substrate having a shape. In addition, foil stamping with a hot stamper requires that metal molds be produced in accordance with the shape of the foil to be pressed, which limits design and has problems in terms of productivity and cost.

  As a method other than the foil stamping process, a synthetic resin film is formed on a member body of a fishing gear or sports equipment by painting or the like, and a metal film or the like is formed on this film by a vacuum deposition method, a sputtering method, an ion plating method, or the like. It is directly formed by a CVD (chemical vapor deposition) method such as PVD (physical vapor deposition) method, P-CVD (plasma CVD), MOCVD (organic metal CVD) method or wet plating method, and used as a decoration layer. However, since this method forms a metal film directly on a non-decorative base material by vapor deposition or the like, the size of the decoration device such as a vapor deposition device used can be reduced. The size of the base material to be decorated is limited by the relationship, the manufacturing is complicated, and the decorative patterns that can be formed are limited, and it is not easy to form a desired decorative pattern on the curved surface.

  For this reason, as a method for performing metallic luster decoration on a three-dimensional object, a method has been proposed in which a transfer sheet provided with a metal thin film layer is transferred to a substrate to be transferred (for example, see Patent Document 2). The transfer sheet used in this method is provided with a water-soluble adhesive layer on a sheet-like base material, and further provided with a heat-sensitive adhesive layer on the water-soluble adhesive layer. Alternatively, it is manufactured by transferring a metal thin film layer (metal foil) with a hot stamper using a known hot stamping transfer foil, and further providing a printing layer, a clear layer, a cover coat layer, etc. on the metal stamp layer as necessary. In order to provide a metallic gloss pattern on a substrate to be decorated using this transfer sheet, for example, on a helmet, the transfer sheet is first put in water, thereby semi-dissolving the water-soluble adhesive layer, and the sheet-like substrate and Separate the laminate (heat-sensitive adhesive layer, metal foil with adhesive layer, cover coat, etc .: transfer mark) and attach the heat-sensitive adhesive layer side to the surface of the substrate to be transferred, for example, the helmet Then, the laminate is fixed (transferred) to the helmet surface by heat treatment. Thereafter, the substrate to be transferred and the laminate (transfer mark) are cooled to room temperature, the cover coat is peeled off, further heat-treated, and if necessary, a clear coat treatment is performed so that the metallic gloss pattern is placed on the helmet. It is formed.

  A transfer sheet having such a water-soluble adhesive layer is also commercially available. The layer structure of a commercially available transfer sheet is shown in FIG. The transfer sheet 41 is provided with a heat-sensitive adhesive layer 44 on a substrate sheet (mounting paper) 42 on which a water-soluble adhesive layer 43 is provided, and a part of the heat-sensitive adhesive layer 44 is subjected to foil pressing. A silver foil 46 composed of a metal thin film layer having a heat-sensitive adhesive layer 45 on the surface and a protective layer 47 on the back surface is transferred. Then, on the heat-sensitive adhesive layer 44 and the protective layer 47, a design layer 48 by printing with colored ink or the like, a clear layer 49 functioning as a protective layer thereon, and a temporary support after the laminate is peeled off from the mount. A cover coat layer 50 that functions as a body is provided.

  In such a transfer sheet, as described above, the transfer foil for hot stamping is used. However, the adhesive and the thermoplastic resin used in the conventionally known transfer foil for hot stamping are not cut off from the foil. From the standpoint of improving, a relatively hard resin is sometimes used, lacking flexibility, and the formed glossy pattern does not have a sufficiently large curved surface followability. For this reason, when transferring a mark having a metallic luster using a transfer mark having a metal thin film layer, if there is a portion having a small radius of curvature on the surface of the substrate to be decorated, when transferring the transfer foil along this surface, There has been a problem that the metal thin film is cracked at a location where the radius of curvature is small. Furthermore, in the conventional transfer sheet, there are two adhesive layers (44, 45) under the metal thin film layer, which increases the film thickness of the lower layer of the metal thin film layer. The fact that the thin film is stretched more greatly has also contributed to the film cracking of the metal thin film.

  Further, in the transfer sheet as described above, one having a hologram layer having a metal thin film layer is also known (see, for example, Patent Document 3). In this case as well, the metal thin film layer side of the protective layer is the hologram surface. The transfer sheet having the metallic gloss pattern is not particularly different from the above, so that there was a problem such as film cracking of the metal thin film of the hologram foil as described above.

In addition to the above problems, transfer sheets such as transfer foils and transfer marks used in conventional foil stamping also have the following problems.
A. Foil stamping process Wrinkles and cracks occur in the foil when storing labels, or due to poor adhesion due to insufficient pressurization during foil stamping process, wrinkles are generated on the foil when topcoat is applied to the object to be decorated There is a case.
B. Since there is no flexibility in the metal vapor deposition film and binder resin that constitute the foil, there is a problem that the foil does not stretch. It is unsuitable.
C. In foil stamping using a metal mold, pressurization control is difficult, and pressing unevenness occurs, so that large area foil stamping cannot be performed.
D. Since there is no means for distinguishing the portion that presses the foil from the portion that does not press, the partial foil cannot be pressed by foil pressing using a hot roller.
E. Foil stamping is difficult to apply to curved surfaces.
F. A transfer sheet without a substrate has no stiffness and cannot hold the unevenness of the light interference part of the hologram.

  In recent years, a UV-curable adhesive is printed on the surface of the substrate to be decorated, and a transfer foil, called a cold foil with a foil layer formed on a peelable support, is layered on top of each other, and then irradiated with ultraviolet rays for adhesion. A method called cold foil transfer is also known, in which a metal foil pattern is formed on the surface of a substrate to be decorated by curing the agent layer and then peeling the transfer foil. However, this method requires that an ultraviolet curable adhesive layer be formed on the surface of the substrate to be decorated by printing, and that the surface of the substrate to be decorated be smooth. Further, the cold foil has problems in weather resistance and heat resistance, and also has a problem that it cannot cope with elongation.

Japanese Patent Laid-Open No. 10-150887 JP 2004-202807 A JP 2008-23944 A

  The present invention has the problems of the conventional heat transfer sheet including the transfer sheet as described above, particularly, when the transfer mark is transferred to the decorated substrate having a curved surface with a small radius of curvature, the metal thin film layer is cracked or broken. It is an object of the present invention to provide a heat transfer sheet capable of transferring and forming a metallic gloss pattern and a hologram pattern without causing such a problem, and a method for producing the same.

  In addition, the present invention is thinner than conventional ones, is flexible, has excellent followability to the surface of the substrate to be decorated, and easily transfers metallic luster or hologram marks to places with complicated surface shapes. It is another object of the present invention to provide a heat transfer sheet having a metal thin film layer and a method for producing the same, which can be performed beautifully.

  In addition, the present invention provides a heat transfer sheet that is simpler to manufacture than a conventional heat transfer sheet having a metal thin film layer by foil stamping and that can express all solid foils in a large area, and a method for manufacturing the same. It is the purpose.

  The heat transfer sheet and the production method thereof according to the present invention for solving the above problems are as follows.

(1) A base material sheet having a release layer, a heat-sensitive adhesive layer provided on the release layer of the base material sheet, a metal thin film layer of the same size and shape as the heat-sensitive adhesive layer on the heat-sensitive adhesive layer, to the metal thin film layer, the heat-sensitive adhesive layer and the university, have a protective layer of conformal, the heat-sensitive adhesive layer has a glass transition point of -35 ℃ ~-15 ℃ polyester resin, glass transition point A heat transfer sheet comprising a heat-sensitive adhesive containing a polyester resin at 10 ° C to 50 ° C and a crosslinking agent .

(2) The heat transfer sheet according to (1), wherein a clear layer is further provided on the protective layer, and a cover coat layer is further provided on the clear layer.

(3) In the heat transfer sheet according to the above (1) or (2), a second heat-sensitive adhesive layer, the second heat-sensitive adhesive layer and / or a protective layer on the release layer and / or the protective layer. A heat transfer sheet characterized in that a design layer is provided thereon.

(4) The heat transfer sheet according to any one of (1) to (3), wherein the metal thin film layer and the protective layer are hologram foils.

(5) The heat transfer sheet according to any one of (1) to (4), wherein the release layer is made of a water-soluble adhesive.

( 6 ) In the heat transfer sheet according to any one of the above (1) to ( 5 ), the heat-sensitive adhesive constituting the second heat-sensitive adhesive layer is the same as the heat-sensitive adhesive of the heat-sensitive adhesive layer. A heating transfer sheet, characterized in that there is.

( 7 ) The heat transfer sheet according to any one of (1) to ( 6 ), wherein the protective layer is made of an ultraviolet curable resin.

( 8 ) On a base sheet having a release layer, it comprises a polyester resin having a glass transition point of -35 ° C to -15 ° C, a polyester resin having a glass transition point of 10 ° C to 50 ° C and a heat-sensitive adhesive containing a crosslinking agent. A heat-sensitive adhesive layer is provided in a predetermined shape by printing, the heat-sensitive adhesive layer and the metal thin film layer provided on the protective layer on the other base sheet are confronted, heated and pressed, and then the other group A method for producing a heat transfer sheet, wherein the metal thin film layer and the protective layer are transferred onto the heat-sensitive adhesive by peeling the material sheet.

( 9 ) In the method for producing a heat transfer sheet according to ( 8 ) , after the metal thin film layer and the protective layer are transferred onto the heat-sensitive adhesive, a second heat-sensitive adhesive layer is further formed on the release layer and / or the above-described method. Provided by printing on the protective layer, a design layer is formed on the second heat-sensitive adhesive layer and / or protective layer by printing, and further a heat-sensitive adhesive layer, a protective layer, a second heat-sensitive adhesive layer, and a design layer A method for producing a heat transfer sheet, wherein a clear layer is provided so as to cover at least a cover coat layer is provided on the clear layer.

( 10 ) In the method for producing a heat transfer sheet described in ( 8 ) or ( 9 ) above, the metal thin film provided on the protective layer on the other substrate sheet is a hologram foil. A method for producing a thermal transfer sheet.

( 11 ) The method for producing a heat transfer sheet according to any one of ( 8 ) to ( 10 ), wherein the release layer is made of a water-soluble adhesive.

( 12 ) The method for producing a heat transfer sheet according to any one of the above ( 8 ) to ( 11 ), wherein the resin constituting the protective layer is an ultraviolet curable resin. .

In the present invention, the following effects are produced.
(1) Since the heat transfer sheet of the present invention has excellent elongation characteristics and excellent curved surface followability, it is possible to easily decorate a cubic curved surface.
(2) The heat transfer sheet of the present invention does not break or break the metal thin film layer even when it is attached to a tertiary curved surface of the substrate to be decorated, particularly a curved surface having a small curvature radius.
(3) In the present invention, transfer of the transfer foil to the heat transfer sheet is performed without printing a heat-sensitive adhesive in a pattern on the base sheet and without providing a heat-sensitive adhesive layer on the transfer foil. The thickness of the heat transfer sheet can be reduced compared to that of the heat transfer sheet, and foil pressing can be performed using a heat roller, so that the heat transfer sheet can be manufactured at a low cost with a simple method.
(4) The heat transfer sheet of the present invention can be manufactured by printing all parts other than foil stamping, for example, by screen printing, eliminating the need for molds necessary for foil stamping and reducing manufacturing process costs. It is.
(5) The method for producing a heat transfer sheet of the present invention can be used as a substitute for plating because foil pressing with a large area and thinning are possible.

It is typical sectional drawing of an example of the heat transfer sheet of this invention. It is a typical top view of an example of the heat transfer sheet of the present invention. It is typical sectional drawing of the transfer foil used when manufacturing the heating transfer sheet of this invention. It is shape explanatory drawing of an elongation measurement sample. It is typical sectional drawing of the transfer foil for conventional hot stamping. It is typical sectional drawing of the conventional transfer sheet.

  Hereinafter, the heating transfer sheet and the manufacturing method of the heating transfer sheet according to the present invention will be specifically described with reference to FIGS. In the figure, the thickness of the layer is expressed by an appropriate thickness for easy explanation, and the figure does not accurately indicate the thickness dimension of the heat transfer sheet of the present invention.

  FIG. 1 is a schematic cross-sectional view showing a typical layer structure of a heat transfer sheet having a thin film metal layer in the present invention using a water-soluble adhesive for a release layer. FIG. 2 is a schematic plan view of the heat transfer sheet of FIG. 1 and 2, 1 is a heat transfer sheet, 2 is a substrate sheet having a water-soluble adhesive layer 3, 4 is a heat-sensitive adhesive layer (first heat-sensitive adhesive layer), 5 is a metal thin film layer, and 6 is A protective layer having a hologram surface, 7 is a second heat-sensitive adhesive layer, 8 is a design layer made of colored printing ink 9, 10 is a clear layer, and 11 is a cover coat layer. 1 and 2, the protective layer has a hologram surface, but may have a normal metallic luster with a flat surface.

  As described above, the heat transfer sheet of the present invention includes a base sheet, a release layer such as a water-soluble adhesive layer on the base sheet, a heat-sensitive adhesive layer provided by printing on the release layer, and the heat-sensitive adhesive. Since the metal thin film and the protective layer formed by transferring the transfer foil on the agent layer are essential requirements, these will be described first.

  As the substrate sheet 2 having the release layer of the heat transfer sheet of the present invention, any material can be used as long as it is conventionally used as a substrate sheet having a release layer of a heat transfer sheet. Examples of the base sheet include synthetic resin films such as paper, foil, and PET (polyethylene terephthalate), and the release layer dissolves with a releasable material such as silicone, polyethylene, wax, paraffin, or water. As a typical example, a water-soluble adhesive that becomes peelable due to the above can be mentioned. When a water-soluble adhesive is used for the release layer, it is preferable to use paper as the base sheet. The thickness of the base material sheet and the release layer may be arbitrary, and the base material sheet having the release layer may be one in which the release material is applied and impregnated on the base material sheet.

  The water-soluble adhesive layer used as the release layer is a laminate (transfer mark or the like) on the base sheet by dissolving, semi-dissolving, or swelling when the heat transfer sheet of the present invention is immersed in water. ) From the base sheet, and any of those conventionally used as water-soluble adhesives for transfer sheets can be used, and dextrin or carboxymethyl cellulose (CMC) is typical. It is mentioned as a thing. The water-soluble adhesive layer is formed by applying a water-soluble resin liquid to the substrate surface.

  The heat-sensitive adhesive layer 4 functions as an adhesive for transferring a transfer foil such as a metal foil or a hologram foil onto a substrate sheet having a release layer such as a water-soluble adhesive layer, and is transferred to a decorated substrate. It also functions as an adhesive for adhering the foil, and is required to have excellent adhesion to the substrate to be decorated and the foil. In addition, after the transfer foil is bonded to the heat-sensitive adhesive, the transfer foil is peeled off, and the transfer foil that is not bonded to the heat-sensitive adhesive is peeled off, and the foil is formed on the heat-sensitive adhesive layer according to the shape of the adhesive. However, for this purpose, it is necessary for the heat-sensitive adhesive to have a good foil breakage. As described above, the heat-sensitive adhesive is required to have the adhesion to the object to be decorated, the adhesion to the foil, and the foil breakage property when the foil is peeled off, and the heating transfer sheet follows the curved surface of the substrate to be decorated. When transferring and sticking, the metal thin film layer is required to have an appropriate elongation so as not to break or break.

The heat-sensitive adhesive having such properties, using polyester as its main component, to which a crosslinking agent is added, polyester heat-sensitive adhesive can be mentioned up. And as polyester of a main ingredient, it has the high glass transition point which can give the adhesiveness with respect to foil, the 1st polyester resin which has a low glass transition point (Tg), and can give foil cutting property. It is preferable to use a blend of the second polyester resin. The glass transition point of the first polyester resin having a pre-Symbol low glass transition temperature, - 35 ℃ ~-15 ℃ , good Mashiku is -30 ℃ ~-20 ℃, a second having a higher glass transition temperature the glass transition point of the polyester resin, 1 0 ℃ ~50 ℃, good Mashiku is 23 ° C. to 45 ° C.. The molecular weight of the first polyester resin is preferably 25,000 to 40,000, more preferably 25,000 to 32,000 in terms of number average molecular weight (Mn), and the molecular weight of the second polyester resin is The number average molecular weight (Mn) is preferably 5,000 to 30,000, more preferably 8,000 to 20,000. As a typical one, for example, a first polyester resin having a number average molecular weight of 25,000 or more and a glass transition temperature (Tg) of from −30 to −20 ° C. and a number average molecular weight of from 8,000 to The combination of 11,000 and the 2nd polyester resin of glass transition temperature 25-45 degreeC is mentioned.

  Examples of polyester resins that can be preferably used in the present invention include saturated polyester resins such as trade names: Elite (Unitika), Byron (Toyobo), Staffix (Fuji Photo Film), Espel (Hitachi Chemical), and urethane-modified polyester resins. Commercially available resins such as these may be mentioned, and from these, those having the above-mentioned properties may be selected and used as appropriate.

  In addition, the blending ratio of the polyester resin having a low glass transition point (Tg) and the polyester resin having a high glass transition point may be arbitrary as long as the object of the present invention can be achieved, and is not particularly limited. It is preferable to blend 10 to 100 parts by weight of the latter with respect to 100 parts by weight of the former.

  As a crosslinking agent, what was conventionally used as a crosslinking agent of a polyester resin when manufacturing a heat sensitive adhesive can be used arbitrarily. Examples of such a crosslinking agent include melamine compounds and isocyanate compounds, and these may be used alone or in combination of two or more kinds of crosslinking agents. In the present invention, it is preferable to use at least one melamine compound and at least one isocyanate compound in combination. The reason is that the melamine compound does not react with the hydroxyl group of the polyester resin as the main agent at the temperature (room temperature) when the heat transfer sheet is pasted, and the temperature when baking the top coat after the pasting (about 80 to 140 ° C.) It is possible to form an adhesive having a good adhesive property with the substrate to be decorated. On the other hand, the isocyanate compound crosslinks the polyester resin at room temperature, thereby preventing cohesive failure of the adhesive that may occur when the transfer foil mount is peeled off after transferring the foil, and obtaining an adhesive with elongation. be able to. Therefore, by using both cross-linking agents in combination, the adhesive does not cause cohesive failure when peeling off the transfer foil mount, while the adhesion to the decorated substrate and An adhesive having elongation without cracking or breaking of the metal foil film can be obtained. The melamine compound is preferably used in an equivalent ratio of 1 or more with respect to the remaining hydroxyl groups of the polyester resin, and the isocyanate compound is used in the same equivalent ratio of 0.07 to 0.20.

  As a melamine compound that can be used in the present invention, a polyfunctional melamine resin is preferable. Examples of such a polyfunctional melamine resin include a high solid perfect alkyl type, a methylol group type, an imino type, and a methylol-imino group type melamine resin. These can be used alone or in combination of two or more. Specific examples include trade name: Super Becamine (manufactured by DIC).

  On the other hand, examples of the isocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and trimethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, methylene bis (cyclohexyl isocyanate) and cyclohexane diisocyanate; xylene diisocyanate. Aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and biphenylene diisocyanate, trimethylolpropane adducts thereof, burettes reacted with water, trimers having an isocyanurate ring, polyfunctional isocyanate resins, etc. Can be mentioned. These can be used alone or in combination of two or more. Specifically, for example, trade name: Duranate (Asahi Kasei Chemicals), which is a blocked isocyanate, may be mentioned.

  In addition, the heat-sensitive adhesive of the present invention can contain various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, and a silane coupling agent as necessary.

  For example, the antioxidant can be used as long as it is conventionally known as an antioxidant for heat-sensitive adhesives, and is not particularly limited. (Monophenol type, bisphenol type, polymer type phenol type), sulfur type, phosphorus type and the like.

  Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based, and benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are particularly preferable from the viewpoint of the ultraviolet absorption effect. A benzotriazole-based ultraviolet absorber is preferred.

  As the light stabilizer, for example, a light stabilizer such as a hindered amine or hindered phenol can be used.

  The content of these additives may be an appropriate amount depending on the type.

  For the heat-sensitive adhesive layer, the heat-sensitive adhesive may be printed, for example, on a release layer such as a water-soluble adhesive layer of the base sheet, or may be printed in a pattern. As a printing method, screen printing is preferable, but other printing methods may be used. The thickness of the coating film is usually 3 to 50 μm, preferably 5 to 10 μm. When the film thickness of the heat-sensitive adhesive layer is thinner than 3 μm, the initial adhesive strength is particularly insufficient, and when it is thicker than 50 μm, the surface smoothness is inferior and it is not economical.

In the present invention, as main agent polymer of the heat-sensitive adhesive, it is used together before Symbol two polyester resins, and as a crosslinking agent, preferably by the combination of the two cross-linking agent, unlike the conventional heat-sensitive adhesive Even when the substrate to be decorated has a cubic surface having a small radius of curvature when transferring the heat transfer sheet onto the substrate to be decorated, the thin film can be obtained. A transfer sheet having good curved surface followability without cracking of the metal layer can be obtained.

  On the heat-sensitive adhesive thus formed, a holographic foil or metal thin-film layer comprising a metal thin film layer 5 and a protective layer 6 having a hologram surface, and a surface-flat protective layer so as to have the same shape as the heat-sensitive adhesive. A metal foil is formed. The metal foil or hologram foil is a metal thin film of a foil pressing hologram foil 21 having a release layer 23, a protective layer 24 made of an ultraviolet curable resin, and a metal thin film layer 25 on a base sheet (mounting paper) 22 shown in FIG. The layer side is directly overlapped with the heat-sensitive adhesive layer, and the foil is bonded to the heat-sensitive adhesive layer by a method such as passing through a heating roller at a temperature of 60 to 120 ° C. with an apparatus such as a heat laminator, and then heat-sensitive bonding This is done by removing the foil not adhered to the agent layer. If a metal foil is used instead of the hologram foil, a pattern having a normal metallic luster can be obtained. This makes it easier and cheaper than conventional hot stamping, eliminates the need for metal molds necessary for foil stamping, and enables simultaneous foil transfer over a larger area, resulting in lower cost and higher quality. A transfer mark can be produced. The protective layer may be colored, whereby a transfer foil having a colored metallic gloss pattern, for example, a gold foil-like gloss pattern can be obtained.

  In the case of a hologram foil, the transfer foil used for transferring the foil onto the heating adhesive layer is, for example, an ultraviolet curable resin is applied on a 10-25 μm peel-treated PET film (base film). With the hologram pattern pressed, it is exposed to UV light from the base film side to cure the resin and form a protective layer. On the other hand, in the case of silver foil, the resin is cured by UV exposure as it is and a smooth protective layer. The transfer foil can be obtained by forming a thin film of tin, aluminum, zinc sulfide, chromium, indium or the like on the protective layer. As a method for forming a thin film, for example, a PVD (physical vapor deposition) method such as a vacuum deposition method, a sputtering method, or an ion plating method, a P-CVD (plasma CVD), a MOCVD (organometallic CVD) method or the like is used. Examples thereof include a CVD (chemical vapor deposition) method and a wet plating method. The mount is not limited to PET, and may be any one as long as it is conventionally used as a mount for a transfer foil, and the thickness thereof may be arbitrary. As the ultraviolet curable resin, polyester-modified, urethane-acrylic, epoxy-acrylic and other acrylic-modified resins and epoxy resin-based resins are known, but those having excellent elongation characteristics after ultraviolet curing are preferable, For example, a urethane acrylate type is particularly preferable. By using such an ultraviolet curable resin having excellent elongation characteristics, the problem of cracking of the foil when the transfer mark is applied is improved as compared with the case where a thermoplastic resin is used as the material of the protective layer.

  Up to now, the base sheet, the release layer such as the water-soluble adhesive layer, the heat-sensitive adhesive layer, the metal thin film layer, and the protective layer, which are essential components of the present invention, have been described. The second heat-sensitive adhesive layer, the design layer, the clear layer, and the cover coat layer will be specifically described.

  The second heat-sensitive adhesive 7 is provided by printing at a predetermined location on the base sheet including the protective layer formed as described above. Since the second heat-sensitive adhesive layer 7 is for transferring the design layer 8 provided by printing with colored ink to the object to be decorated, the metal layer is a portion where the design layer is provided. It is necessary to form at least portions other than the portion where the foil or hologram foil is formed. That is, the second heat-sensitive adhesive layer excludes a required portion including a portion where a design layer is provided, including a portion where a metal foil or a hologram foil is formed, or a portion where a metal foil or a hologram foil is formed. It can be provided at any of the required locations including the portion where the design layer is provided. If the heat-sensitive adhesive of the second heat-sensitive adhesive layer is the same as the adhesive of the heat-sensitive adhesive layer (first heat-sensitive adhesive layer) described above, the first heat-sensitive adhesive has adhesiveness to the substrate to be decorated. Since it becomes the same as a part, it is preferable that the adhesive of a 1st heat sensitive adhesive layer and the adhesive of a 2nd heat sensitive adhesive layer are the same. However, unlike the metal foil or hologram foil, the colored printing ink has the ability to follow elongation, so the adhesive of the second heat-sensitive adhesive layer is different from the adhesive of the first heat-sensitive adhesive layer. There may be. The printing of the second heat-sensitive adhesive layer may be performed by a method similar to the method used for the first heat-sensitive adhesive layer. For example, screen printing is a preferable method.

  A desired layer on the second heat-sensitive adhesive layer and / or metal foil or hologram foil is printed with a colored ink to form a design layer 8. As the colored printing ink 9, a known commercially available colored printing ink (including white or black ink and achromatic printing ink), for example, most ink such as screen ink can be used. Among these inks, those having a two-component reaction type and using an isocyanate curing agent as a curing agent are particularly preferable. By using blocked isocyanate as a curing agent, flexibility can be maintained until transfer, and it can be cured after heating to give durability. For example, 100 parts by weight of an epoxy resin is blended with 10 to 50 parts by weight of the blocked isocyanate that starts the curing reaction at 60 ° C. or more and 80 ° C. or less. Things can be printing inks. In addition, as a vehicle, at least of a low molecular epoxy resin having a number average molecular weight of 500 to 4,000 and a softening point of 50 to 100 ° C. and a tackifier resin with respect to 100 parts by weight of a high molecular epoxy resin having a number average molecular weight of 10,000 or more One obtained by blending 20 to 200 parts by weight of one is also preferred. An auxiliary additive such as an antifoaming agent, a leveling agent, a thickener, a filler, and a diluting solvent can be further added to the colored printing ink as long as the ink performance is not impaired. If necessary, a catalyst for lowering the dissociation temperature of the blocked isocyanate, a catalyst for promoting the reaction, or the like may be added.

  The colored printing ink layer may be formed by any known printing method, but is preferably formed by screen printing. The colored printing ink layer may consist of one layer, or two or more layers may be overprinted to form a multicolor pattern.

  The clear layer 10 is formed in order to increase the scratch resistance and scratch resistance of the sheet itself and to maintain the durability. As a material for forming the clear layer, a known commercially available UV curable transparent clear may be used. As long as the pencil hardness of the surface is H or more and the elongation of the heat transfer sheet after printing and curing the clear becomes 5 to 50%, any of them can be preferably used. As the UV curable clear ink, there are known clear inks such as polyester acrylic, urethane acrylic, and epoxy acrylic modified resins and epoxy resins, and those having the above characteristics are selected from these. . Examples of commercially available UV curable transparent clears include trade names: UVSPS5300 (manufactured by Teikoku Ink), UV Z0235 (manufactured by Seiko Advance), and the like. These UV-curable transparent clears usually comprise a polymerizable monomer or oligomer, a resin or oligomer that serves as a binder, a photopolymerization initiator, and additives that are added as necessary. Further, a composition having the same performance as described above, for example, a composition obtained by adding 0.1 to 10 parts by weight of a photopolymerization initiator to a mixture of 100 parts by weight of a polymerizable urethane oligomer and 0 to 35 parts by weight of a polymerizable acrylic monomer. Uses products that are supplemented with defoaming agents, leveling agents, thickeners, UV absorbers, fillers, organic solvents for viscosity adjustment, etc., which are auxiliary additives normally used in printing, for example, screen printing can do

  These transparent clears are printed by printing, preferably screen printing, and can be laminated by curing by irradiating with ultraviolet rays by a metal halide lamp. The film thickness is 2 to 50 μm, preferably 5 to 30 μm. Printing is performed in a range covering the heat-sensitive adhesive layer on at least the colored printing ink layer.

  The cover coat layer 11 can be omitted for reasons such as the size of the pattern and the shape of the object to be decorated, but it is generally applied from the viewpoint of workability at the time of attachment. As a material for forming the cover coat layer, any flexible resin that can be easily peeled off from the transparent clear layer 10 can be used. For example, 100 parts by weight of polyester resin such as acrylic resin, saturated polyester resin, alkyd resin, vinyl chloride resin or vinyl chloride-vinyl acetate copolymer resin, phthalate ester, adipate ester, azelate ester, etc. It is preferable to use a plasticizer for plastic, which is used alone or in combination of 10 to 30 parts by weight in combination of two or more. As a more preferable composition, 10 to 30 parts of a polyester plasticizer is added to 100 parts by weight of an acrylic resin having a glass transition point in the range of 30 ° C. to 75 ° C., and further a filler, an antifoaming agent and a dilution solvent are added. The composition added suitably is mentioned. Further, a colorant such as a color pigment or a dye may be added to the cover coat layer so that peeling of the cover coat layer can be confirmed.

  The cover coat layer preferably has an elongation of 30% or more at room temperature, more preferably in the range of 30 to 500%, from the standpoint of following the curved structure to be decorated and ensuring good peelability. It is. When the elongation percentage of the cover coat layer is less than 30%, the followability to the decorative body with a curved surface structure is remarkably impaired, and when the cover coat layer is peeled off, it is easily broken and difficult to remove cleanly. . On the other hand, when the elongation percentage exceeds 500%, there is a problem that the pattern is distorted in handling, pasting, etc., and it is not preferable in terms of work to form a layer thickness to prevent this, and the ink solvent for the cover coat May adversely affect seat performance.

  To the cover coat layer, beads such as acrylic resin, styrene resin, polyolefin resin, and nylon resin having an average particle diameter of 1 to 50 μm are added so that the squeegee moves smoothly when the heat transfer sheet is applied to the object to be decorated. You can also. In addition, for example, auxiliary additives used in normal screen printing, such as an antifoaming agent, a leveling agent, a thickening agent, a diluting solvent, etc., can be optionally added as long as the performance of the cover coat is not impaired. .

  These cover coat layer forming compositions are printed by a printing method, preferably a screen printing method, and are laminated on the transparent clear layer 10. The film thickness is 10 to 100 μm, preferably 30 to 70 μm.

  When the heat transfer sheet of the present invention is applied to an object to be decorated, when a water-soluble resin layer is used as a release layer, the heat transfer sheet is first immersed in a water tank to form a transfer mark or the like. Temporarily place the transfer mark with the heat-sensitive adhesive layer side on the object to be decorated, peeled off the material sheet and wet with water, along the surface of the object to be decorated while extruding water using a rubber spatula or squeegee To temporarily bond. Thereafter, heating at 100 ° C. or lower, preferably 90 ° C. or lower, more specifically 75 to 80 ° C. is performed, and after cooling, the cover coat is peeled off to obtain a durable high gloss pattern or the like.

  On the other hand, when polyethylene, wax, paraffin, etc. are used as the release layer material, the transfer mark, etc. is peeled directly from the base sheet, and the heat-sensitive adhesive layer side of the transfer mark is temporarily placed on the surface of the object to be decorated. The heat-sensitive adhesive is temporarily bonded along the shape of the object to be decorated. At this time, if necessary, adhesion is performed using a spatula or the like, taking care that air is not caught between the heat-sensitive adhesive and the surface of the object to be decorated. Subsequent processing is performed in the same manner as the transfer mark using the water-soluble adhesive layer, and a durable high gloss pattern or the like can be obtained. However, when there is no water, air is likely to remain between the heat-sensitive adhesive and the surface of the object to be decorated, so a water-soluble adhesive is used as the release layer material, and the transfer sheet is immersed in water as described above. It is preferable that the transfer mark or the like is peeled off from the base material sheet by dissolving the adhesive or the like, and temporarily adhered to the object to be decorated while wetted with water.

  As the substrate to be decorated to which the heat transfer sheet of the present invention is attached, metals, plastics, porcelain and the like are preferable. These materials may be coated on the surface. Examples of such objects to be decorated include fishing equipment, golf clubs, rackets and other sports equipment, automobiles, motorcycles, boats, toys, helmets, vending machines, tableware, etc., but are not limited thereto. Absent.

  Hereinafter, the present invention will be described more specifically with reference to examples using a water-soluble adhesive as a release layer, but the present invention is not limited to the following examples.

Example 1
As a first polyester resin, a urethane-modified copolymer polyester having a Tg of −30 ° C. and a Mn of 25,000 (byron manufactured by Toyobo Co., Ltd.) is applied to the surface of the base sheet (mounting paper) made of paper. UR6100) 400 parts by weight, as a second polyester resin, 360 parts by weight of thermoplastic saturated copolyester resin having a Tg of 45 ° C. and Mn of 8,000 (manufactured by Unitika, Elitel UE3300; diluted 50% cyclohexanone), melamine crosslinking 108 parts by weight of an agent (methylated melamine, manufactured by DIC, Super Becamine L-105-60) and 50 parts by weight of an isocyanate crosslinking agent (hexamethylene diisocyanate, manufactured by Asahi Kasei Chemicals, Duranate E-402-90T) Furthermore, antifoaming agent (made by Seiko Advance, care ) 20 parts by weight, the heat-sensitive adhesive compounded with 200 parts by weight diluting solvent (cyclohexanone), was printed into a predetermined shape by 300 mesh by screen printing, to form a heat-sensitive adhesive layer.

  On the obtained heat-sensitive adhesive layer, the hologram foil was thermally transferred at 100 ° C. using a thermal laminator (manufactured by FujiPura, Lamipacker LPA330), then the foil mount was peeled off, and the hologram foil was transferred onto the heat-sensitive adhesive layer. did.

  The hologram foil is an ultraviolet curable resin film that is formed by pressure bonding an ultraviolet curable resin (urethane acrylate) film formed on a PET (polyethylene terephthalate) film and an ultraviolet transmissive hologram substrate, and irradiating ultraviolet rays. After the film is cured and the film is peeled off from the support substrate, aluminum is vapor-deposited by about 300 mm.

  The same adhesive as the above-mentioned heat-sensitive adhesive was printed in a predetermined shape with a screen mesh of 300 mesh on the base sheet having the hologram foil transferred onto the heat-sensitive adhesive thus formed. Further, a colored printing ink (black ink) is printed on the second heat-sensitive adhesive layer with 225 mesh by screen printing to form an ink layer, and then includes at least the second heat-sensitive adhesive layer and the hologram foil. A UV-curable transparent clear (manufactured by Teikoku Ink Manufacturing Co., Ltd., SPS5300) was printed on the portion by screen printing, and ultraviolet rays were irradiated to form a clear layer.

  On the obtained transparent clear layer, 100 parts by weight of a cover coat comprising 100 parts by weight of acrylic resin (Mitsubishi Rayon, Dianar BR101), 20 parts of polyester resin (ADEKA, Adeka Sizer PN150) and 150 parts by weight of xylene. A composition comprising 1 part by weight of an antifoaming agent (manufactured by Seiko Advance, care 6), 6 parts by weight of a matting agent (manufactured by Fuji Silysia Chemical Ltd., Cylysia 350), and 15 parts of xylene is printed with 60 mesh by screen printing. A coat layer was formed and dried at room temperature overnight to obtain a heat transfer sheet.

  The “elongation” and “adhesion” of the transfer mark on the water-soluble adhesive of the obtained heat transfer sheet were measured by the following methods. The results are shown in Table 1.

<Elongation>
The hologram foil portion of the transfer mark was cut out with a width of 10 mm, and the elongation was measured at a pulling speed of 200 mm / min using an autograph AGS-100D manufactured by Shimadzu. As shown in FIG. 4, the measurement sample was stretched with both ends fixed with a reinforcing tape so that the stretch measurement area was 50 × 10 mm. From the measurement results, elongation (%) was calculated by the following formula.
Elongation (%) = {Length stretched (mm) / 50 (mm)} × 100

<Adhesion>
The heated transfer sheet is immersed in a water tank, the transfer mark is peeled off from the mount, placed on an adherend (stainless steel plate), water is pushed out using a squeegee, and then heated at 60 ° C. for 15 minutes to peel off the cover coat. . After the adherend was cooled to room temperature, a clear paint (urethane system) was applied and baked at 80 ° C. for 30 minutes. A cross-cut test (JIS D0202, 1 mm × 10 × 10 pieces) was performed on the pasted and painted transfer marks using Nichiban's cello tape (registered trademark), and the number remaining without peeling was counted.

Example 2
As the first polyester resin, instead of 400 parts by weight of urethane-modified copolymer polyester (Toyobo, Byron UR6100) having Tg of −30 ° C. and Mn of 25,000, Tg of −20 ° C. and Mn of 25,000 A heat transfer sheet was prepared in the same manner as in Example 1 except that 800 parts by weight of a thermoplastic saturated copolymerized polyester (manufactured by Unitika, Elitel UE3400; diluted product of 50% cyclohexanone) was used. The transfer marks were measured for elongation and adhesion. The results are shown in Table 1.

Example 3
As a first polyester resin, a urethane-modified copolymer having a Tg of −22 ° C. and a Mn of 32,000 was used instead of a urethane-modified copolymer polyester (Toyobo, Byron UR6100) having a Tg of −30 ° C. and a Mn of 25,000. A heated transfer sheet was prepared in the same manner as in Example 1 except that polymerized polyester (Toyobo, Byron UR8700) was used, and the elongation and adhesion of the obtained transfer mark were measured in the same manner as in Example 1. . The results are shown in Table 1.

Example 4
A heat transfer sheet was prepared in the same manner as in Example 1 except that a silver foil was used instead of the hologram foil, and the elongation and adhesion of the transfer mark obtained in the same manner as in Example 1 were measured. The results are shown in Table 1.

Example 5
In Example 4, a heat transfer sheet was prepared in the same manner as in Example 1 except that ultraviolet curable ink (color clear) printing of a color equivalent to gold foil was further printed on the transferred silver foil. The elongation and adhesion of the transfer mark were measured. The results are shown in Table 1.

Example 6
As a first polyester resin, a urethane-modified copolymer having a Tg of −22 ° C. and a Mn of 32,000 was used instead of a urethane-modified copolymer polyester (Toyobo, Byron UR6100) having a Tg of −30 ° C. and a Mn of 25,000. Polymerized polyester (by Toyobo, Byron UR8700) is used, and as the second polyester resin, Tg is 45 ° C. and Mn is 8,000, instead of thermoplastic saturated copolymer polyester resin (Unitika, Elitel UE3300), Tg A heated transfer sheet was prepared in the same manner as in Example 1 except that a branched saturated polyester resin (Espel 9940D, manufactured by Hitachi Chemical Co., Ltd.) having a Mn of 11,000 was used. The elongation and adhesion of the obtained transfer mark were measured. The results are shown in Table 1.

Example 7
As the first polyester resin, instead of 400 parts by weight of urethane-modified copolymer polyester (Toyobo; Byron UR6100) having a Tg of −30 ° C. and an Mn of 25,000, a Tg of −20 ° C. and an Mn of 25,000 800 parts by weight of thermoplastic saturated copolymerized polyester (manufactured by Unitika, Elitel UE3400; diluted product of 50% cyclohexanone), and as the second polyester resin, thermoplastic saturated copolymerized polyester having Tg of 45 ° C. and Mn of 8,000 Instead of resin (Eritel UE3300, manufactured by Unitika; diluted product of 50% cyclohexanone), a branched saturated copolymerized polyester resin (Hitachi Chemical Industries, Espel 9940E-37) having a Tg of 25 ° C. and an Mn of 11,000 is used. A heat transfer sheet was prepared in the same manner as in Example 1 except that As were measured elongation and adhesion of the transfer marks obtained. The results are shown in Table 1.

Example 8
As a first polyester resin, a urethane-modified copolymer having a Tg of −22 ° C. and a Mn of 32,000 was used instead of a urethane-modified copolymer polyester (Toyobo, Byron UR6100) having a Tg of −30 ° C. and a Mn of 25,000. Polymerized polyester (Toyobo, Byron UR8700) is used, and as the second polyester resin, a thermoplastic saturated copolymer polyester resin having a Tg of 45 ° C. and an Mn of 8,000 (Unitika, Elitel UE3300; 50% cyclohexanone diluted product) ), A heat transfer sheet was prepared in the same manner as in Example 1 except that a branched saturated polyester resin (Esper 9940E-37, manufactured by Hitachi Chemical Co., Ltd.) having a Tg of 25 ° C. and a Mn of 10,000 was used. In the same manner as in Example 1, the elongation and adhesion of the obtained transfer mark were measured. The results are shown in Table 1.

Comparative Example 1
In Example 1, a heat transfer sheet was prepared in the same manner as in Example 1 except that a hot stamping transfer foil having a structure shown in FIG. 5 (“BL Silver” manufactured by Murata Gold Foil Co., Ltd.) was used. The elongation and adhesion of the transferred transfer mark were measured. The results are shown in Table 1.

Comparative Example 2
The second polyester resin is not blended as a heat-sensitive adhesive, and the first polyester resin is a thermoplastic saturated copolymer polyester resin having a Tg of −20 ° C. and an Mn of 25,000 (Elitel 3400 manufactured by Unitika; 50% cyclohexanone diluted product) ) A heat-sensitive adhesive layer was formed in the same manner as in Example 1 except that 1,000 parts by weight were used. The hologram foil and the heat-sensitive adhesive layer were subjected to thermocompression bonding at 100 ° C. using a thermal laminator, and then the foil mount was peeled off. As a result, the heat-sensitive adhesive layer caused cohesive failure, and the foil could not be transferred.

Comparative Example 3
Branched saturated polyester resin (Espel 9940E-37, manufactured by Hitachi Chemical Co., Ltd.) having a Tg of 25 ° C. and a Mn of 10,000 as the second polyester resin without blending the first polyester resin as the heat-sensitive adhesive 1,000 A heat-sensitive adhesive layer was formed in the same manner as in Example 1 except that parts by weight were used. The hologram foil and the thermosensitive adhesive layer were thermocompression bonded at 100 ° C. using a thermal laminator, but the foil did not adhere to the thermosensitive adhesive layer.

Comparative Example 4
Except for using 1,000 parts by weight of a thermoplastic saturated copolymer polyester resin (manufactured by Unitika, Elitel 3220; 50% cyclohexanone diluted product) having a Tg of 5 ° C. and an Mn of 25,000 as the resin component of the heat-sensitive adhesive. In the same manner as in Example 1, a heat-sensitive adhesive layer was formed. The hologram foil and the thermosensitive adhesive layer were thermocompression bonded at 100 ° C. using a thermal laminator, but the foil did not adhere to the end of the thermosensitive adhesive layer.

  As is clear from Table 1, the heat transfer sheet of the present invention was excellent in both elongation and adhesion, whereas the heat transfer sheet of Comparative Example 1 prepared by a conventional method had no elongation. Also, the adhesion was poor. In Comparative Examples 2 to 4 in which two kinds of resins, ie, a low glass transition point polyester resin and a high glass transition point polyester resin are not used as the heat sensitive adhesive, a problem occurs in the transfer of the foil. It can be seen that it is preferable to use the two kinds of resins as the agent.

  When the mark was transferred to the head portion of the golf club using the heat transfer sheet produced in Example 1, the mark could be stuck without cracking of the foil even in the portion where the radius was small and bent at a steep angle. However, in the heat transfer sheet of Comparative Example 1, a foil crack occurred at a portion bent at a steep angle.

1 Heat transfer sheet 2, 22, 32, 42 Base sheet (mounting paper)
3, 43 Water-soluble adhesive layer 4, 7, 36, 44, 45 Heat-sensitive adhesive layer 5, 25, 35 Metal thin film layer 6, 24, 34, 47 Protective layer 8, 48 Design layer 9 Colored printing ink 10, 49 Clear layer 11, 50 Cover coat layer 21 Hologram foil for pressing 23, 33 Release layer 31 Transfer foil for hot stamping 41 Transfer sheet 46 Silver foil

Claims (12)

A base material sheet having a release layer, a heat-sensitive adhesive layer provided on the release layer of the base material sheet, a metal thin film layer of the same size and shape as the heat-sensitive adhesive layer on the heat-sensitive adhesive layer, and the metal thin film on the layer, the heat-sensitive adhesive layer and the university, have a protective layer of conformal, the heat-sensitive adhesive layer has a glass transition point of -35 ℃ ~-15 ℃ polyester resin, a glass transition point of 10 ° C. ~ A heat transfer sheet comprising a heat-sensitive adhesive containing a polyester resin at 50 ° C. and a crosslinking agent .   2. The heat transfer sheet according to claim 1, wherein a clear layer is further provided on the protective layer, and a cover coat layer is further provided on the clear layer.   3. The heat transfer sheet according to claim 1, wherein a second heat-sensitive adhesive layer is provided on the release layer and / or protective layer, and a design layer is provided on the second heat-sensitive adhesive layer and / or protective layer. A heat transfer sheet characterized by that.   The heat transfer sheet according to any one of claims 1 to 3, wherein the metal thin film layer and the protective layer are hologram foils.   The heat transfer sheet according to any one of claims 1 to 4, wherein the release layer is made of a water-soluble adhesive. The heat transfer sheet according to any one of claims 1 to 5 , wherein the heat-sensitive adhesive constituting the second heat-sensitive adhesive layer is the same as the heat-sensitive adhesive of the heat-sensitive adhesive layer. Heat transfer sheet. The heat transfer sheet according to any one of claims 1 to 6 , wherein the protective layer is made of an ultraviolet curable resin. A heat-sensitive adhesive comprising a polyester resin having a glass transition point of −35 ° C. to −15 ° C., a polyester resin having a glass transition point of 10 ° C. to 50 ° C., and a crosslinking agent on a base sheet having a release layer. A layer is provided in a predetermined shape by printing, the heat-sensitive adhesive layer and the metal thin film layer provided on the protective layer on the other base sheet are confronted, heated and pressurized, and then the other base sheet is A method for producing a heat transfer sheet, wherein the metal thin film layer and the protective layer are transferred onto the heat-sensitive adhesive by peeling. 9. The method for producing a heat transfer sheet according to claim 8, wherein after the metal thin film layer and the protective layer are transferred onto the heat-sensitive adhesive, a second heat-sensitive adhesive layer is further formed on the release layer and / or the protective layer. Provided by printing, forming a design layer on the second heat-sensitive adhesive layer and / or protective layer by printing, and further covering at least the heat-sensitive adhesive layer, the protective layer, the second heat-sensitive adhesive layer, and the design layer A method for producing a heat transfer sheet, wherein a clear layer is provided on the cover layer, and a cover coat layer is provided on the clear layer. The method for producing a heat transfer sheet according to claim 8 or 9 , wherein the metal thin film provided on the protective layer on the other base sheet is a hologram foil. The method for producing a heat transfer sheet according to any one of claims 8 to 10 , wherein the release layer is a water-soluble adhesive. The method for manufacturing a heat transfer sheet according to any one of claims 8 to 11 , wherein the resin constituting the protective layer is an ultraviolet curable resin.

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